WO2017094490A1 - 液晶表示装置および液晶表示装置の製造方法 - Google Patents

液晶表示装置および液晶表示装置の製造方法 Download PDF

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WO2017094490A1
WO2017094490A1 PCT/JP2016/083761 JP2016083761W WO2017094490A1 WO 2017094490 A1 WO2017094490 A1 WO 2017094490A1 JP 2016083761 W JP2016083761 W JP 2016083761W WO 2017094490 A1 WO2017094490 A1 WO 2017094490A1
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group
liquid crystal
structural unit
polymer
protective layer
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PCT/JP2016/083761
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English (en)
French (fr)
Japanese (ja)
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山田　悟
若彦 金子
秀人 田鍋
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富士フイルム株式会社
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Priority to KR1020187013001A priority Critical patent/KR102061587B1/ko
Priority to CN201680064694.2A priority patent/CN108351558A/zh
Publication of WO2017094490A1 publication Critical patent/WO2017094490A1/ja

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • G09F9/35—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements being liquid crystals

Definitions

  • the present invention relates to a liquid crystal display device and a method for manufacturing the liquid crystal display device.
  • Liquid crystal displays are widely used in monitors and television applications such as personal computers and smartphones because of their various advantages such as low voltage and low power consumption, and enabling miniaturization and thinning.
  • Such a liquid crystal display device has a liquid crystal cell and two polarizing plates disposed on both sides of the liquid crystal cell, and the liquid crystal cell is disposed to face each other with the liquid crystal layer and the liquid crystal layer interposed therebetween.
  • the two substrates are generally provided with an alignment film for aligning the liquid crystal constituting the liquid crystal layer.
  • Patent Document 1 discloses that “a polymer having a silicone group or a fluorine-substituted alkyl group and a photoalignment group as a first component, and methacrylic acid and methacrylic acid as a second component”.
  • a photoalignable polymer composition comprising a non-photoalignable polymer obtained by polymerizing a monomer containing at least one selected from the group consisting of esters” ([Claim 1]). [Claim 28]).
  • a liquid crystal display device is provided with a color filter on the viewing side.
  • the color filter has a viewpoint of preventing permeation of impurities from the color filter and a viewpoint of flattening a step of the color filter. Therefore, it is known to provide a protective layer (overcoat layer).
  • the present inventors examined providing an alignment film that does not require a protective layer when a color filter is provided on the viewing side, that is, an alignment protective layer having a function of the protective layer and the alignment film.
  • the present invention provides a liquid crystal display device that maintains excellent flatness even when a color filter is provided on the viewing side, and has good display performance even when exposed to high temperature and high humidity, and its liquid crystal display device It is an object to provide a manufacturing method.
  • the present inventors have provided an orientation protective layer having an orientation group and a cross-linked structure connected to each other through a covalent bond, and the surface in contact with the liquid crystal layer. It is found that even when a color filter is provided on the viewing side, the flatness is maintained even when the color filter is provided on the viewing side, and the display performance is improved even when exposed to high temperatures and high humidity.
  • the present invention has been completed. That is, it has been found that the above-described problem can be achieved by the following configuration.
  • a liquid crystal display device having a first substrate, a liquid crystal layer, and a second substrate in this order from the viewing side
  • the first substrate comprises a base material and an orientation protective layer
  • the second substrate comprises a base material, a thin film transistor, a display electrode, and an alignment film
  • the alignment protective layer has a surface in contact with the liquid crystal layer;
  • the alignment protective layer has an alignment group and a crosslinked structure linked to each other via a covalent bond;
  • the intensity ELq of the mass analysis of the fragment derived from the orientation group on the surface in contact with the liquid crystal layer of the orientation protection layer, and the orientation protection layer The strength ESsub of the mass spectrometry of the fragment derived from the orientation group on the surface of the base material side satisfies the following condition 1 or 2:
  • a liquid crystal display device, wherein the crosslinked structure includes any one of structures represented by formulas (A-1) to (A-3) described later.
  • Condition 1 The intensity ELq is 2 to 20 times the intensity ESub.
  • Condition 2 The intensity ELq is significantly measured and the intensity ESub is below the measurement limit.
  • [5] The liquid crystal display device according to any one of [1] to [4], wherein the liquid crystal constituting the liquid crystal layer is a horizontally aligned liquid crystal.
  • the fragment derived from the orientation group is a fragment derived from at least one photoalignment group selected from the group consisting of a cinnamate group and a chalcone group.
  • the polymer P includes a structural unit represented by s1 below as a structural unit having an orientation group, The method for producing a liquid crystal display device according to [7], wherein the polymer P and the polymer A satisfy the following condition 3 or 4.
  • s1 a structural unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton and an alkyl group having 10 to 30 carbon atoms, and a structural unit having a photoalignment group
  • Condition 3 Heavy
  • the coalescence P includes a structural unit a2 having a crosslinkable group
  • the polymer A includes a structural unit a3 having an acid group.
  • the polymer P includes a structural unit a3 having an acid group
  • the polymer A includes a structural unit a2 having a crosslinkable group.
  • composition for forming an alignment protective layer further contains a crosslinking agent B having a molecular weight of 5000 or less.
  • the crosslinking agent B includes a crosslinking agent having an epoxy group, The method for producing a liquid crystal display device according to [11], wherein the mass ratio of the crosslinking agent B to the total mass of the crosslinking agent B, the polymer P, and the polymer A is 30% by mass or less.
  • the orientation group is a photo-alignment group
  • a liquid crystal display device that maintains excellent flatness even when a color filter is provided on the viewing side and has good display performance even when exposed to high temperature and high humidity, and its liquid crystal display device A manufacturing method can be provided.
  • FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of the liquid crystal display device of the present invention.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • substitution and non-substitution includes what does not have a substituent and what has a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • (meth) acrylate is a notation representing “acrylate” or “methacrylate”
  • (meth) acryl is a notation representing “acryl” or “methacryl”
  • (meth) The “) acryloyl” is a notation representing “acryloyl” or “methacryloyl”.
  • the liquid crystal display device of the present invention is a liquid crystal display device having a first substrate, a liquid crystal layer, and a second substrate in this order from the viewing side, wherein the first substrate includes a base material and orientation protection. And the second substrate includes a base material, a thin film transistor, a display electrode, and an alignment film.
  • the orientation protective layer has a surface in contact with the liquid crystal layer, and any of the orientation groups and formulas (A-1) to (A-3) described later. And a structure in which the orientation group and the crosslinked structure are linked to each other through a covalent bond.
  • the liquid crystal display device of the present invention alignment protection is provided for fragments derived from alignment groups detected by time-of-flight secondary ion mass spectrometry (TOF-SIMS).
  • TOF-SIMS time-of-flight secondary ion mass spectrometry
  • the intensity ELq of the mass analysis of the fragment derived from the orientation group on the surface in contact with the liquid crystal layer of the layer and the intensity ESub of the mass analysis of the fragment derived from the orientation group on the substrate side surface of the orientation protective layer are as follows: Condition 1 or 2 is satisfied.
  • Condition 1 The intensity ELq is 2 to 20 times the intensity ESub.
  • Condition 2 The intensity ELq is significantly measured and the intensity ESub is below the measurement limit.
  • the measurement by TOF-SIMS in the present invention is performed as follows.
  • the alignment protective layer and the adjacent layer adjacent to the alignment protective layer are peeled off, and the surface of the alignment protective layer (referring to the surface in contact with the liquid crystal layer; hereinafter the same) and the back surface of the alignment protective layer (base material) Or the surface in contact with the adjacent layer on the substrate side, the same shall apply hereinafter), derived from the orientation group on the surface of the orientation protective layer with the apparatus and conditions shown in (3) below.
  • the mass analysis intensity ELq of the fragment to be analyzed and the mass analysis intensity ESsub of the fragment derived from the orientation group on the back surface of the alignment protective layer are measured.
  • the cutting surface is determined by using the CYCUS method (Surface and Interfacial Cutting Analysis System: SAICAS) for the laminate having the alignment protective layer and the adjacent layer. Cutting is performed in an oblique direction so as to reach the front and back surfaces of the alignment protective layer, and the cross section of the alignment protective layer is exposed. With respect to the exposed cross section, the intensity of the mass analysis of the fragment derived from the orientation group measured with the apparatus and conditions shown in (3) below in the depth (thickness) direction from the surface of the orientation protective layer is 10 nm.
  • SAICAS Surface and Interfacial Cutting Analysis System
  • the alignment protective layer has a crosslinking structure containing an orientation group and any of the structures represented by formulas (A-1) to (A-3) described later.
  • the orientation group is unevenly distributed on the surface of the orientation protective layer, And it is thought that the orientation group has couple
  • the intensity ELq by the TOF-SIMS measurement is 5 to 20 times the intensity ESub because the display performance is improved even when exposed to high temperature and high humidity.
  • FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of the liquid crystal display device of the present invention.
  • the liquid crystal display device 10 illustrated in FIG. 1 includes a first substrate 30, a liquid crystal layer 20, and a second substrate 40 in this order from the viewing side.
  • the first substrate 30 is provided with a base material 15 to which a polarizing film is attached, an RGB color filter 22 on which a black matrix is disposed, and an alignment protective layer 21 having a surface in contact with the liquid crystal layer 20.
  • the second substrate 40 is provided with the base material 14 to which the polarizing film is attached and the element of the thin film transistor 16.
  • the liquid crystal display device 10 shown in FIG. 1 has a backlight unit 12 on the back surface, and the light source of the backlight is not particularly limited, and a known light source can be used. For example, white LEDs (light emitting diodes), multicolor LEDs such as blue, red, and green, fluorescent lamps (cold cathode tubes), organic electroluminescence, and the like can be given. Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and can be used as the second interphase insulating film (48) of JP 2011-145686A or the interphase insulating film (520) of JP 2009-258758A.
  • substrate which the liquid crystal display device of this invention has is a board
  • a transparent substrate used in a liquid crystal cell of a conventionally known liquid crystal display device can be used.
  • a glass substrate, a quartz substrate, a transparent resin substrate, or the like can be used.
  • the alignment protective layer has a surface in contact with a liquid crystal layer described later, and has an alignment group and any structure represented by formulas (A-1) to (A-3) described later. And having a structure in which the orientation group and the crosslinked structure are linked to each other through a covalent bond.
  • the alignment group possessed by the alignment protective layer is not particularly limited as long as it is a group in which a functional group having a function of aligning a liquid crystalline compound is aligned, but in the present invention, the alignment protective layer is brought into contact with the surface when the alignment protective layer is formed. However, it is preferably a group obtained by photoreacting a photoalignable group for the reason that it is possible to prevent deterioration of the surface state.
  • the photoalignment group refers to a photoreactive group that imparts orientation by any of a photodimerization reaction, a photoisomerization reaction, and a photolysis reaction.
  • the group that imparts orientation by a photodimerization reaction include groups introduced from at least one derivative selected from the group consisting of maleimide derivatives, cinnamic acid derivatives, and coumarin derivatives.
  • Preferred examples include cinnamate group and chalcone group.
  • the cinnamate group and the chalcone group for example, the following structure (in the following formula, * represents a connecting site to a polymer chain, and R represents a hydrogen atom or a monovalent organic group) is introduced.
  • the connecting site to the polymer chain represented by * may be directly connected to the main chain of the polymer or may be bonded via a divalent linking group.
  • the monovalent organic group represented by R is preferably an alkyl group or an aryl group.
  • the monovalent organic group represented by R preferably has 1 to 10 carbon atoms, and more preferably 1 to 7 carbon atoms.
  • the reactive group that isomerizes by the action of light specifically, for example, a group composed of a skeleton of at least one compound selected from the group consisting of an azobenzene compound, a stilbene compound, and a spiropyran compound is preferable. It is mentioned in.
  • Specific examples of the reactive group capable of decomposing by the action of light include a group composed of a skeleton of a cyclobutane compound.
  • the reaction is preferably a group that imparts orientation by a photodimerization reaction that reacts with shorter wave light, and is at least one selected from the group consisting of a cinnamate group and a chalcone group. More preferably.
  • the crosslinked structure of the orientation protective layer is a crosslinked structure including any one of the structures represented by the following formulas (A-1) to (A-3).
  • each R 1 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, hexyl group and the like.
  • examples of the crosslinked structure including the structures represented by the above formulas (A-1) to (A-3) include, for example, a crosslinkable group (for example, epoxy group, oxetanyl group) and an acid group (for example, carboxyl group). And the like, specifically, represented by the following formula (A-1-1), formula (A-2-1) and formula (A-3-1).
  • a crosslinked structure is mentioned.
  • * represents a bonding position
  • R in the following formula (A-3-1) 1 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the orientation protective layer has a structure in which the orientation group and the crosslinked structure are connected to each other through a covalent bond. Therefore, in the present invention, a polymer containing a structural unit having a crosslinkable group (for example, an epoxy group, an oxetanyl group, etc.) described later, and / or a structural unit having an acid group (for example, a carboxyl group, etc.) described later. It is preferable that the polymer containing contains further the structural unit which has the said orientation group.
  • a crosslinkable group for example, an epoxy group, an oxetanyl group, etc.
  • an acid group for example, a carboxyl group, etc.
  • the thickness of the alignment protective layer is preferably 1 to 4 ⁇ m, more preferably 2 to 3 ⁇ m.
  • substrate which the liquid crystal display device of this invention has may have comprised the color filter between the base material mentioned above and the alignment protective layer.
  • the color filter is not particularly limited, and, for example, a commonly known color filter for a liquid crystal display device can be used.
  • a color filter is usually composed of transparent colored patterns of red, green and blue, and each transparent colored pattern is made of a resin composition in which a colorant is dissolved or dispersed, preferably pigment fine particles are dispersed. Composed.
  • the color filter may be formed by preparing an ink composition colored in a predetermined color and printing it for each colored pattern.
  • a paint-type photosensitive material containing a colorant of a predetermined color may be used. It is more preferable to carry out by a photolithography method using a conductive resin composition.
  • the liquid crystal layer included in the liquid crystal display device of the present invention is a liquid crystal layer sandwiched between the first substrate described above and a second substrate described later. Further, as described above, the liquid crystal layer is provided so as to be in contact with the alignment protective layer included in the first substrate described above.
  • Driving methods for driving the liquid crystal layer used in the liquid crystal display device of the present invention include TN (Twisted-Nematic) method, VA (Vertical-Alignment) method, IPS (In-Plane-Switching) method, FFS (Fringe-Field). Switching) method, OCB (Optically Compensated Bend) method, etc.
  • the IPS method is preferable.
  • the IPS liquid crystal cell rod-like liquid crystal molecules are aligned substantially parallel to the substrate, and the liquid crystal molecules respond in a planar manner when an electric field parallel to the substrate surface is applied. That is, in the IPS system, the liquid crystal constituting the liquid crystal layer is a horizontally aligned liquid crystal.
  • black is displayed when no electric field is applied, and the absorption axes of a pair of upper and lower polarizing plates are orthogonal.
  • the second substrate included in the liquid crystal display device of the present invention is a substrate provided on the opposite side (backlight side) of the liquid crystal layer described above, and includes a base material, a thin film transistor, a display electrode, and an orientation. And a membrane.
  • a transparent substrate used in a liquid crystal cell of a conventionally known liquid crystal display device can be used, for example, a glass substrate, a quartz substrate, a transparent substrate, as in the first substrate described above.
  • a resin substrate or the like can be used. Among these, it is preferable to use a glass substrate.
  • a thin film transistor (TFT) included in the second substrate a thin film transistor (TFT) used in a known liquid crystal display device can be used as appropriate, and the configuration is not particularly limited. Or a bottom gate type.
  • Specific examples of the thin film transistor include an amorphous silicon TFT, a low temperature polysilicon TFT, an oxide semiconductor TFT, and the like.
  • Display electrodes As the display electrodes provided in the second substrate, those used in known liquid crystal display devices can be used as appropriate, and examples of the constituent material thereof include indium tin oxide (ITO) and oxidation.
  • ITO indium tin oxide
  • a transparent conductive material such as zinc aluminum (Aluminum doped Zinc Oxide: AZO) or indium zinc oxide (IZO) can be used.
  • the alignment film provided in the second substrate generally used as a main component of a polymer, which is used in a known liquid crystal display device, can be appropriately used.
  • the polymer material for alignment film is described in many documents, and many commercially available products can be obtained.
  • the polymer material used in the present invention is preferably polyvinyl alcohol or polyimide, and derivatives thereof. In particular, modified or unmodified polyvinyl alcohol is preferred.
  • liquid crystal display device for example, a polarizing plate, a backlight, and the like
  • the descriptions in JP-A-2007-328210 and JP-A-2014-238438 can be referred to, and the contents thereof are incorporated in this specification. I will do it.
  • the method for producing a liquid crystal display device of the present invention comprises an alignment protective layer containing, on a substrate, a polymer P containing a structural unit having an orientation group and a polymer A not containing a structural unit having an orientation group. After forming a protective layer using the composition for formation, the protective layer is subjected to an alignment treatment to form an alignment protective layer, and a first step of producing a first substrate is included.
  • the method for manufacturing a liquid crystal display device of the present invention includes a second substrate including a base material, a thin film transistor, a display electrode, and an alignment film, and a first substrate bonded to each other to enclose liquid crystal, A liquid crystal layer is formed between the second substrate and the second step of manufacturing a liquid crystal display device.
  • the first step uses a composition for forming an alignment protective layer containing, on a substrate, a polymer P containing a structural unit having an orientation group and a polymer A not containing a structural unit having an orientation group.
  • the protective layer is subjected to an alignment treatment to form an alignment protective layer, thereby producing a first substrate.
  • the base material in a 1st process is the same as the base material with which the 1st board
  • the composition for forming an alignment protective layer lowers the phase difference of the alignment protective layer, increases transparency, and facilitates the formation of the above-described crosslinked structure in the alignment protective layer. It is preferable that the structural unit represented by the following s1 is included as the structural unit having a group, and the polymer P and the polymer A satisfy the following condition 3 or 4.
  • s1 a structural unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton and an alkyl group having 10 to 30 carbon atoms, and a structural unit having a photoalignment group
  • Condition 3 Heavy The coalescence P includes a structural unit a2 having a crosslinkable group, and the polymer A includes a structural unit a3 having an acid group.
  • Condition 4 The polymer P includes a structural unit a3 having an acid group, and the polymer A includes a structural unit a2 having a crosslinkable group.
  • the crosslinkable group possessed by the polymer P and / or the polymer A is an oxiranyl group, a 3,4-epoxycyclohexyl group, because the above-mentioned crosslinked structure is more easily formed in the alignment protective layer. And at least one selected from the group consisting of oxetanyl groups.
  • a polymer containing a structural unit represented by the following s1 (hereinafter also referred to as “structural unit s1”) is preferably exemplified.
  • structural unit s1 a structural unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton and an alkyl group having 10 to 30 carbon atoms (hereinafter also referred to as “unevenly-distributed group”), and Constituent unit having photo-alignment group
  • the fluorine-substituted hydrocarbon group may be a hydrocarbon group substituted with at least one fluorine atom, and is at least one of an alkyl group or an alkylene group (hereinafter abbreviated as “alkyl group etc.” in this paragraph).
  • alkyl group etc.” examples include alkyl groups in which hydrogen atoms are substituted with fluorine atoms, and alkyl groups in which all hydrogen atoms such as alkyl groups are substituted with fluorine atoms are more preferable.
  • Such a fluorine-substituted hydrocarbon group is preferably a group represented by the following formula (I) from the viewpoint of uneven distribution.
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a site connected to a polymer chain.
  • X represents a single bond or a divalent linking group
  • m represents an integer of 1 to 3
  • n represents an integer of 1 or more
  • r represents 0 or an integer of 1 to 2.
  • m 1, the plurality of R 2 may be the same or different.
  • M in the above formula (I) represents an integer of 1 to 3, and is preferably 1 or 2.
  • N in the above formula (I) represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and particularly preferably 1 or 2.
  • R in the general formula I represents 0 or an integer of 1 to 2, preferably 1 or 2, and more preferably 2.
  • the connecting part to the polymer chain represented by * may be directly connected to the main chain of the polymer such as the above-mentioned polymer A1-1, or a polyoxyalkylene group, an alkylene group, an ester group, a urethane group. And may be bonded via a divalent linking group such as a cyclic alkylene group which may contain a hetero atom, poly (caprolactone), or amino group. It is preferable that they are bonded via a polyoxyalkylene group.
  • alkyl group having 1 to 4 carbon atoms represented by R 2 in the above formula (I) examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and the like. Preferably, they are a hydrogen atom or a methyl group, More preferably, it is a hydrogen atom.
  • X when X is a single bond, it means that the polymer main chain and the carbon atom to which R 2 is bonded are directly connected.
  • examples of the linking group include —O—, —S—, —N (R 4 ) —, —CO—, and the like. Among these, —O— is more preferable.
  • R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group, and a hydrogen atom and a methyl group are preferable.
  • a method of introducing a fluorine-substituted hydrocarbon group into a polymer a method of introducing a fluorine-substituted hydrocarbon group into a polymer by a polymer reaction; a monomer having a fluorine-substituted hydrocarbon group (hereinafter referred to as “fluorine-substituted hydrocarbon group-containing” And a method of introducing a structural unit having a fluorine-substituted hydrocarbon group into the polymer.
  • the fluorine-substituted hydrocarbon group-containing monomer is a monomer represented by the following formula (II) Is preferable.
  • R 1 represents a hydrogen atom, a halogen atom, a methyl group which may have a substituent, or an ethyl group which may have a substituent.
  • R 2 , X, m, n and r all have the same meaning as R 2 , X, m, n and r in formula I, and preferred examples are also the same.
  • the halogen atom represented by R 1 in the above-mentioned formula (II) for example, a fluorine atom, a chlorine atom, a bromine atom.
  • the monomer represented by the above formula (II) include tetrafluoroisopropyl methacrylate represented by the following formula (IIa), hexafluoroisopropyl methacrylate represented by the following formula (IIb), and the like.
  • Other specific examples include compounds described in paragraph numbers [0058] to [0061] of JP 2010-18728 A. Of these, a structure in which a fluorine-substituted hydrocarbon group is bonded to a polyoxyalkylene group is preferable.
  • the siloxane skeleton is not particularly limited as long as it has “—Si—O—Si—”, and preferably contains a polyoxyalkylene group.
  • the siloxane skeleton is copolymerized with a compound having a (meth) acryloyloxy group and an alkoxysilyl group and introduced into a constituent unit having a partial structure of the siloxane skeleton in the polymer.
  • a compound having a (meth) acryloyloxy group and an alkoxysilyl group is preferable.
  • the alkoxysilyl group for example, a group represented by the following formula (X) is preferable.
  • R 3 to R 5 each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group or an alkoxy group, and at least one is an alkoxy group. * Represents a binding position.
  • At least one of R 3 to R 5 is an alkoxy group, and the alkoxy group is preferably an alkoxy group having 1 to 15 carbon atoms, and an alkoxy group having 1 to 8 carbon atoms. It is more preferably a group, more preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably an ethoxy group or a methoxy group.
  • Specific examples of the compound having such an alkoxysilyl group and a (meth) acryloyloxy group include 3- (meth) acryloxypropylmethyldimethoxysilane and 3- (meth) acryloxypropyltrimethoxysilane. 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, and the like.
  • the siloxane skeleton is polymerized with a compound represented by the following structural formula (A) (hereinafter also referred to as “specific siloxane compound”), and the siloxane skeleton is converted into a polymer. It is preferable to introduce.
  • R 7 represents a linear or branched alkylene group having 2 to 6 carbon atoms which may have a substituent such as a hydroxyl group, an amine group, or a halogen atom, or the following structural formula (B ) Represents a divalent linking group.
  • R 4 represents a hydrogen atom, a methyl group, or an ethyl group.
  • n1, n2, and n3 are each independently an integer of 0 to 100.
  • two or more R 4 s exist in the structural formula (B), but they may be different or the same.
  • x1, x2 and x3 are integers whose sum satisfies 1 to 100.
  • Y1 is an integer of 1 to 30.
  • X 2 is a single bond or a divalent group represented by the following structural formula (C).
  • R 8 represents a linear or branched alkylene group having 1 to 6 carbon atoms which may have a substituent such as a hydroxyl group, an amine group, or a halogen atom
  • Q 1 , Q 2 represents an oxygen atom, a sulfur atom, or —NRB—, and Q 1 and Q 2 may be different from each other or the same.
  • RB represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • Q 2 is bonded to R 7 in the structural formula (A).
  • Y 2 represents a monovalent group represented by the following structural formula (D) to the following structural formula (F).
  • R 5 represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.
  • Z 1 , Z 2 , and Z 3 each independently represent a monovalent group represented by the following structural formula (G).
  • R 6 represents an unsubstituted alkyl group having 1 to 4 carbon atoms
  • y2 represents an integer of 1 to 100, preferably an integer of 1 to 50, more preferably 1 to 20 It is an integer.
  • siloxane skeleton examples include the structures described in paragraphs [0092] to [0094] of JP 2010-18728 A, as specific examples of the above formula (A), but are not limited thereto. Absent. Of these, a structure in which a siloxane structure is bonded to a polymer via a polyoxyalkylene group is preferable.
  • the alkyl group having 10 to 30 carbon atoms may contain a branched structure or a cyclic structure, but the linear structure portion preferably has a carbon number in the range of 10 to 30, and all have a linear structure. Is more preferable.
  • the alkyl group preferably has 10 to 20 carbon atoms.
  • the side chain of the polymer preferably has a group represented by the following general formula (a3-1).
  • n a3 represents an integer of 10 to 30, and * represents a position linked to the main chain or side chain of the polymer. na3 is preferably an integer of 10 to 20.
  • the method for introducing the structure of the general formula (a3-1) into the main chain or side chain of the polymer For example, a monomer having the structure of (a3-1) is appropriately selected during synthesis and applied. In this case, the structure (a3-1) can be introduced into the repeating unit of the obtained polymer.
  • the monomer having the structure of the general formula (a3-1) a commercially available compound can be used, but it is included in (a3-1) with respect to a commercially available monomer having no structure of (a3-1).
  • a desired structure may be introduced as appropriate.
  • the method of introducing the structure (a3-1) into a commercially available monomer and a known method may be applied as appropriate.
  • the monomer having the structure of the general formula (a3-1) can be appropriately selected according to the main chain structure of the polymer.
  • the polymer has a (meth) acrylic structure in the main chain, the following general It is preferable to use a monomer represented by the formula (a3-2).
  • R 32 represents a hydrogen atom, a methyl group, an ethyl group, or a halogen atom
  • X 31 represents a divalent linking group
  • R 33 represents a single bond or an alkyleneoxy group.
  • N a3 has the same meaning as the general formula (a3-1), including the preferred range.
  • R 32 represents a hydrogen atom, a methyl group, an ethyl group, or a halogen atom, more preferably a hydrogen atom or a methyl group, and still more preferably a methyl group.
  • examples of the divalent linking group as X 31 include —O—, —S—, —N (R 4 ) —, and the like. Among these, —O— is more preferable.
  • R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group may be a linear structure or a branched structure, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.
  • they are a hydrogen atom and a methyl group.
  • the alkyleneoxy group for R 33 preferably has 1 to 4 carbon atoms.
  • the alkyleneoxy group may have a branched structure. Moreover, even if it has a substituent, it may be unsubstituted. Examples of the substituent that may have include a halogen atom. Specific examples of the alkyleneoxy group include a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, and the like.
  • R 33 is preferably an unsubstituted linear alkyleneoxy group having 1 to 4 carbon atoms, or a single bond, and more preferably a single bond.
  • a polymer having a repeating unit represented by the following general formula (U-a3-1) can be obtained.
  • Such a polymer is one of preferred embodiments having a repeating unit represented by the following general formula (U-a3-1).
  • n a3 has the same meaning as that of the general formula (a3-1), including a preferable range, and R 32 , X 31 , and R 33 represent the general formula (a3- It is synonymous including 2) and a preferable range.
  • the polymer P has a photoalignable group together with the above-described structural unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton, and an alkyl group having 10 to 30 carbon atoms.
  • the photo-alignment group is the same as that described for the orientation group.
  • the main chain skeleton of the polymer having a structural unit having a photo-alignment group is not particularly limited, but the side chain molecular design is diversified, and the main chain formation by radical polymerization reaction of an ethylenically unsaturated compound is simple.
  • a polymer having a repeating unit represented by the following formula (III) is preferable.
  • R 1 represents a hydrogen atom or an alkyl group.
  • X represents an arylene group, — (C ⁇ O) —O—, or — (C ⁇ O) —NR— (R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
  • L represents a single bond or a divalent linking group
  • P represents a photoalignment group.
  • R 1 represents a hydrogen atom or an alkyl group
  • the alkyl group is an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, n-propyl group, isopropyl group, n- Butyl group and the like are preferable.
  • R 1 is preferably a hydrogen atom or a methyl group.
  • L represents a single bond or a divalent linking group, and the divalent linking group may be —O—, —S—, an alkylene group, an arylene group, or a combination thereof. Is preferred.
  • the alkylene group represented by L may be a linear, branched, or cyclic structure, but is preferably a linear structure.
  • the alkylene group represented by L preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
  • a phenylene group is preferable.
  • P represents a photoalignable group, and specific examples thereof include a chalcone group, a cinnamate group, a stilbenyl group, a maleimide group, and an azobenzyl group.
  • the photoalignable group represented by P may have a substituent as long as the photoalignment is not lost.
  • the substituent include a halogeno group, an alkyl group, and an aryl group, and an alkyl group or an aryl group is preferable.
  • the alkyl group or aryl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 7 carbon atoms.
  • the polymer having a repeating unit represented by the above formula (I) may be synthesized by (a) a method in which a corresponding monomer is polymerized to directly introduce a photoreactive group, and (b) any functional group. It may be synthesized by a method in which a photoreactive group is introduced into a polymer obtained by polymerizing a monomer having a polymer reaction. Moreover, it can also synthesize
  • radical polymerization, cation polymerization, anion polymerization, etc. are mentioned as a polymerization reaction which can be utilized in the method of (a) and (b) mentioned above.
  • the polymer having a repeating unit represented by the above formula (I) may be a copolymer composed of a plurality of types of repeating units represented by the above formula (I). ) May be a copolymer containing a repeating unit other than (for example, a repeating unit not containing an ethylenically unsaturated group).
  • the structural unit s1 is preferably 0.01 to 10% by mole, more preferably 0.1 to 10% by mole, still more preferably 0.1 to 5% by mole, based on the structural unit of all polymer components. 1 to 3 mol% is particularly preferred, and 0.5 to 3 mol% is most preferred.
  • the content of the structural unit having a ubiquitous group is preferably 0.01 to 3% by mole, more preferably 0.1 to 3% by mole, and 0.5 to 3% by mole. Is more preferable.
  • the content of the structural unit having a photo-alignment group is preferably 0.01 to 5% by mole, more preferably 0.1 to 5% by mole, and 1 to 3% by mole. Further preferred.
  • the content of the structural unit s1 is preferably 20 to 90% by mole, more preferably 20 to 80% by mole, and more preferably 20 to 70% by mole based on all the structural units of the polymer. Is more preferable.
  • the content of the structural unit having a ubiquitous group is preferably 1 to 50 mol%, more preferably 5 to 30 mol%, and still more preferably 10 to 20 mol%.
  • the content of the structural unit having a photoalignable group is preferably 1 to 70 mol%, more preferably 10 to 60 mol%, still more preferably 20 to 50 mol%.
  • the “structural unit” is synonymous with the “monomer unit”.
  • the “monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.
  • Examples of the polymer P include, in addition to the structural unit s1 described above, a structural unit a1 having a group in which an acid group is protected by an acid-decomposable group, a structural unit a2 having a crosslinkable group, and a structural unit having an acid group. a3, other structural units a4 may be included.
  • the structural unit a2 having a crosslinkable group and / or the structural unit a3 having an acid group is included for the reason that the above-described crosslinked structure is easily formed in the alignment protective layer. Is preferred.
  • the structural unit a1 is a structural unit having an acid group protected with an acid-decomposable group (hereinafter also referred to as the structural unit a1).
  • the “group in which an acid group is protected with an acid-decomposable group” in the present invention is a group that causes a deprotection reaction using an acid as a catalyst (or an initiator) to generate an acid group, a regenerated acid, and a decomposed structure. Means.
  • the “group in which the acid group is protected with an acid-decomposable group” in the present invention those known as an acid group and an acid-decomposable group can be used, and are not particularly limited.
  • the acid group include a carboxyl group and a phenolic hydroxyl group.
  • an acid-decomposable group a group that is relatively easily decomposed by an acid (for example, an acetal functional group such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group) or an acid-decomposable group is relatively difficult to decompose by an acid.
  • Groups for example, tertiary alkyl groups such as tert-butyl ester groups and tertiary alkyl carbonate groups such as tert-butyl carbonate groups).
  • the structural unit a1 having a group in which an acid group is protected with an acid-decomposable group is a structural unit having a protected carboxyl group in which a carboxyl group is protected with an acid-decomposable group (hereinafter referred to as “protection protected with an acid-decomposable group”).
  • a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected with an acid-decomposable group hereinafter referred to as “protected phenolic hydroxyl group protected with an acid-decomposable group”. It is also preferable that it is also referred to as a “structural unit”.
  • the structural unit a1-1 having a protected carboxyl group protected with an acid-decomposable group and the structural unit a1-2 having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in order.
  • the structural unit a1-1 having a protected carboxyl group protected with an acid-decomposable group has a carboxyl group in the structural unit having a carboxyl group as a protected carboxyl group protected by an acid-decomposable group described in detail below. It is a structural unit.
  • the structural unit having a carboxyl group that can be used for the structural unit a1-1 having a protected carboxyl group protected by the acid-decomposable group is not particularly limited, and a known structural unit can be used.
  • the structural unit a1-1-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid; And a structural unit a1-1-2 having both an unsaturated group and a structure derived from an acid anhydride.
  • ⁇ Structural unit a1-1-1 derived from unsaturated carboxylic acid having at least one carboxyl group in the molecule examples include those described in JP-A-2014-238438. And the compounds described in paragraph 0043. Among these, from the viewpoint of developability, in order to form the structural unit a1-1-1, acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxy are used.
  • ethyl hexahydrophthalic acid 2- (meth) acryloyloxyethyl-phthalic acid, or an anhydride of an unsaturated polyvalent carboxylic acid.
  • the structural unit a1-1-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule may be composed of one kind alone, or may be composed of two or more kinds. Good.
  • ⁇ Structural unit a1-1-2 having both an ethylenically unsaturated group and a structure derived from an acid anhydride The structural unit a1-1-2 having both an ethylenically unsaturated group and a structure derived from an acid anhydride is obtained by reacting a hydroxyl group present in a structural unit having an ethylenically unsaturated group with an acid anhydride.
  • the unit is preferably derived from a monomer.
  • the acid anhydride known ones can be used, and specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, etc.
  • phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
  • the reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol% from the viewpoint of developability.
  • the above-mentioned acid-decomposable groups can be used.
  • the carboxyl group is a protected carboxyl group protected in the form of an acetal, so that the basic physical properties of the resin composition, particularly sensitivity and pattern shape, contact hole formation, and storage of the resin composition It is preferable from the viewpoint of stability.
  • the carboxyl group is more preferably a protected carboxyl group protected in the form of an acetal represented by the following formula (a1-10) from the viewpoint of sensitivity.
  • the entire protected carboxyl group is — (C ⁇ O) —O—CR 101 R 102 ( OR 103 ).
  • R 101 and R 102 each independently represent a hydrogen atom or a hydrocarbon group, except that R 101 and R 102 are both hydrogen atoms.
  • R 103 represents an alkyl group.
  • R 101 or R 102 and R 103 may be linked to form a cyclic ether.
  • R 101 and R 102 each independently represents a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched or cyclic.
  • both R 101 and R 102 do not represent a hydrogen atom, and at least one of R 101 and R 102 represents an alkyl group.
  • the alkyl group may be linear, branched or cyclic.
  • the linear alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
  • the branched chain preferably has 3 to 6 carbon atoms, and more preferably has 3 or 4 carbon atoms.
  • methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.
  • the cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms.
  • Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.
  • the alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group.
  • R 101 , R 102 and R 103 When it has a halogen atom as a substituent, R 101 , R 102 and R 103 become a haloalkyl group, and when it has an aryl group as a substituent, R 101 , R 102 and R 103 become an aralkyl group.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
  • the aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms.
  • Specific examples include a phenyl group, an ⁇ -methylphenyl group, a naphthyl group, and the like, and examples of the entire alkyl group substituted with an aryl group, that is, an aralkyl group include a benzyl group, an ⁇ -methylbenzyl group, a phenethyl group, A naphthylmethyl group etc. can be illustrated.
  • the alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and still more preferably a methoxy group or an ethoxy group.
  • the alkyl group is a cycloalkyl group
  • the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is a linear chain. Or a branched alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent. These substituents may be further substituted with the above substituents.
  • R 101 , R 102 and R 103 represent an aryl group
  • the aryl group preferably has 6 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms.
  • the aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.
  • R 101 , R 102 and R 103 can be bonded together to form a ring together with the carbon atom to which they are bonded.
  • Examples of the ring structure when R 101 and R 102 , R 101 and R 103 or R 102 and R 103 are bonded include, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.
  • any one of R 101 and R 102 is preferably a hydrogen atom or a methyl group.
  • radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the above formula (a1-10) a commercially available one may be used, or one synthesized by a known method Can also be used. For example, it can be synthesized by the synthesis method described in paragraphs 0037 to 0040 of JP2011-212494A.
  • a first preferred embodiment of the structural unit a1-1 having a protected carboxyl group protected by the acid-decomposable group is a structural unit represented by the following formula.
  • R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 1 and R 2 is an alkyl group or an aryl group, and R 3 is an alkyl group or Represents an aryl group, R 1 or R 2 and R 3 may be linked to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group;
  • R 1 and R 2 are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred. When R 1 and R 2 are aryl groups, a phenyl group is preferred. R 1 and R 2 are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. X represents a single bond or an arylene group, and a single bond is preferable.
  • a second preferred embodiment of the structural unit a1-1 having a protected carboxyl group protected by the acid-decomposable group is a structural unit represented by the following formula.
  • R 121 represents a hydrogen atom or a methyl group
  • L 1 represents a carbonyl group
  • R 122 to R 128 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom is preferred.
  • R represents a hydrogen atom or a methyl group.
  • ⁇ Structural unit a1-2 having a protected phenolic hydroxyl group protected with an acid-decomposable group examples include a structural unit in a hydroxystyrene-based structural unit and a novolac-based resin. Of these, a structural unit derived from hydroxystyrene or ⁇ -methylhydroxystyrene is preferred from the viewpoint of sensitivity. As the structural unit having a phenolic hydroxyl group, the structural units described in paragraphs 0065 to 0073 of JP-A-2014-238438 are also preferable from the viewpoint of sensitivity.
  • the structural unit a2 is a structural unit having a crosslinkable group (hereinafter also referred to as a structural unit a2).
  • the crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment.
  • Preferred embodiments of the structural unit having a crosslinkable group include an epoxy group (for example, oxiranyl group, 3,4-epoxycyclohexyl group, etc.), oxetanyl group, —NH—CH 2 —O—R (R is a hydrogen atom or carbon atom) And a structural unit containing at least one selected from the group consisting of a group represented by formula (1) to (20), an ethylenically unsaturated group, and a blocked isocyanate group, such as an epoxy group and an oxetanyl group.
  • an epoxy group for example, oxiranyl group, 3,4-epoxycyclohexyl group, etc.
  • oxetanyl group —NH—CH 2 —O—R (R is a hydrogen atom or carbon atom)
  • R is a hydrogen atom or carbon atom
  • a group represented by the group: —NH—CH 2 —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), a (meth) acryloyl group, and a blocked isocyanate group. is preferably a structural unit containing at least one selected, epoxy group, oxetanyl group, and, -NH-CH 2 -O-R (R is a hydrogen atom or a carbon atoms ⁇ And more preferably a structural unit containing at least one selected from the group consisting of groups represented by.) Represents an alkyl group of 20.
  • the polymer component A1 preferably contains a polymer having a structural unit a2-1 having an epoxy group and / or an oxetanyl group.
  • a 3-membered cyclic ether group is also called an epoxy group, and a 4-membered cyclic ether group is also called an oxetanyl group.
  • the structural unit a2-1 having an epoxy group and / or oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, and may be one or more epoxy groups and one or more oxetanyl groups.
  • Group, two or more epoxy groups, or two or more oxetanyl groups may be included, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups. It is more preferable to have one or two oxetanyl groups in total, and it is even more preferable to have one epoxy group or oxetanyl group.
  • radical polymerizable monomer used for forming the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, and glycidyl ⁇ -n-propyl acrylate.
  • radical polymerizable monomer used for forming the structural unit having an oxetanyl group include, for example, a (meth) acryl having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Acid esters, and the like, the contents of which are incorporated herein.
  • radical polymerizable monomer used for forming the structural unit a2-1 having the epoxy group and / or oxetanyl group include a monomer having a methacrylic ester structure and an acrylic ester structure. A monomer is preferred.
  • These structural units can be used individually by 1 type or in combination of 2 or more types.
  • R represents a hydrogen atom or a methyl group.
  • ⁇ Structural unit a2-2 having an ethylenically unsaturated group Another example of the structural unit a2 having a crosslinkable group includes the structural unit a2-2 having an ethylenically unsaturated group.
  • the structural unit a2-2 having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in the side chain, having an ethylenically unsaturated group at the terminal, and having 3 to 16 carbon atoms.
  • Another example of the structural unit a2 having a crosslinkable group has a group represented by —NH—CH 2 —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms).
  • the structural unit a2-3 is also preferable.
  • R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 9 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
  • the structural unit a2-3 is more preferably a structural unit having a group represented by the following formula (a2-30).
  • R 31 represents a hydrogen atom or a methyl group
  • R 32 represents an alkyl group having 1 to 20 carbon atoms.
  • R 32 is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
  • Specific examples of R 32 include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl group, n-butyl group and methyl group are preferable.
  • the structural unit a3 is a structural unit having an acid group (hereinafter also referred to as a structural unit a3).
  • the acid group in the present invention means a proton dissociable group having a pKa smaller than 11.
  • Examples of the acid group used in the present invention include a carboxylic acid group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, a sulfonamide group, a sulfonylimide group, and acid anhydride groups of these acid groups, And the group etc.
  • the structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. .
  • the structural unit a3 having an acid group from the viewpoint of sensitivity, a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group is preferable, and a structural unit having a carboxyl group is more preferable.
  • Specific examples of the structural unit a3 having an acid group include the structural unit a1-1-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, an ethylenically unsaturated group, and an acid anhydride. Examples thereof include a structural unit a1-1-2 having both a structure derived from a product and a structural unit a1-2-1 having a phenolic hydroxyl group, and preferred embodiments are also the same.
  • the structural unit a3 having an acid group is a structural unit derived from a compound selected from the group consisting of methacrylic acid, acrylic acid and p-hydroxystyrene [of the following formulas (a3-1) to (a3-3):
  • a structural unit represented by any of the above formulas preferably a structural unit derived from methacrylic acid [a structural unit represented by the following formula (a3-1)] or a structural unit derived from acrylic acid [the following formula (a3-2) Is more preferably a structural unit derived from methacrylic acid [a structural unit represented by the following formula (a3-1)].
  • Structural Unit a4 >>>
  • the monomer which forms the other structural unit a4 can be used individually by 1 type or in combination of 2 or more types.
  • the other structural unit a4 include styrene, methylstyrene, ⁇ -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, 4-hydroxybenzoic acid ( 3-methacryloyloxypropyl) ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth And a structural unit such as 2-hydroxypropyl acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate, and the like.
  • compounds described in paragraphs compounds described in paragraph
  • a structural unit derived from a monomer having a styrene or an aliphatic cyclic skeleton is preferable from the viewpoint of electrical characteristics.
  • Specific examples include styrene, methylstyrene, ⁇ -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate.
  • a structural unit derived from (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion.
  • Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable.
  • the content of the structural unit a4 is preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less.
  • 0 mol% may be sufficient, it is preferable to set it as 1 mol% or more, for example, and it is more preferable to set it as 5 mol% or more.
  • various properties of the cured film obtained from the resin composition are improved.
  • polymer A examples include a polymer that does not include the above-described structural unit s1, but includes any one or more of the above-described structural units a1 to a4.
  • a polymer having a structural unit a2 having a crosslinkable group and / or a structural unit a3 having an acid group is preferable because the above-described crosslinked structure is easily formed in the layer.
  • the molecular weight of the above-mentioned polymer P and polymer A is a polystyrene-converted weight average molecular weight, preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and still more preferably 10,000 to 20,000. 000 range. Various characteristics are favorable in the range of said numerical value.
  • the ratio (dispersity, Mw / Mn) between the number average molecular weight Mn and the weight average molecular weight Mw is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.
  • GPC gel permeation chromatography
  • HLC-8020GPC manufactured by Tosoh Corporation
  • TSKgel Super HZ MH TSK gel Super HZ4000
  • TSKgel SuperHZ200 manufactured by Tosoh Corporation
  • THF tetrahydrofuran
  • the polymer P and the polymer A include a radical polymerizable monomer used to form each structural unit described above. It can be synthesized by polymerizing a radical polymerizable monomer mixture in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
  • the mass ratio of the polymer P to the total mass of the polymer P and the polymer A described above is preferably less than 10% by mass. More preferably, the content is 1 to 5% by mass.
  • the alignment protective layer has a molecular weight of 5000 or less because the flatness when a color filter is provided on the viewing side is improved and the display performance after being exposed to high temperature and high humidity becomes better. It is preferable to contain the crosslinking agent B.
  • the crosslinking agent B any crosslinking agent can be used as long as it causes a crosslinking reaction by heat. For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, a blocked isocyanate compound (a compound having a protected isocyanato group), an alkoxymethyl group-containing compound, or at least one ethylenic group.
  • the crosslinking agent B preferably used in this invention is demonstrated.
  • crosslinking agent B examples include polyfunctional small ring cyclic ether compounds. That is, it means a compound having two or more epoxy groups and / or oxetanyl groups in one molecule.
  • the compound having two or more epoxy groups in the molecule include aliphatic epoxy compounds. These are available as commercial products. For example, Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321 , EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX -920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301 DLC-402 (manufactured by Nagase ChemteX Corporation), Celoxide 2021
  • Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX above, manufactured by Toagosei Co., Ltd.
  • the compound containing an oxetanyl group is preferably used alone or mixed with a compound containing an epoxy group.
  • Block isocyanate compound As the crosslinking agent B, a blocked isocyanate compound can also be preferably employed.
  • the blocked isocyanate compound is not particularly limited as long as the isocyanate group has a chemically protected blocked isocyanate group, but is a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability. It is preferable.
  • the blocked isocyanate group in this invention is a group which can produce
  • the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably.
  • the blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
  • the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and may be aliphatic, alicyclic or aromatic.
  • Polyisocyanates may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2, '-Diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • Examples of the matrix structure of the blocked isocyanate compound include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
  • Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to.
  • a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.
  • Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
  • Examples of the lactam compound include ⁇ -caprolactam and ⁇ -butyrolactam.
  • Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
  • Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
  • amine compound a primary amine and a secondary amine are mentioned, Any of an aromatic amine, an aliphatic amine, and an alicyclic amine may be sufficient, An aniline, diphenylamine, ethyleneimine, polyethyleneimine etc. can be illustrated.
  • Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
  • pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
  • the mercaptan compound include alkyl mercaptans and aryl mercaptans.
  • the blocked isocyanate compound is available as a commercial product.
  • Coronate AP Stable M Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (above, manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate B -830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (manufactured by Mitsui Chemicals, Inc.), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above, manufactured by Asahi Kasei Chemicals Corporation), Death Module BL1100, BL1265 MPA / X BL3575 / 1, BL3272MPA, BL
  • alkoxymethyl group-containing crosslinking agent alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferable. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylolated urea to an alkoxymethyl group, respectively.
  • the type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group.
  • a methyl group is particularly preferred.
  • alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are preferable compounds, and alkoxymethylated glycoluril is particularly preferable from the viewpoint of transparency.
  • alkoxymethyl group-containing crosslinking agent a compound having a molecular weight of 1,000 or less is used for the curable composition. These alkoxymethyl group-containing compounds are available as commercial products.
  • Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid), Nicarax MX-750, -032, -706, -708, -40, -31, -270, -280, -290, Nicarak MS-11, Nicarak MW-30HM, -100LM, -390, (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.
  • the content is preferably 30% by mass or less, and preferably 10 to 30% by mass with respect to the total mass of the crosslinking agent B, the polymer P and the polymer A. More preferred.
  • the protective layer-forming composition preferably contains an organic solvent in addition to the polymer described above.
  • organic solvent known organic solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene.
  • Glycol monoalkyl ether acetates diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, butylene glycol diacetates, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, alcohol , Esters, ketones, amides, lactones, etc. Kill.
  • these organic solvents reference can be made to paragraph 0062 of JP-A-2009-098616.
  • Preferred examples include propylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, 1,3-butylene glycol diacetate, methoxypropyl acetate, cyclohexanol acetate, propylene glycol diacetate, tetrahydroflur Examples include furyl alcohol.
  • the boiling point of the organic solvent is preferably 100 ° C. to 300 ° C., more preferably 120 ° C. to 250 ° C. from the viewpoint of applicability.
  • the organic solvent which can be used for this invention can be used individually by 1 type or in combination of 2 or more types. It is also preferred to use solvents having different boiling points in combination.
  • the content is preferably from 100 to 3,000 parts by mass, preferably from 200 to 2 parts per 100 parts by mass of the total solid content of the composition, from the viewpoint of adjusting the viscosity to be suitable for coating. More preferably, it is 1,000,000 parts by mass, and even more preferably 250-1,000 parts by mass.
  • the solid content concentration of the composition is preferably 3 to 50% by mass, and more preferably 20 to 40% by mass.
  • the protective layer forming composition may contain a surfactant.
  • a surfactant any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant.
  • nonionic surfactants are preferable, and fluorine-based surfactants are more preferable.
  • surfactant that can be used in the first embodiment, for example, commercially available products such as Megafac F142D, F172, F173, F176, F177, F183, F479, F482, F554, F780, F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (manufactured by DIC Corporation), Florard FC-135, FC- 170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC -105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, 802 (manufactured by Mitsubishi Materials Denka Kasei),
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Polyflow manufactured by Kyoeisha Chemical Co., Ltd.
  • F-Top manufactured by Mitsubishi Materials Denka Kasei Co., Ltd.
  • MegaFuck manufactured by DIC Corporation
  • FLORARD manufactured by Sumitomo 3M
  • Asahi Guard Asahi Guard
  • Surflon manufactured by Asahi Glass Co., Ltd.
  • PolyFox manufactured by OMNOVA
  • the content is preferably 0.001 to 5.0 parts by mass and more preferably 0.01 to 2.0 parts by mass with respect to 100 parts by mass in the total solid content of the composition. . Only one type of surfactant may be included, or two or more types of surfactants may be included. When two or more types are included, the total amount is preferably within the above range.
  • the protective layer forming composition may contain an adhesion improving agent.
  • the adhesion improving agent include alkoxysilane compounds.
  • the alkoxysilane compound is a compound that improves the adhesion between an insulating material and an inorganic material serving as a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum. It is preferable.
  • adhesion improver examples include, for example, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycol.
  • ⁇ -glycidoxypropyltrimethoxysilane and ⁇ -methacryloxypropyltrimethoxysilane are preferred, and ⁇ -glycidoxypropyltrimethoxysilane is more preferred.
  • the content of the adhesion improving agent is preferably 0.001 to 15 parts by mass, and more preferably 0.005 to 10 parts by mass with respect to 100 parts by mass of the total solid components of the composition. Only one type of adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • the protective layer forming composition may contain a photosensitizer.
  • the photosensitizer include a photoacid generator, a quinonediazide compound, and a photoradical initiator.
  • the method for applying the protective layer-forming composition on the substrate is not particularly limited. Specifically, for example, a printing method (for example, gravure printing method, screen printing method, flexographic printing method, inkjet printing method, imprinting) Method), spin coating method, slit coating method, slit and spin coating method, dip coating method, curtain coating method and the like.
  • a printing method for example, gravure printing method, screen printing method, flexographic printing method, inkjet printing method, imprinting
  • spin coating method for example, gravure printing method, screen printing method, flexographic printing method, inkjet printing method, imprinting
  • spin coating method for example, slit coating method, slit and spin coating method, dip coating method, curtain coating method and the like.
  • solvent removal In this invention, it is after the application
  • the solvent removal step varies depending on the type and amount of the solvent. For example, when NMP is used as the solvent, it is a step of heating at about 80 to 150 ° C. for about 0.5 to 3 minutes. The step of heating at about 90 to 120 ° C. for about 0.5 to 2 minutes is more preferable.
  • orientation protective layer ⁇ Formation of orientation protective layer (orientation treatment)>
  • the alignment treatment include non-contact alignment methods such as rubbing treatment, photo-alignment treatment, and magnetic alignment.
  • the orientation treatment is preferably a photo-alignment treatment using light having a wavelength of 365 nm or less.
  • the photo-alignment treatment is not particularly limited except that light having a wavelength of 365 nm or less is used, but it is preferable to use polarized ultraviolet rays for obtaining uniform alignment.
  • the method of irradiating polarized ultraviolet rays is not particularly limited.
  • limiting in particular as polarized light For example, linearly polarized light, circularly polarized light, elliptically polarized light etc. are mentioned, Among these, linearly polarized light is preferable.
  • non-polarized light may be irradiated at an angle inclined from the normal line of the thin film.
  • non-polarized light may be irradiated from an oblique direction on the surface of the thin film.
  • “Inclined irradiation” is not particularly limited as long as it is a direction inclined by a polar angle ⁇ (0 ⁇ ⁇ 90 °) with respect to the normal direction of the thin film surface, and can be appropriately selected according to the purpose.
  • ⁇ is preferably 20 to 80 °.
  • Examples of the light source used include a xenon lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, and a metal halide lamp.
  • a xenon lamp By using an interference filter, a color filter, or the like for ultraviolet rays obtained from such a light source, the wavelength range of irradiation can be limited.
  • linearly polarized light can be obtained by using a polarizing filter or a polarizing prism for the light from these light sources.
  • the first step is preferably a step of performing a heat treatment before or after the alignment treatment.
  • a method of performing the heat treatment for example, a method of heating the protective layer or the alignment protective layer subjected to the alignment treatment at a temperature of 180 to 350 ° C., preferably 200 to 300 ° C., for 20 to 60 minutes is preferable. It is mentioned in.
  • the heat treatment is preferably performed using a heating device such as a hot plate or an oven. Further, the transparency can be further improved by performing the heat treatment in a nitrogen atmosphere.
  • the liquid crystal is sealed by bonding the second substrate having the base material, the thin film transistor, the display electrode, and the alignment film together with the first substrate, and between the first substrate and the second substrate.
  • Forming a liquid crystal layer and manufacturing a liquid crystal display device Note that the second substrate in the second step is similar to the second substrate of the liquid crystal display device of the present invention, and a manufacturing method thereof is not particularly limited.
  • the method for encapsulating the liquid crystal in the second step is not particularly limited.
  • reaction solution was poured into 1 L of water, neutralized with 2N HCl, extracted with 700 mL of ethyl acetate, washed with saturated brine, and concentrated. Subsequently, it fractionated by silica gel column chromatography, and 23g of intermediate compounds were obtained. 15 g (0.05 mol) of the intermediate compound and triethylamine (manufactured by Wako Pure Chemical Industries, Ltd., 5.6 g, 0.056 mol) were dissolved in 100 mL of THF and cooled to 0 ° C.
  • methacrylic acid chloride manufactured by Tokyo Chemical Industry Co., Ltd., 5.8 g, 0.056 mol
  • the reaction solution was poured into 500 g of water, extracted with ethyl acetate, and concentrated.
  • fractionation was performed by silica gel column chromatography to obtain 20 g of monomer a-2 having a cinnamate group as a photo-alignment group.
  • reaction solution was poured into 1 L of water, neutralized with 2N HCl, extracted with 700 mL of ethyl acetate, washed with saturated brine, and concentrated. Crude crystals were taken out and fractionated by silica gel column chromatography to obtain 18 g of an intermediate compound.
  • 18 g of the intermediate compound and triethylamine (Wako Pure Chemical Industries, Ltd., 7.79 g, 0.07 mol) were dissolved in 100 mL of THF and cooled to 0 ° C.
  • cinnamoyl chloride Tokyo Chemical Industry Co., Ltd., 13.1 g, 0.07 mol
  • reaction solution was poured into 500 g of water, extracted with ethyl acetate, and concentrated. Subsequently, fractionation was performed by silica gel column chromatography to obtain 22 g of monomer a-3 having a chalcone group as a photo-alignment group.
  • Synthesized monomer a-1 (11.1 g, 45 mol%), hexafluoroisopropyl methacrylate (hereinafter abbreviated as “HFIP”) (manufactured by Tokyo Chemical Industry Co., Ltd., 3.5 g, 15 mol%), methacrylic acid (hereinafter referred to as “HFIP”) (Hereinafter abbreviated as “MAA”) (manufactured by Wako Pure Chemical Industries, Ltd., 1.7 g, 20 mol%), glycidyl methacrylate (hereinafter abbreviated as “GMA”) (manufactured by Wako Pure Chemical Industries, Ltd.), 2.
  • HFIP hexafluoroisopropyl methacrylate
  • MAA methacrylic acid
  • GMA glycidyl methacrylate
  • HFIP Hexafluoroisopropyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • 6FM trifluoroethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
  • KBM-503 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • C18MA Octadecane methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • MAA Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
  • MMA Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
  • St Styrene (Wako Pure Chemical Industries, Ltd.)
  • AA Acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
  • GMA Gly
  • reaction product solution was dropped into a large amount of water to coagulate the reaction product.
  • This coagulated product was washed with water, redissolved in THF (200 g), and coagulated again with a large amount of water.
  • This re-dissolution and coagulation operation was performed three times in total, and then the obtained coagulated product was dried under reduced pressure at 60 ° C. for 48 hours to obtain a polymer A-5.
  • a polymer A-5 solution was prepared using diethylene glycol so that the solid content concentration was 25% by mass.
  • Polymer A-6 was synthesized in the same manner as the non-oriented polymer (E-1) described in paragraph [0165] (Preparation Example 5) of JP2013-177561A.
  • Crosslinking agent B As the crosslinking agent B, those shown below were used.
  • a polyfunctional epoxy compound (Ogsol EG, manufactured by Osaka Gas Co., Ltd.) was used as the crosslinking agent B-1 having a molecular weight of 5,000 or less.
  • a polyfunctional epoxy compound (EX-321L, manufactured by Nagase ChemteX Corporation) was used as the crosslinking agent B-2 having a molecular weight of 5,000 or less.
  • ⁇ F-554> As the surfactant, a perfluoroalkyl group-containing nonionic surfactant (F-554, manufactured by DIC Corporation) was used.
  • F-554 a perfluoroalkyl group-containing nonionic surfactant
  • KBM-403> As the adhesion improving agent, ⁇ -glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was used.
  • Examples 1 to 24 and Comparative Examples 1 to 6 Each component shown in Table 2 below is dissolved and mixed in a solvent (PGMEA) until the solid content is 18% by mass, filtered through a polytetrafluoroethylene filter having a diameter of 0.2 ⁇ m, and each example and comparative example. A resin composition was prepared. In addition, the addition amount in a table
  • surface represents the addition amount in solid content of each component, and a unit is a mass part.
  • the obtained resin composition was applied onto a glass substrate by a spin coat method, pre-dried on a hot plate at 80 ° C. for 1 minute, and then baked in a clean oven at 230 ° C. for 60 minutes to give a 3 ⁇ m overcoat.
  • a cured film of layers was formed.
  • the formed cured film was subjected to oblique cutting with a surface / interface cutting device (DN-20S type, manufactured by Daipura Wintes) to expose the cross section.
  • the intensity ELq and the intensity ESsub of the mass analysis of the fragment derived from the orientation group were measured using the measurement apparatus and conditions described above, and the intensity ratio (intensity ELq / intensity ESub) was measured.
  • the evaluation was based on the following criteria. The results are shown in Table 2 below.
  • C The intensity ratio is 5 times to less than 8 times.
  • F No fragment peak
  • the formed protective layer was irradiated with 750 mJ / cm 2 of polarized light using an ultraviolet polarized light exposure apparatus (HC-2150PUFM, manufactured by Run Technical Service Co., Ltd.) to form an alignment protective layer. . Thereafter, a horizontally aligned liquid crystal was applied, and the alignment state was observed with a polarizing microscope at a magnification of 20 times. The place was changed, and it observed in five visual fields (about 1 square micrometer), and evaluated with the following references
  • ⁇ Flatness> Create an L / S pattern with a height of 1 ⁇ m and a width of 10 ⁇ m (L / S width ratio is 1: 1), apply the resin composition on it with a spin coater, pre-bake at 90 ° C./120 seconds, And cured at 230 ° C./30 minutes to obtain a cured film of 2 ⁇ m.
  • the flatness of the obtained cured film was defined by the following formula and calculated. The results are shown in Table 3 below. As the flatness, the closer the value is to 100, the higher the flattening ability, and 70% or more is required for practical use.
  • a transparent conductive layer made of ITO was formed on the interlayer insulating film using a sputtering method.
  • the transparent conductive layer was etched using a photolithography method, and a comb-like pixel electrode was formed on the inorganic insulating film.
  • the array substrate of this example was manufactured.
  • a contact hole of a desired size is formed at a desired position of the insulating film, and electrical connection between the pixel electrode and the source-drain electrode of the active element is realized. It was.
  • the surface of the coating film polarized ultraviolet rays 200 J / m 2, including a bright line of 313nm using a Hg-Xe lamp and Gran Taylor prism, irradiated from 40 ° inclined direction with respect to the direction perpendicular to the substrate surface, An array substrate having a liquid crystal alignment film was manufactured.
  • a color filter substrate produced by a known method was prepared.
  • fine coloring patterns of three colors of red, green, and blue and a black matrix are arranged in a lattice pattern on a transparent substrate.
  • a coating film was formed on the color pattern of the color filter substrate and the black matrix using the resin compositions of Examples 1 to 24 and Comparative Examples 1 to 6 shown in Table 2 above, and the coating was formed at 90 ° C./120 After pre-baking for 2 seconds, it was thermally cured in an oven at 230 ° C./30 minutes to produce a protective film.
  • the protective film was subjected to a photo-alignment treatment by irradiating polarized light with 750 mJ / cm 2 using an ultraviolet polarized light exposure apparatus (HC-2150PUFM, manufactured by Run Technical Service Co., Ltd.), and a 2 ⁇ m alignment protective film.
  • the counter substrate was manufactured.
  • liquid crystal layer was sandwiched between the obtained counter substrate with an alignment protective film and the array substrate to manufacture a color liquid crystal display element.
  • the liquid crystal layer a layer made of nematic liquid crystal and aligned parallel to the substrate surface was used. The display characteristics and reliability of these liquid crystal display elements were evaluated.
  • the formed alignment protective layer has a covalent bond.
  • an intensity ratio (strength ELq / strength ESub) of mass analysis intensity ELq and intensity ESub of the fragment derived from the orientation group satisfies a predetermined condition.

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WO2019220970A1 (ja) * 2018-05-18 2019-11-21 富士フイルム株式会社 光配向性共重合体、光配向膜および光学積層体

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JP7135328B2 (ja) * 2018-01-31 2022-09-13 Jsr株式会社 液晶配向剤、液晶配向膜及び液晶素子
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