TW201728977A - Liquid crystal display device and method for manufacturing liquid crystal display device - Google Patents

Abstract

The present invention addresses the problem of providing a liquid crystal display apparatus that maintains high flatness even when a color filer is provided on a visual recognition side, and exhibits high display performance even under a high temperature and a high humidity, and a manufacturing method therefor. A liquid crystal display apparatus according to the present invention has a first substrate, a liquid crystal layer, and a second substrate in this order from the visual recognition side, wherein: the first substrate is provided with a base material and an oriented protective layer; the second substrate is provided with a base material, a thin-film transistor, a display electrode, and an oriented film; the oriented protective layer has a surface which comes into contact with the liquid crystal layer; the oriented protective layer has an orientation group and a crosslink structure mutually connected through covalent bonding; regarding fragments derived from the orientation group and detected by time-of-flight secondary ion mass spectrometry, the strength ELq of a fragment on the surface of the oriented protective layer that is in contact with the liquid crystal layer and the strength ESub of a fragment on a surface of the oriented protective layer on the base material side satisfy a prescribed relationship; and the crosslink structure is represented by a prescribed structural formula.

Description

Liquid crystal display device and method of manufacturing liquid crystal display device

The present invention relates to a liquid crystal display device and a method of fabricating the liquid crystal display device.

A liquid crystal display (LCD) is widely used for monitors such as personal computers or smart phones because of its low voltage, low power consumption, and miniaturization and thinning. (monitor), TV use. The liquid crystal display device includes a liquid crystal cell and two polarizing plates disposed on both sides of the liquid crystal cell, and the liquid crystal cell has a liquid crystal layer and two substrates sandwiching the liquid crystal layer and facing each other, and the two substrates are An alignment film which is useful for aligning liquid crystals constituting the liquid crystal layer is usually provided.

As a material for forming such an alignment film, for example, Patent Document 1 discloses "a photo-alignment polymer composition containing an anthracene group or a fluorine-substituted alkyl group as a first component and a photo-alignment group. And a non-photoalignable polymer obtained by polymerizing a monomer selected from at least one selected from the group consisting of methacrylic acid and methacrylic acid as a second component" ([Request Item 1], [Request Item 28]). [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2013-177561

[Problems to be Solved by the Invention] In the liquid crystal display device, a color filter is usually provided on the viewing side, and a viewpoint of preventing the transmission of impurities from the color filter or a color filter is known. From the viewpoint of flattening the step, a protective layer (overcoat layer) is provided in the color filter. Here, the inventors of the present invention have studied the case where the alignment film of the protective layer, that is, the alignment of the protective layer and the alignment film is not required when the color filter is provided on the viewing side. The protective layer. In addition, the inventors of the present invention have studied the alignment film described in Patent Document 1, and as a result, it has been found that there are problems in that depending on the alignment agent of the photo-alignment polymer composition, The flatness is poor, and in addition, when the liquid crystal display device is exposed to high temperature and high humidity, the display performance is poor. Therefore, an object of the present invention is to provide a liquid crystal display device which maintains excellent flatness even when a color filter is provided on the viewing side, and which exhibits excellent display performance when exposed to high temperature and high humidity. Production method. [Means for solving the problem]

In order to achieve the above-mentioned problems, the inventors of the present invention have conducted intensive studies and found that an alignment protective layer having an alignment group and a crosslinked structure which are linked to each other via a covalent bond is provided, and the alignment group is biased to exist. On the side of the surface in contact with the liquid crystal layer, excellent flatness is maintained even when a color filter is provided on the viewing side, and the display performance is also good when exposed to high temperature and high humidity, thereby completing The invention has been made. That is, it was found that the above problem can be achieved by the following configuration.

[1] A liquid crystal display device comprising a first substrate, a liquid crystal layer, and a second substrate in order from the viewing side, wherein the first substrate includes a substrate and an alignment protective layer, and the second substrate includes a substrate, a thin film transistor, and a display The electrode and the alignment film, the alignment protective layer has a surface in contact with the liquid crystal layer, and the alignment protection layer has an alignment group and a crosslinked structure which are connected to each other via a covalent bond, and is detected by time-of-flight secondary ion mass spectrometry a fragment derived from an alignment group, an intensity ELq of a mass spectrum of a segment derived from an alignment group in a surface of the alignment protective layer contacting the liquid crystal layer, and an orientation from the surface of the substrate on the side of the alignment protective layer The intensity ESub of the mass spectrum of the fragment of the base satisfies the following condition 1 or condition 2, and the crosslinked structure includes any one of the formulas (A-1) to (A-3) described later, and the condition 1: the intensity ELq is The strength ESub is 2 to 20 times. Condition 2: The intensity ELq was effectively measured, and the intensity ESub was below the measurement limit. [2] The liquid crystal display device according to [1], wherein the intensity ELq is 5 to 20 times the intensity ESub. [3] The liquid crystal display device according to [1], wherein the aligning group is a group obtained by reacting a photoalignment group. [4] The liquid crystal display device according to any one of [1] to [3] wherein the thickness of the alignment protective layer is from 1 μm to 4 μm. [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 horizontal alignment liquid crystal. [6] The liquid crystal display device according to any one of [1] to [5] wherein the fragment derived from the alignment group is derived from a group selected from the group consisting of a cinnamate group and a chalcone group. At least one fragment of a photo-alignment group.

[7] A method of producing a liquid crystal display device, comprising: in the first step, forming a protective layer on a substrate using a composition for forming an alignment protective layer containing a polymer P and a polymer A, and then performing an alignment treatment on the protective layer And forming an alignment protective layer to form a first substrate, wherein the polymer P includes a constituent unit having an alignment group, the polymer A does not contain a constituent unit having an alignment group; and the second step includes a substrate, The second substrate of the thin film transistor, the display electrode, and the alignment film is adhered to the first substrate to seal the liquid crystal, and a liquid crystal layer is formed between the first substrate and the second substrate to fabricate a liquid crystal display device. [8] The method for producing a liquid crystal display device according to the above [7], wherein the polymer P contains a constituent unit represented by the following s1 as a constituent unit having an alignment group, and the polymer P and the polymer A satisfy the following conditions. 3 or condition 4, s1: a constituent unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a decane skeleton, and an alkyl group having 10 to 30 carbon atoms, and a composition having a photo-alignment group Unit Condition 3: The polymer P contains the constituent unit a2 having a crosslinkable group, and the polymer A contains the constituent unit a3 having an acid group. Condition 4: The polymer P contains the constituent unit a3 having an acid group, and the polymer A contains the constituent unit a2 having a crosslinkable group. [9] The method for producing a liquid display device according to [8], wherein the crosslinkable group is selected from the group consisting of oxiranyl, 3,4-epoxycyclohexyl, and oxetanyl ( At least one of the group consisting of oxetanyl). [10] The method for producing a liquid crystal display device according to any one of [7], wherein a mass ratio of the polymer P to a total mass of the polymer P and the polymer A is less than 10% by mass. [11] The method for producing a liquid crystal display device according to any one of the aspects of the present invention, wherein the composition for forming an alignment protective layer further contains a crosslinking agent B having a molecular weight of 5,000 or less. [12] The method for producing a liquid crystal display device according to [11], wherein the crosslinking agent B comprises a crosslinking agent having an epoxy group, and the crosslinking agent B is relative to the crosslinking agent B, the polymer P, and the polymer A. The mass ratio of the total mass is 30% by mass or less. [13] The method for producing a liquid crystal display device according to any one of [7] to [12] wherein the alignment group is a photo-alignment group, and the alignment treatment is a photo-alignment treatment using light having a wavelength of 365 nm or less. [14] The method of manufacturing a liquid crystal display device according to any one of [7] to [13] wherein the first step includes a step of performing heat treatment before or after the alignment treatment. [Effects of the Invention]

According to the present invention, it is possible to provide a liquid crystal display device which maintains excellent flatness even when a color filter is provided on the viewing side, and which exhibits good display performance when exposed to high temperature and high humidity, and a method of manufacturing the same .

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be performed according to a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the present specification, the numerical range expressed by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit. In the expression of the group (atomic group) in the present specification, the substituted and unsubstituted expressions are not described as including a group having no substituent (atomic group), and also a group having a substituent (atomic group). For example, 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). In the present specification, "(meth)acrylate" means "acrylic acid ester" or "methacrylic acid ester", and "(meth)acrylic acid" means "acrylic acid" or "methacrylic acid". The "(meth)acryloyl group" is an expression indicating "acryloyl group" or "methacryl fluorenyl group".

[Liquid Crystal Display Device] 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 order from the viewing side, and the first substrate includes a substrate and an alignment protective layer, and the second substrate includes Substrate, thin film transistor, display electrode and alignment film. Further, in the liquid crystal display device of the present invention, the alignment protective layer has a surface in contact with the liquid crystal layer, and has an alignment group and any one of the formulas (A-1) to (A-3) to be described later. The crosslinked structure of the structure further has a structure in which an alignment group and a crosslinked structure are linked to each other via a covalent bond. Further, in the liquid crystal display device of the present invention, the alignment-derived group-derived fragment detected by Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) is used for the alignment protection. The intensity ELq of the mass spectrum of the fragment derived from the alignment group in the surface of the layer in contact with the liquid crystal layer, and the intensity ESub of the mass spectrum of the fragment derived from the alignment group in the surface on the substrate side of the alignment protective layer satisfy the following condition 1 Or condition 2. Condition 1: The intensity ELq is 2 to 20 times the intensity ESub. Condition 2: The intensity ELq was effectively measured, and the intensity ESub was below the measurement limit.

<Measurement Conditions of TOF-SIMS> The measurement by TOF-SIMS in the present invention was carried out as follows. (1) 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 (referred to as a surface in contact with the liquid crystal layer, the same applies hereinafter) and the back surface of the alignment protective layer (referred to as When the substrate or the surface on which the adjacent layer on the substrate side is in contact with the surface is exposed, the excimer-derived fragment in the surface of the alignment protective layer is formed under the apparatus and conditions shown in the following (3). The intensity ELq of the mass spectrum and the intensity ESub of the mass spectrum of the fragment derived from the alignment group in the back surface of the alignment protective layer were measured. (2) When the surface and the back surface of the alignment protective layer cannot be exposed, the Say and Kass method (Surface and Interfacial Cutting Analysis System) is used for the laminate having the alignment protective layer and the adjacent layer. : SAICAS), the cutting surface is cut in the oblique direction so as to reach the surface and the back surface of the alignment protective layer, and the cross section of the alignment protective layer is exposed. The exposed cross section is obtained by measuring the region from the surface of the protective layer to a depth of 10 nm in the depth (thickness) direction under the apparatus and conditions shown in the following (3). The intensity of the mass spectrum of the fragment is set to the intensity ELq, and is obtained by measuring a region of 2000 nm in the depth (thickness) direction from the back surface of the protective layer under the apparatus and conditions shown in the following (3). The intensity of the mass spectrum of the fragment of the alignment group is set to the intensity ESub. (3) Measurement was carried out under the following apparatus and conditions. ·Device: TOF-SIMS IV (manufactured by ION-TOF) · Primary ion: Bi ³⁺ (beam diameter 2 μm) · Measurement range: raster scan of each pair of 256 points in one direction and its orthogonal direction (raster scan · Polarity: positive (posi), negative (nega)

In the liquid crystal display device of the present invention, by providing the alignment protective layer, excellent flatness is maintained when a color filter is provided on the viewing side, and display performance is also changed when exposed to high temperature and high humidity. Good. Although the details are not clear, the inventors of the present invention presume as follows. In other words, the alignment protective layer has an alignment group and a crosslinked structure including any one of the structures represented by the following formulas (A-1) to (A-3), and has an alignment group and a crosslinked structure via covalent The structure in which the bonds are connected to each other, and the intensity ELq and the intensity ESub measured by TOF-SIMS satisfy the condition 1 or the condition 2, whereby the alignment group is considered to exist on the surface of the alignment protective layer, and the alignment The group is strongly bonded to the polymer constituting the alignment protective layer. Therefore, it is considered that when a color filter is provided on the back side of the alignment protective layer, the alignment group also does not lose flatness, and the alignment group can also maintain the liquid crystal layer when exposed to high temperature and high humidity. Orientation, so the display performance becomes good.

In the present invention, the reason why the display performance is also better when exposed to high temperature and high humidity is preferably that the intensity ELq measured by TOF-SIMS is 5 times to 20 times the intensity ESub. Times.

Next, the outline of the configuration of the liquid crystal display device of the present invention will be described in detail with reference to Fig. 1, and the first substrate, the liquid crystal layer, and the second substrate included in the liquid crystal display device of the present invention will be described in detail.

1 is a schematic cross-sectional view showing an example of an embodiment of a liquid crystal display device of the present invention. The liquid crystal display device 10 shown in FIG. 1 has the first substrate 30, the liquid crystal layer 20, and the second substrate 40 in this order from the viewing side. Further, the first substrate 30 is provided with a base material 15 to which a polarizing film is attached, an RGB color filter 22 in which a black matrix is disposed, and an alignment protective layer 21 having a surface in contact with the liquid crystal layer 20. Further, the second substrate 40 is provided with elements of the substrate 14 to which the polarizing film is attached and the thin film transistor 16. In each of the elements formed on the substrate 14, an Indium Tin Oxide (ITO) transparent electrode 19 on which a display electrode is formed is formed by a contact hole 18 formed in the cured film 17, on the ITO transparent electrode 19. An alignment film 23 is provided. Further, 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, a white light emitting diode (LED), a multicolor LED such as blue, red, or green, a fluorescent lamp (cold cathode tube), and an organic electroluminescence (electroluminescence) may be mentioned. Further, the liquid crystal display device may be a three-dimensional (3D) (stereoscopic) type device or a touch panel type device. Further, it can be used as a flexible type, and can be used as the second interphase insulating film (48) of JP-A-2011-145686 or the interphase insulating film (520) of JP-A-2009-258758.

[First Substrate] The first substrate included in the liquid crystal display device of the present invention is a substrate provided on the side of the viewing side of the liquid crystal layer to be described later, and includes a substrate and an alignment protective layer. Further, since the alignment protective layer has a surface in contact with a liquid crystal layer to be described later, the first substrate is provided with a substrate and an alignment protective layer in this order from the viewing side. Further, when the liquid crystal display device of the present invention is provided with an arbitrary color filter on the viewing side, the first substrate is provided with a substrate, a color filter, and an alignment protective layer in this order.

<Substrate> As the substrate, a transparent substrate used in a liquid crystal cell of a conventionally known liquid crystal display device can be used, and for example, a glass substrate, a quartz substrate, a transparent resin substrate, or the like can be used. Among them, a glass substrate is preferably used.

<Alignment Protective Layer> As described above, the alignment protective layer has a surface in contact with a liquid crystal layer to be described later, and has an alignment group and includes a formula (A-1) to (A-3) which will be described later. Further, the crosslinked structure of any one of the structures has a structure in which an alignment group and a crosslinked structure are linked to each other via a covalent bond.

(Orientation group) The alignment group of the alignment layer is not particularly limited as long as it is a group having a function of aligning a liquid crystal compound, and in the present invention, it is an alignment layer. The reason why the surface state is prevented from coming into contact with the surface at the time of formation without being in contact with the surface is preferably a group obtained by reacting a photo-alignment-based light.

Here, the photo-alignment group refers to a photoreactive group which imparts an alignment property by any of a photodimerization reaction, a photoisomerization reaction, and a photodecomposition reaction. In addition, examples of the group imparting an alignment property by photodimerization reaction include, for example, at least one selected from the group consisting of a maleimide derivative, a cinnamic acid derivative, and a coumarin derivative. Specific examples of the group to be introduced into the substance include a cinnamate group and a chalcone group. In addition, as the cinnamate group and the chalcone group, for example, the following structure can be introduced (in the following formula, * represents a linking site to a polymer chain, and R represents a hydrogen atom or a monovalent organic group), and The linking site to the polymer chain indicated by * can be directly bonded to the main chain of the polymer or bonded via a divalent linking group. The monovalent organic group represented by R is preferably an alkyl group or an aryl group. Further, the number of carbon atoms of the monovalent organic group represented by R is preferably from 1 to 10, more preferably from 1 to 7.

On the other hand, as a reactive group which is isomerized by the action of light, specifically, for example, a group selected from the group consisting of an azobenzene compound, a stilbene compound, and a spiropyran compound can be suitably used. a group of the skeleton of at least one of the compounds, and the like. In addition, as the reactive group which is decomposed by the action of light, specifically, for example, a group containing a skeleton of a cyclobutane compound or the like can be suitably mentioned.

Among these, in view of the irreversibility of the reaction, it is preferred to impart an aligning group by photodimerization reaction of a shorter-wave reaction, and more preferably from a cinnamate group and a chalcone. At least one of the groups consisting of.

(Crosslinked structure) The crosslinked structure of the alignment protective layer is a crosslinked structure including any one of the following formulas (A-1) to (A-3).

In the formulae (A-1) to (A-3), * represents a bonding position, and in the formula (A-3), R ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. . The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group or a hexyl group.

Here, examples of the crosslinked structure including the structure represented by the above formula (A-1) to formula (A-3) include a crosslinkable group (for example, an epoxy group, an oxetanyl group, etc.) Specific examples of the crosslinked structure formed by the reaction with an acid group (for example, a carboxyl group) include the following formula (A-1-1), formula (A-2-1), and formula (A-3-1). Indicates the crosslinked structure. In the following formula (A-1-1), formula (A-2-1), and formula (A-3-1), * represents a bonding position, and is represented by the following formula (A-3-1). R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

As described above, the alignment protective layer has a structure in which the alignment group and the crosslinked structure are linked to each other via a covalent bond. Therefore, in the present invention, a polymer having a structural unit having a crosslinkable group (for example, an epoxy group or an oxetanyl group) to be described later, and/or an acid group (for example, a carboxyl group) to be described later is preferable. The polymer of the constituent unit of the above) further comprises a constituent unit having the above-mentioned alignment group.

In the present invention, the film thickness of the alignment protective layer is preferably from 1 μm to 4 μm, more preferably from 2 μm to 3 μm.

<Color Filter> The first substrate of the liquid crystal display device of the present invention may include a color filter between the substrate and the alignment protective layer. The color filter is not particularly limited, and for example, a color filter which is generally used as a liquid crystal display device can be used. Such a color filter generally includes transparent coloring patterns of respective colors of red, green, and blue, and each of the transparent coloring patterns includes a resin composition in which a coloring agent is dissolved or dispersed, preferably, pigment fine particles are dispersed. Furthermore, the formation of the color filter can be performed by preparing an ink composition colored to a predetermined color and printing each colored pattern, more preferably using a paint type containing a coloring agent of a predetermined color. The resin composition is carried out by photolithography.

[Liquid Crystal Layer] 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 and a second substrate to be described later. Further, as described above, the liquid crystal layer is provided in contact with the alignment protective layer provided on the first substrate.

Examples of the driving method for driving the liquid crystal layer which can be used in the liquid crystal display device of the present invention include a twisted nematic (TN) method, a vertical alignment (VA) method, and a coplanar switching (In-Plane). -Switching, IPS), Fringe Field Switching (FFS), and Optically Compensated Bend (OCB).

Among these driving methods, the IPS method is preferred. In the liquid crystal cell of the IPS method, the rod-like liquid crystal molecules are aligned substantially in parallel with respect to the substrate, and the liquid crystal molecules respond in a plane by applying a parallel electric field to the substrate surface. That is, in the IPS method, the liquid crystal constituting the liquid crystal layer is a horizontal alignment liquid crystal. The IPS method is black in a state where no electric field is applied, and the absorption axes of the upper and lower polarizing plates are orthogonal.

[Second Substrate] 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 from the first substrate, and includes a substrate, a thin film transistor, a display device, and Orientation film.

<Substrate> As the substrate provided in the second substrate, a transparent substrate used in a liquid crystal cell of a conventionally known liquid crystal display device can be used similarly to the first substrate, and for example, a glass substrate, a quartz substrate, or a transparent substrate can be used. Resin substrate, etc. Among them, a glass substrate is preferably used.

<Thin Film Transistor> A thin film transistor (TFT) provided as the second substrate can be suitably used in a known liquid crystal display device, and the configuration thereof is not particularly limited, and may be a top gate type. Can be the bottom gate type. Specific examples of the thin film transistor include an amorphous germanium-TFT, a low-temperature polycrystalline germanium-TFT, an oxide semiconductor TFT, and the like.

<Display electrode> As the display electrode provided in the second substrate, a user of a known liquid crystal display device can be suitably used. As a constituent material, for example, indium tin oxide (ITO) or zinc aluminum oxide can be used. Transparent conductive material such as aluminum oxide (Aluminum doped Zinc Oxide: AZO) or indium zinc oxide (Indium Zinc Oxide: IZO).

<Alignment film> As the alignment film provided in the second substrate, a user of a known liquid crystal display device containing a polymer as a main component can be suitably used. As a polymer material for an alignment film, it is described in many documents, and many commercially available products are available. The polymer material utilized in the present invention is preferably polyvinyl alcohol or polyamine, and derivatives thereof. Particularly preferred are modified or unmodified polyvinyl alcohols. The alignment film which can be used in the present invention is, for example, an alignment film described in International Publication No. 01/88574, page 24, line 24 to page 49, line 8; paragraph [0071] to paragraph of Japanese Patent No. 3907735 [0095] The modified polyvinyl alcohol described in JP-A-2012-155308, which is a liquid crystal alignment film formed by a liquid crystal alignment agent.

For other configurations of the liquid crystal display device (for example, a polarizing plate, a backlight, etc.), the descriptions of Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei.

[Manufacturing Method of Liquid Crystal Display Device] The method for producing a liquid crystal display device of the present invention includes the first step of forming a protective layer on a substrate using a composition for forming an alignment protective layer containing the polymer P and the polymer A, and then protecting the liquid crystal display device. The layer is subjected to an alignment treatment to form an alignment protective layer to form a first substrate, and the polymer P includes a constituent unit having an alignment group, and the polymer A does not contain a constituent unit having an alignment group. Further, the method for manufacturing a liquid crystal display device of the present invention includes a second step of adhering a second substrate including a substrate, a thin film transistor, a display electrode, and an alignment film to a first substrate, and sealing the liquid crystal on the first substrate and the second substrate. A liquid crystal layer was formed between the substrates to fabricate a liquid crystal display device.

[First Step] In the first step, a protective layer is formed on the substrate by using the composition for forming an alignment protective layer containing the polymer P and the polymer A, and then the protective layer is subjected to an alignment treatment to form an alignment protective layer to prepare the first layer. In the step of a substrate, the polymer P contains a constituent unit having an alignment group, and the polymer A does not contain a constituent unit having an alignment group. In addition, the base material in the first step is the same as the base material provided in the first substrate of the liquid crystal display device of the present invention.

<Orientation of formation of an alignment protective layer> The composition for forming an alignment protective layer is preferably a reason why the phase difference of the alignment protective layer is lowered, the transparency is improved, and the crosslinked structure is easily formed in the alignment protective layer. The polymer P includes a constituent unit represented by the following s1 as a constituent unit having the alignment group, and the polymer P and the polymer A satisfy the following condition 3 or condition 4. S1: a constituent unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a decane skeleton, and an alkyl group having 10 to 30 carbon atoms, and a constituent unit having a photo-alignment group. Condition 3: Polymerization The substance P contains the constituent unit a2 having a crosslinkable group, and the polymer A contains the constituent unit a3 having an acid group. Condition 4: The polymer P contains the constituent unit a3 having an acid group, and the polymer A contains the constituent unit a2 having a crosslinkable group.

In the present invention, in the reason that the crosslinked structure is more easily formed in the alignment protective layer, it is preferred that the polymer P and/or the polymer A have a crosslinkable group selected from oxygen. At least one of the group consisting of a heterocyclic group, a 3,4-epoxycyclohexyl group, and an oxetanyl group.

Specific examples of the polymer P and the polymer A contained in the composition for forming an alignment protective layer, and arbitrary additives and the like will be described in detail below.

(Polymer P) As the polymer P, as described above, a polymer comprising a constituent unit represented by the following s1 (hereinafter also referred to as "constitutive unit s1") is preferably used. S1: a constituent unit having at least one partial structure (hereinafter also referred to as "biased existence group") selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane chain, and an alkyl group having 10 to 30 carbon atoms, and Constituent unit having a photo-alignment group

<<Structural unit having a fluorine-substituted hydrocarbon group partial structure>> The fluorine-substituted hydrocarbon group may be an alkyl group or an alkyl group as long as it is a hydrocarbon group substituted with at least one fluorine atom (hereinafter, simply referred to as "alkyl group" in this paragraph. In the above, at least one hydrogen atom is substituted with an alkyl group having a fluorine atom, and the like, and more preferably an alkyl group in which all hydrogen atoms such as an alkyl group are substituted with a fluorine atom.

The fluorine-substituted hydrocarbon group is preferably a group represented by the following formula (I) from the viewpoint of bias.

In the formula (I), R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a linking site 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, and r represents an integer of 0 or 1-2. Further, when m is 1, the plurality of R ^{2 's} may be the same or different.

m in the formula (I) represents an integer of 1 to 3, preferably 1 or 2. n in the formula (I) represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 4, particularly preferably 1 or 2. r in the formula I represents 0 or an integer of 1 to 2, preferably 1 or 2, more preferably 2. In addition, the linking site to the polymer chain represented by * may be directly bonded to the main chain of the polymer such as the polymer A1-1, or may be through a polyoxyalkylene group, an alkyl group, an ester group or an amine group. The formate group may also be bonded by a divalent linking group such as a cyclic alkyl group of a hetero atom, a poly(caprolactone) or an amine group. It is preferred to bond via a polyoxyalkylene group.

In the above formula (I), examples of the alkyl group having 1 to 4 carbon atoms represented by R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. The third butyl group or the like is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom. In the formula (I), the case where X is a single bond means that the polymer main chain is directly bonded to a carbon atom to which R ² is bonded. In the case where X is a divalent linking group, examples of the linking group include -O-, -S-, -N(R ⁴ )-, -CO-, and the like. More preferably, these are -O-. Here, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a tert-butyl group, and is preferably a hydrogen atom or a methyl group.

The method of introducing a fluorine-substituted hydrocarbon group into a polymer includes a method of introducing a fluorine-substituted hydrocarbon group into a polymer by a polymer reaction, and a monomer having a fluorine-substituted hydrocarbon group (hereinafter referred to as a "single containing a fluorine-substituted hydrocarbon group". The method of copolymerizing and introducing a constituent unit having a fluorine-substituted hydrocarbon group into a polymer.

The monomer containing a fluorine-substituted hydrocarbon group in the method of introducing a fluorine-substituted hydrocarbon group-containing monomer into a polymer and introducing a monomer having a fluorine-substituted hydrocarbon group, the monomer represented by the following formula (II) As a better.

In the formula (II), 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. Further, R ^2, X, m, n and r have the general formula I is R ^2, X, m, n and r have the same meaning as the preferred embodiments are also the same. In the above formula (II), examples of the halogen atom represented by R ¹ include a fluorine atom, a chlorine atom, and a bromine atom.

In addition, the production method of such a monomer containing a fluorine-substituted hydrocarbon group is, for example, "Synthesis and function of a fluorine compound" (editor: Ishikawa Yoshio, issue: CMC Corporation, 1987), pages 117 to 118, or "Chemistry of Organic Fluorine Compounds II" (Monograph 187, Milos Hudlicky and Attila E. Pavlath, USA It is described on pages 747 to 752 of the American Chemical Society 1995.

In addition, specific examples of the monomer represented by the formula (II) include tetrafluoroisopropyl methacrylate represented by the following formula (IIa) and methacrylic acid represented by the following formula (IIb). Hexafluoroisopropyl ester and the like. Further, as another specific example, a compound described in Paragraph No. [0058] to Paragraph No. [0061] of JP-A-2010-18728 can be cited. Among these, a structure in which a fluorine-substituted hydrocarbon group is bonded to a polyoxyalkylene group is preferred.

<<Structural unit having a partial structure of a siloxane skeleton>> The siloxane skeleton is not particularly limited as long as it has "-Si-O-Si-", and preferably contains a polyoxyalkylene group.

In the present invention, as for the oxoxane skeleton, it is preferred to copolymerize a compound having a (meth) propylene fluorenyl group and an alkoxy fluorenyl group from the viewpoint of the existence of the oxoxane skeleton, and to introduce it into the polymer. A constituent unit having a partial structure of a siloxane skeleton. Here, as the alkoxyalkyl group, for example, a group represented by the following formula (X) is preferable.

In the formula (X), 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 of them is an alkoxy group. * indicates the bonding position.

In the formula (X), 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, more preferably an alkyl group having 1 to 8 carbon atoms. The oxy group is more preferably an alkoxy group having 1 to 4 carbon atoms, particularly preferably an ethoxy group or a methoxy group. In the present invention, it is preferred that two of R ³ to R ⁵ are alkoxy groups and one is an alkyl group or three are alkoxy groups. Among them, more preferred are three alkoxy groups, that is, a trialkoxyalkylene group.

Specific examples of such a compound having an alkoxyalkyl group and a (meth) acryloxy group include 3-(meth)acryloxypropylmethyldimethoxydecane, and 3 -(Meth)acryloxypropyltrimethoxydecane, 3-(meth)acryloxypropylmethyldiethoxydecane, 3-(meth)acryloxypropyltriethyl Oxydecane, etc.

In the present invention, the compound represented by the following structural formula (A) (hereinafter also referred to as "specific alkoxylate compound") is preferred from the viewpoint of the presence of the oxoxane skeleton. Polymerization, while introducing a oxoxane skeleton to the polymer.

In the structural formula (A), R ⁷ represents a linear or branched alkyl 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) A divalent linking group represented.

In the structural formula (B), 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. Here, R ⁴ may be two or more in the structural formula (B), and may be different from each other or may be the same.

In the structural formula (A), x1, x2, and x3 are integers satisfying the total of 1 to 100. Further, y1 is an integer of 1 to 30. In the structural formula (A), X ² is a single bond or a divalent group represented by the following structural formula (C).

In the structural formula (C), R ⁸ represents a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent such as a hydroxyl group, an amine group or a halogen atom, and Q ¹ and Q ² represent an oxygen atom. The sulfur atom or -NRB-, Q ¹ and Q ² may be different, respectively, and may be the same. RB represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In the structural formula (C), Q ^{2 is} bonded to R ⁷ in the structural formula (A).

In the structural formula (A), Y ² represents a monovalent group represented by the following structural formula (D) to the following structural formula (F).

In the structural formula (D) to the structural formula (F), R ⁵ represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms.

In the structural formula (A), Z ¹ , Z ² and Z ³ each independently represent a monovalent group represented by the following structural formula (G).

In the structural formula (G), R ⁶ represents an unsubstituted alkyl group having 1 to 4 carbon atoms, and y ² represents an integer of 1 to 100, preferably an integer of 1 to 50, more preferably 1 to 20 Integer.

In addition, the structure described in Paragraph No. [0092] to Paragraph No. [0094] of JP-A-2010-18728 is a specific example of the above formula (A), but is not limited. For that. Among these, a structure in which a oxoxane structure is bonded to a polymer via a polyoxyalkylene group is preferred.

<<Structural unit having an alkyl moiety structure having a carbon number of 10 to 30>> The alkyl group having 10 to 30 carbon atoms may further comprise a branched structure or a cyclic structure, and preferably has a carbon number of 10 to 30 in the linear structural portion. The range is better for all linear structures. Further, the alkyl group preferably has 10 to 20 carbon atoms.

Specifically, it is preferred that the side chain of the polymer has a group represented by the following formula (a3-1).

In the above formula (a3-1), n _a3 represents an integer of 10 to 30, and * represents a position to be bonded to a main chain or a side chain of the polymer. n _{a3 is} preferably an integer of 10 to 20.

The method of introducing the structure of the above formula (a3-1) into the main chain or the side chain of the polymer is not particularly limited, and for example, as long as the monomer having the structure of (a3-1) is appropriately selected at the time of synthesis, Then, the structure of (a3-1) can be introduced into the repeating unit of the obtained polymer. Further, a commercially available compound can be used as the monomer having the structure of the above formula (a3-1), and a commercially available monomer having a structure of (a3-1) can be appropriately introduced (a3-1). Used in the required structure contained in it. The method of introducing the structure of (a3-1) into a commercially available monomer is not limited, and a known method can be suitably applied.

The monomer having the structure of the above formula (a3-1) can be appropriately selected depending on the main chain structure of the polymer, and for example, if it is a polymer having a (meth)acrylic structure in the main chain, it is preferably used. The monomer represented by the formula (a3-2).

In the above 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, and R ³³ represents a single bond or an alkoxy group. Further, n _a3 and the above formula (a3-1) also have the same meanings including the preferred ranges.

In the above formula (a3-2), R ³² is a hydrogen atom, a methyl group, an ethyl group or a halogen atom, more preferably a hydrogen atom or a methyl group, and further preferably a methyl group.

In the above formula (a3-2), examples of the divalent linking group of X ³¹ include -O-, -S-, -N(R ⁴ )- and the like. More preferably, these are -O-. Here, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group may have a linear structure or a branched structure, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a t-butyl group and the like, and preferably hydrogen. Atom, methyl.

Further, as the alkyleneoxy group of R ³³ , a carbon number of 1 to 4 is preferred. The alkoxy group may also have a branched structure. Further, it may have a substituent or may be unsubstituted. Examples of the substituent which may be possessed include a halogen atom and the like. Specific examples of the alkoxy group include a methyleneoxy group, an exoethoxy group, a propenyloxy group, a butylated oxy group and the like.

Among these, R ^{33 is} preferably an unsubstituted linear alkyleneoxy group having 1 to 4 carbon atoms or a single bond, more preferably a single bond.

By using the monomer represented by the above formula (a3-2), a polymer having a repeating unit represented by the following formula (U-a3-1) can be obtained. One of the preferred embodiments of such a polymer is a repeating unit represented by the formula (U-a3-1).

In the above formula (U-a3-1), n _a3 and the above formula (a3-1) also have the same meanings including the preferred ranges, and R ³² , X ³¹ , and R ^{33 are} as described above. The general formula (a3-2) also has the same meanings including the preferred ranges.

Specific examples of the monomer represented by the above formula (a3-2) are shown below. However, the present invention is not limited to these specific examples.

<<Constituent unit having a photo-alignment group>> The polymer P is at least one partial structure including the group selected from the group consisting of a fluorine-substituted hydrocarbon group, a decane skeleton, and an alkyl group having 10 to 30 carbon atoms A constituent unit and a polymer comprising a constituent unit having a photo-alignment group. Here, the photo-alignment group is the same as those described for the alignment group.

The polymer having a constituent unit having a photo-alignment group is not particularly limited, and the molecular structure of the side chain is various, and the main chain of the radical polymerization reaction of the ethylenically unsaturated compound is easily formed. In other words, a polymer having a repeating unit represented by the following formula (III) is preferred. Here, in the formula (III), R ¹ represents a hydrogen atom or an alkyl group. X represents an exoaryl 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, and P represents a photoalignment group.

In the formula (III), R ¹ represents a hydrogen atom or an alkyl group, and as the alkyl group, an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, n-propyl group, isopropyl group, or n-butyl group) is preferred. Base, etc.). R ^{1 is} preferably a hydrogen atom or a methyl group. Further, in the formula (III), L represents a single bond or a divalent linking group, and as a divalent linking group, preferably -O-, -S-, an alkylene group, an extended aryl group, or A combination of a plurality of groups. The alkylene group represented by L may be a linear, branched or cyclic structure, and is preferably a linear structure. The carbon number of the alkylene group represented by L is preferably from 1 to 10, more preferably from 1 to 6, more preferably from 2 to 4. Further, examples of the aryl group represented by L include a stretching phenyl group, a methylphenyl group, a xylyl group, and the like, and a phenyl group is preferred. In the formula (III), P represents a photo-alignment group, and specific examples thereof include a chalcone group, a cinnamate group, a distyryl group, a maleimine group, and an azobenzyl group. . Among them, a chalcone group and a cinnamate group are more preferable. Further, the photo-alignment group represented by P may have a substituent as long as it does not lose photo-alignment properties. Specific examples of the substituent include a halogen group, an alkyl group, and an aryl group, and an alkyl group or an aryl group is preferred. The alkyl group or aryl group preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms.

Preferred specific examples of the polymer having the repeating unit represented by the formula (III) are shown below, but the present invention is not limited to the specific examples.

The polymer having the repeating unit represented by the formula (I) can be synthesized by (a) a method of directly introducing a photoreactive group by polymerizing a corresponding monomer, or by using (b) a polymer reaction. The photoreactive group is synthesized by introducing a polymer obtained by polymerizing a monomer having an arbitrary functional group. Alternatively, the methods of (a) and (b) may be combined to carry out the synthesis. Here, examples of the polymerization reaction which can be used in the methods (a) and (b) include radical polymerization, cationic polymerization, anionic polymerization, and the like.

Further, the polymer having the repeating unit represented by the formula (I) may be a copolymer containing a plurality of repeating units represented by the above formula (I), or may be other than the formula (I). A copolymer of repeating units (e.g., repeating units that do not contain ethylenically unsaturated groups).

{Preferred aspect of the constituent unit s1} The constituent unit s1 is preferably 0.01 mol% to 10 mol%, more preferably 0.1 mol% to 10 mol%, based on the constituent units of all the polymer components. Further preferably, it is 0.1 mol% to 5 mol%, particularly preferably 0.1 mol% to 3 mol%, and most preferably 0.5 mol% to 3 mol%. Further, in the constituent unit s1, the content of the constituent unit having a biasing-existing group is preferably 0.01 mol% to 3 mol%, more preferably 0.1 mol% to 3 mol%, and still more preferably 0.5. Mole% to 3 mol%. Further, in the constituent unit s1, the content of the constituent unit having a photo-alignment group is preferably from 0.01 mol% to 5 mol%, more preferably from 0.1 mol% to 5 mol%, and still more preferably 1 Mole% to 3 mol%. In the polymer having the constituent unit s1, the content of the constituent unit s1 is preferably from 20 mol% to 90 mol%, more preferably from 20 mol% to 80, based on all constituent units of the polymer. Mohr%, and thus preferably 20% by mole to 70% by mole. In this case, the content of the constituent unit having a biasing-existing group is preferably from 1 mol% to 50 mol%, more preferably from 5 mol% to 30 mol%, and still more preferably from 10 mol% to 20 Moer%. Further, the content of the constituent unit having a photo-alignment group is preferably from 1 mol% to 70 mol%, more preferably from 10 mol% to 60 mol%, further preferably from 20 mol% to 50 mol%. . In the present invention, when the content of the "constituting unit" is defined by the molar ratio, the "constituting unit" has the same meaning as the "single unit". Further, in the present invention, the "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same is true below.

<<Other constituent unit>> The polymer P may include a constituent unit a1 having a group having an acid group protected by an acid-decomposable group, and a crosslinkable group, in addition to the constituent unit s1. The unit a2, the constituent unit a3 having an acid group, and the constituent unit a4 other than the above. In the above-mentioned constituent units, as described above, the reason why the crosslinked structure is easily formed in the alignment protective layer is preferably a constituent unit a2 having a crosslinkable group and/or a constituent unit having an acid group. A3.

<<<Structural unit a1>>> The constituent unit a1 is a constituent unit having a group in which an acid group is protected by an acid-decomposable group (hereinafter also referred to as a constituent unit a1). The "group protected by an acid-decomposable group" in the present invention means a group which causes an acid-based catalyst (or a starter) to cause a deprotection reaction, an acid group and a regenerated acid, and a decomposed structure. group. The "group protected by an acid-decomposable group" in the present invention can be used as an acid group or an acid-decomposable group, and is not particularly limited. The acid group is preferably, for example, a carboxyl group or a phenolic hydroxyl group. Further, examples of the acid-decomposable group include groups which are 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 a relatively difficult acid. The group to be decomposed (for example, a tertiary alkyl group such as a tertiary butyl ester group or a tertiary alkyl carbonate group such as a third butyl carbonate group).

The constituent unit a1 having a group having an acid group which is protected by an acid-decomposable group is preferably a constituent unit having a carboxyl group protected by an acid-decomposable group (hereinafter also referred to as "protective carboxyl group having an acid-decomposable group-protected group". The constituent unit ") or a constituent unit for protecting a phenolic hydroxyl group having a phenolic hydroxyl group protected by an acid-decomposable group (hereinafter also referred to as "a constituent unit having a protective phenolic hydroxyl group protected by an acid-decomposable group"). Hereinafter, the constituent unit a1-1 having a protective carboxyl group protected by an acid-decomposable group and the constituent unit a1-2 having a protective phenolic hydroxyl group protected by an acid-decomposable group will be described in order.

{Structural unit a1-1 having a protective carboxyl group protected by an acid-decomposable group} The constituent unit a1-1 having a protective carboxyl group protected by an acid-decomposable group is a carboxyl group containing a constituent unit having a carboxyl group, which will be described in detail below. The acid-decomposable group protects the constituent unit of the protected carboxyl group. As the constituent unit having a carboxyl group which can be used for the structural unit a1-1 having a protective carboxyl group protected by an acid-decomposable group, a known constituent unit can be used without particular limitation. For example, a constituent unit a1-1-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in a molecule such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid or an unsaturated tricarboxylic acid, or an ethylenic group may be mentioned. The constituent unit a1-1-2 of the saturated group and the structure derived from the acid anhydride. In the following, a1-1-1 used as a constituent unit having a carboxyl group is derived from a constituent unit of an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and a-1-1-2 is simultaneously ethylenic. The constituent units of the unsaturated group and the structure derived from the acid anhydride are separately described.

{{Constituent unit a1-1-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule}} as a constituent unit a1-1 regarding the unsaturated carboxylic acid or the like derived from at least one carboxyl group in the molecule The unsaturated carboxylic acid used in the present invention is, for example, a compound described in paragraph 0043 of JP-A-2014-238438. Among them, from the viewpoint of developability, in order to form the constituent unit a1-1-1, acrylic acid, methacrylic acid, 2-(meth)acrylomethoxyethyl-succinic acid, 2- (meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloxyethyl-phthalic acid, or an anhydride of an unsaturated polycarboxylic acid, etc., more preferably acrylic acid , methacrylic acid, 2-(meth)acryloxyethyl hexahydrophthalic acid. The constituent unit a1-1-1 derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule may be contained alone or in combination of two or more.

{{Constituent unit a1-1-2 having both an ethylenically unsaturated group and an acid anhydride-derived structure}} The constituent unit a1-1-2 having both an ethylenically unsaturated group and an acid anhydride-derived structure is preferably a source A unit of a monomer obtained by reacting a hydroxyl group present in a constituent unit having an ethylenically unsaturated group with an acid anhydride. As the acid anhydride, a known one may be used, and specific examples thereof include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chloro-anhydride. An acid anhydride such as trimellitic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, or biphenyltetracarboxylic anhydride. Among these acid anhydrides, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferred from the viewpoint of developability. The reaction rate of the acid anhydride to the hydroxyl group is preferably from 10 mol% to 100 mol%, more preferably from 30 mol% to 100 mol%, from the viewpoint of developability.

(Available as an acid-decomposable group constituting the unit a1-1) The acid-decomposable group which can be used for the constituent unit a1-1 having a protective carboxyl group protected by an acid-decomposable group can be used. base. Among these acid-decomposable groups, the carboxyl group is preferably an acetal from the viewpoint of the basic physical properties of the resin composition, particularly in terms of sensitivity, pattern shape, contact hole formation property, and storage stability of the resin composition. The form is protected by a protected carboxyl group. Further, in the acid-decomposable group, the carboxyl group is more preferably a protected carboxyl group which is protected in the form of an acetal represented by the following formula a1-10. In the case where the carboxyl group is a protected carboxyl group which is protected in the form of an acetal represented by the following formula (a1-10), the entire protected carboxyl group becomes -(C=O)-O-CR ¹⁰¹ R ¹⁰² ( OR ¹⁰³ ) structure.

In the formula (a1-10), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or a hydrocarbon group, except for the case where R ¹⁰¹ and R ^{102 are} simultaneously a hydrogen atom. R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be bonded to form a cyclic ether.

In the formula (a1-10), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, and the alkyl group may be any of a linear chain, a branched chain, and a cyclic group. Here, there is no case where both of R ¹⁰¹ and R ¹⁰² represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

In the formula (a1-10), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an alkyl group, the alkyl group may be any of a linear chain, a branched chain or a cyclic group. The linear alkyl group is preferably a carbon number of from 1 to 12, more preferably a carbon number of from 1 to 6, more preferably a carbon number of from 1 to 4. The branched chain is preferably a carbon number of 3 to 6, more preferably a carbon number of 3 or 4. Specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, second butyl group, tert-butyl group, n-pentyl group, neopentyl group, n-hexyl group and third hexyl group. (thexyl) (2,3-dimethyl-2-butyl), n-heptyl, n-octyl, 2-ethylhexyl, n-decyl, n-decyl, and the like.

The cyclic alkyl group is preferably a carbon number of from 3 to 12, more preferably a carbon number of from 4 to 8, more preferably a carbon number of from 4 to 6. 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. In the case where a halogen atom is used as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ are a halogenated alkyl group, and when an aryl group is used as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ are an aralkyl group. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Among these halogen atoms, a fluorine atom or a chlorine atom is preferred. Further, the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms. Specific examples thereof include a phenyl group, an α-methylphenyl group, a naphthyl group and the like. As the aryl group-substituted alkyl group as a whole, that is, an aralkyl group, a benzyl group, an α-methylbenzyl group, a phenethyl group, a naphthyl group can be exemplified. Methyl and the like. 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, more preferably a methoxy group or an ethoxy group. Further, when 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 may be linear. In the case of a branched alkyl group, a cycloalkyl group having 3 to 12 carbon atoms may be used as a substituent. These substituents may also be further substituted via the substituents.

In the formula (a1-10), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an aryl group, the aryl group is preferably a carbon number of 6 to 12, more preferably a carbon number of 6 to 10. The aryl group may have a substituent, and as the substituent, an alkyl group having 1 to 6 carbon atoms is preferably exemplified. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.

Further, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may be bonded to each other to form a ring together with the bonded carbon atoms. As the R ¹⁰¹ and R ^102, ring structure when the case of R ¹⁰¹ or R ¹⁰³ R ¹⁰² and R ¹⁰³ and bonded, for example, include: cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, tetrahydrofuranyl, adamantyl Alkyl groups, tetrahydropyranyl groups and the like.

Further, in the formula (a1-10), any of R ¹⁰¹ and R ¹⁰² is preferably a hydrogen atom or a methyl group.

A commercially available product may be used as the radical polymerizable unitary substance for forming a structural unit having a protective carboxyl group represented by the above formula (a1-10), or may be synthesized by a known method. For example, it can be synthesized by the synthesis method described in paragraphs 0037 to 0040 of JP-A-2011-221494.

The first preferred aspect of the constituent unit a1-1 having a protective carboxyl group protected by an acid-decomposable group is a constituent unit represented by the following formula.

Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ represents an alkyl group or an aryl group, and R ¹ Or R ² and R ³ may be bonded to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an extended aryl group.

When R ¹ and R ² are an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferred. In the case where R ¹ and R ² are an aryl group, a phenyl group is preferred. R ¹ and R ² are 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 extended aryl group, preferably a single bond.

A second preferred embodiment of the constituent unit a1-1 having a protective carboxyl group protected by an acid-decomposable group is a constituent unit represented by the following formula.

In the formula, R ¹²¹ represents a hydrogen atom or a methyl group, L ¹ represents a carbonyl group, and R ¹²² to R ¹²⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom.

A preferred specific example of the constituent unit a1-1 having the protective carboxyl group protected by the acid-decomposable group is exemplified by the following constituent unit. Further, R represents a hydrogen atom or a methyl group.

{Structural unit a1-2 having a phenolic hydroxyl group protected by an acid-decomposable group} As the constituent unit a1-2 having a protective phenolic hydroxyl group protected by an acid-decomposable group, a hydroxystyrene-based constituent unit is exemplified. Or a constituent unit in a novolak-based resin. Among these constituent units, from the viewpoint of sensitivity, a constituent unit derived from hydroxystyrene or α-methylhydroxystyrene is preferred. In addition, as a constituent unit having a phenolic hydroxyl group, the constituent unit described in paragraphs 0065 to 0073 of JP-A-2014-238438 is also preferable from the viewpoint of sensitivity.

<<<Structural unit a2>>> The constituent unit a2 is a constituent unit having a crosslinkable group (hereinafter also referred to as a constituent unit a2). The crosslinkable group is not particularly limited as long as it is a group which causes a curing reaction by heat treatment. Examples of the preferred constituent unit having a crosslinkable group include an epoxy group (e.g., oxiranyl group, 3,4-epoxycyclohexyl group, etc.), oxetanyl group, and a constituent unit of at least one of a group consisting of a group represented by NH—CH ₂ —OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), an ethylenically unsaturated group, and a blocked isocyanate group, It preferably contains a group represented by an epoxy group, an oxetanyl group, an -NH-CH ₂ -OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), (meth)acryl oxime More preferably, the constituent unit of at least one of the group consisting of a group and a blocked isocyanate group is selected from the group consisting of an epoxy group, an oxetanyl group, and -NH-CH ₂ -OR (R represents a hydrogen atom or carbon A constituent unit of at least one of the groups consisting of the groups represented by the alkyl groups represented by 1 to 20).

{Structural unit a2-1 having an epoxy group and/or oxetanyl group} The polymer component A1 preferably contains a polymer containing an epoxy group and/or an oxetanyl group. The unit a2-1 is constructed. Further, a cyclic ether group of a three-membered ring is also called an epoxy group, and a cyclic ether group of a four-membered ring is also called an oxetanyl group. The constituent unit a2-1 having an epoxy group and/or an oxetanyl group may have at least one epoxy group or oxetanyl group in one constituent unit, and may have one or more rings. The oxy group and one or more oxetanyl groups, two or more epoxy groups, or two or more oxetanyl groups are not particularly limited, and preferably have a total of one to three epoxy groups and The oxetanyl group is more preferably one or two epoxy groups and/or oxetanyl groups, and further preferably has one epoxy group or oxetanyl group.

Specific examples of the radical polymerizable unitary body for forming a structural unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, and α- Glycidyl propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxy acrylate Cyclohexyl methyl ester, 3,4-epoxycyclohexylmethyl methacrylate, α-ethyl acrylate-3,4-epoxycyclohexyl methyl ester, o-vinylbenzyl glycidyl ether, m-vinyl benzyl a glycidyl ether, a p-vinylbenzyl glycidyl ether, a compound containing an alicyclic epoxy skeleton described in paragraphs 0031 to 0035 of Japanese Patent No. 4,164,843, etc., which are incorporated herein by reference. In the manual. Specific examples of the radically polymerizable unitary substance for forming a structural unit having an oxetanyl group include an oxygen heterocyclic ring described in paragraphs 0011 to 0016 of JP-A-2001-330953. Butyl (meth) acrylates and the like, which are incorporated into the specification of the present application. Specific examples of the radical polymerizable unitary substance for forming the structural unit a2-1 having an epoxy group and/or an oxetanyl group are preferably a monomer having a methacrylate structure and containing Monomer of acrylate structure.

Among them, preferred are glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, and acrylic acid (3-ethyloxycyclohexane). Butan-3-yl)methyl ester, and (3-ethyloxetan-3-yl)methyl methacrylate. These constituent units may be used alone or in combination of two or more.

A preferred specific example of the structural unit a2-1 having an epoxy group and/or an oxetanyl group is exemplified by the following constituent unit. Further, R represents a hydrogen atom or a methyl group.

{Structural unit a2-2 having an ethylenically unsaturated group} As another example of the structural unit a2 having a crosslinkable group, a constituent unit a2-2 having an ethylenically unsaturated group is exemplified. The constituent unit a2-2 having an ethylenically unsaturated group is preferably a constituent unit having an ethylenically unsaturated group in a side chain, more preferably an ethylenically unsaturated group at the terminal, and having a carbon number of 3 The constituent unit of the side chain of ～16.

In addition, as for the structural unit a2-2 having an ethylenically unsaturated group, the description of paragraphs 0072 to 0090 of JP-A-2011-215580 and paragraph 0013 of JP-A-2008-256974 can be referred to. The description of paragraph 0031 is incorporated into the specification of the present application.

{A constituent unit a2-3 having a group represented by -NH-CH ₂ -OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) as the constituent unit a2 having the crosslinkable group In the example, a constituent unit a2-3 having a group represented by -NH-CH ₂ -OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) is also preferable. By having the constituent unit a2-3, a hardening reaction can be caused by a slow heat treatment, and a cured film excellent in characteristics can be obtained. Here, 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. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, preferably a linear or branched alkyl group. The constituent unit a2-3 is more preferably a constituent unit having a group represented by the following formula (a2-30).

In the formula (a2-30), R ³¹ represents a hydrogen atom or a methyl group, and 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. Further, the alkyl group may be any of a linear, branched or cyclic alkyl group, preferably a linear or branched alkyl group. Specific examples of R ³² include a methyl group, an ethyl group, an n-butyl group, an isobutyl group, a cyclohexyl group, and a n-hexyl group. Among them, isobutyl, n-butyl and methyl groups are preferred.

<<<Structural unit a3>>> The constituent unit a3 is a constituent unit having an acid group (hereinafter also referred to as a constituent unit a3). The acid group in the present invention means a proton dissociable group having a pKa of less than 11. The acid group used in the present invention may, for example, be a carboxylic acid group, a sulfonylamino group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, a sulfonylamino group, a sulfonyl fluorenylene group, and the like. The acid anhydride group of the group and the group which neutralizes the acid groups to form a salt structure are preferably a carboxylic acid group and/or a phenolic hydroxyl group. The salt is not particularly limited, and an alkali metal salt, an alkaline earth metal salt, and an organic ammonium salt are preferably exemplified. The constituent unit containing an acid group used in the present invention is more preferably a constituent unit derived from styrene, a constituent unit derived from a vinyl compound, or a constituent unit derived from (meth)acrylic acid and/or an ester thereof. For example, the compounds described in paragraphs 0021 to 0023 and paragraphs 0029 to 0044 of JP-A-2012-88459 can be used, and the contents are incorporated into the specification of the present application. Among them, a constituent unit derived from p-hydroxystyrene, (meth)acrylic acid, maleic acid or maleic anhydride is preferred.

The structural unit a3 having an acid group is preferably a constituent unit having a carboxyl group or a constituent unit having a phenolic hydroxyl group from the viewpoint of sensitivity, and more preferably a constituent unit having a carboxyl group. Specific examples of the structural unit a3 having an acid group include a constituent unit a1-1-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and an ethylenically unsaturated group and an acid anhydride-derived structure. The constituent unit a1-1-2 and the constituent unit a1-2-1 having a phenolic hydroxyl group are also preferably the same. In particular, the constituent unit a3 having an acid group is preferably a constituent unit derived from a compound selected from the group consisting of methacrylic acid, acrylic acid, and p-hydroxystyrene [the following formula (a3-1) to formula] More preferably, the structural unit represented by any one of (a3-3) is a structural unit derived from methacrylic acid (a structural unit represented by the following formula (a3-1)) or a constituent unit derived from acrylic acid [ The constituent unit represented by the following formula (a3-2) is more preferably a constituent unit derived from methacrylic acid [a structural unit represented by the following formula (a3-1)].

<<<Structural unit a4>>> The monomer which is the constituent unit a4 other than the constituent unit s1, the constituent unit a1, the constituent unit a2, and the constituent unit a3 is not particularly limited, and examples thereof include styrene and Alkyl (meth)acrylate, cyclic alkyl (meth)acrylate, aryl (meth)acrylate, unsaturated dicarboxylic acid diester, bicyclic unsaturated compound, maleimide compound , unsaturated aromatic compounds. The monomers forming the other constituent unit a4 may be used alone or in combination of two or more.

Specific constituent units a4 may specifically be exemplified by styrene, methyl styrene, α-methyl styrene, ethoxylated styrene, methoxystyrene, ethoxystyrene, chlorostyrene, vinylbenzoic acid. Methyl ester, ethyl vinyl benzoate, 4-hydroxypropenyl propyl 4-hydroxybenzoate, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate N-propyl ester, isopropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate A constituent unit derived from ester, acrylonitrile, monoethylammonium acetate mono(meth)acrylate or the like. In addition, the compound described in paragraphs 0021 to 0024 of JP-A-2004-264623 can be cited.

Further, the other constituent unit a4 is preferably a constituent unit derived from a styrene or a monomer having an aliphatic cyclic skeleton from the viewpoint of electrical characteristics. Specific examples thereof include styrene, methyl styrene, α-methylstyrene, dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and (methyl) Benzyl acrylate and the like.

Further, as the other constituent unit a4, from the viewpoint of adhesion, a constituent unit derived from an alkyl (meth)acrylate is preferable. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and n-butyl (meth)acrylate, and more preferably methyl (meth)acrylate. In all the constituent units constituting the polymer, the content of the constituent unit a4 is preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less. The lower limit value may be 0% by mole, but is preferably, for example, 1% by mole or more, and more preferably 5% by mole or more. When it is in the range of the said numerical value, the characteristics of the cured film obtained from the resin composition are favorable.

(Polymer A) The polymer A includes, for example, a polymer containing no more than the constituent unit s1 and containing the constituent unit a1 to the constituent unit a4, and as described above, The reason why the crosslinked structure is easily formed in the protective layer is preferably a polymer comprising a structural unit a2 having a crosslinkable group and/or a constituent unit a3 having an acid group.

<<Molecular weight>> The molecular weight of the polymer P and the polymer A is preferably from 1,000 to 200,000, more preferably from 2,000 to 50,000, still more preferably from 10,000 to 20,000, in terms of polystyrene-equivalent weight average molecular weight. If it is within the range of the numerical value, the characteristics are good. The ratio (dispersion, Mw/Mn) of the number average molecular weight Mn to the weight average molecular weight Mw is preferably from 1.0 to 5.0, more preferably from 1.5 to 3.5. Further, the measurement of the weight average molecular weight or the number average molecular weight in the present invention is preferably carried out by a gel permeation chromatography (GPC) method. Regarding the measurement by gel permeation chromatography in the present invention, it is preferred to use HLC-8020GPC (manufactured by Tosoh Co., Ltd.), and use TSKgel Super HZ MH, TSKgel Super HZ4000, TSKgel Super HZ200 (East) Manufactured by Tosoh (4.6 mm ID × 15 cm) as a column, THF (tetrahydrofuran) was used as a solution.

<<Preparation method>> Various methods are also known for the synthesis method of the polymer P and the polymer A, and an example may be used to form the respective constituents by using a radical polymerization initiator. The radically polymerizable single-body mixture of the radically polymerizable unit of the unit is polymerized in an organic solvent to be synthesized. Further, it can also be synthesized by a so-called polymer reaction.

In the present invention, the mass ratio of the polymer P to the total mass of the polymer P and the polymer A is preferably less than 10% by mass, because the retardation (Rth) in the thickness direction is kept low. More preferably, it is 0.1 mass% - 5% by mass.

(Crosslinking Agent B) In the present invention, the flatness is improved when the color filter is provided on the viewing side, and the display performance after exposure to high temperature and high humidity is also improved. The alignment protective layer preferably contains a crosslinking agent B having a molecular weight of 5,000 or less. The crosslinking agent B can be used without limitation as long as it is a crosslinking reaction by heat. For example, it is preferably selected from 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 isocyanate group), and an alkoxymethyl group-containing compound. At least one selected from the group consisting of a compound or at least one ethylenically unsaturated double bond (ethylenically unsaturated group), more preferably selected from the group consisting of two or more epoxy groups or oxetanyl groups in the molecule. At least one of a group consisting of a compound and a blocked isocyanate compound. Hereinafter, the crosslinking agent B which can be preferably used in the present invention will be described.

<<Compound having two or more epoxy groups or oxetanyl groups in the molecule>> As the crosslinking agent B, for example, a polyfunctional small ring cyclic ether compound can be mentioned. That is, it means a compound having two or more epoxy groups and/or oxetanyl groups in one molecule.

Specific examples of the compound having two or more epoxy groups in the molecule include an aliphatic epoxy compound and the like. These can be obtained as commercial products. For example, Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-614B, Dina Denacol EX-622, Denacol EX-512, Denacol EX-521, Denacol EX-411, Denacol EX -421, Denacol EX-313, Denacol EX-314, Denacol EX-321, Denacol EX-211, Dinaco Denacol EX-212, Denacol EX-810, Denacol EX-811, Denacol EX-850, Denacol EX- 851, Denacol EX-821, Denacol EX-830, Denacol EX-832, Denacol EX-841, Dinacourt (Denacol) EX-911, Denacol EX-941, Denacol EX-920, Denacol EX-931, Denacol EX-212L , Denacol EX-214L, Denacol EX -216L, Denacol EX-321L, Denacol EX-850L, Denacol DLC-201, Denacol DLC-203, Dinaco Denacol DLC-204, Denacol DLC-205, Denacol DLC-206, Denacol DLC-301, Denacol DLC- 402 (above is manufactured by Nagase ChemteX), Celloxide 2021P, Celloxide 2081, Celloxide 3000, Celloxide EHPE3150, EPOLEAD GT400, Serubinasu B0134, Serubinasu B0177 (made by Daicel). These may be used alone or in combination of two or more.

As a specific example of a compound having two or more oxetanyl groups in the molecule, Aron Oxetane OXT-121, Aron Oxetane OXT-221 can be used. , Aron Oxetane OX-SQ, Aron Oxetane PNOX (above manufactured by East Asia Synthetic Co., Ltd.).

Further, the compound containing an oxetanyl group is preferably used singly or in combination with a compound containing an epoxy group.

<<Blocking Isocyanate Compound>> As the crosslinking agent B, a blocked isocyanate compound can also be preferably used. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group which is chemically protected by an isocyanate group, and is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability. In addition, the blocked isocyanate group in the present invention means a group which can form an isocyanate group by heat, and for example, a group which protects an isocyanate group by reacting a blocking agent with an isocyanate group can be preferably exemplified. Further, the blocked isocyanate group is preferably a group capable of forming an isocyanate group by heat of from 90 ° C to 250 ° C. In addition, the skeleton of the blocked isocyanate compound is not particularly limited, and may be any compound as long as it has two isocyanate groups in one molecule, and may be an aliphatic, alicyclic or aromatic polyisocyanate, for example, suitably Using 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetra Methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1 , 10-methylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate , m-xylene diisocyanate, p-xylene diisocyanate, methylene bis(cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1,4-dimethylene Diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methylene xylene-4,4'-diisocyanate Isocyanate compounds such as 4,4'-diphenyl ether diisocyanate, tetrachlorobenzene diisocyanate, norbornane diisocyanate, hydrogenated 1,3-xylene diisocyanate, hydrogenated 1,4-xylene diisocyanate, and the like A compound of a compound-derived prepolymer type skeleton. Among these, particularly preferred are tolylene diisocyanate (TDI) or diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate ( Isophorone diisocyanate, IPDI).

Examples of the parent structure of the blocked isocyanate compound include a biuret type, an isomeric cyanurate type, an adduct type, and a difunctional prepolymer type. Examples of the blocking agent for forming the closed structure of the blocked isocyanate compound include an anthracene compound, an indoleamine compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a thiol compound, and an imidazole system. a compound, a quinone imine compound, or the like. Among these, a blocking agent selected from the group consisting of an anthracene compound, an indoleamine compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound is particularly preferred.

Examples of the hydrazine compound include hydrazine and ketoxime, and specific examples thereof include acetoxime, fordoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, and diphenyl benzoate. Ketone oxime, acetone oxime, and the like. The intrinsic amine compound may, for example, be ε-caprolactam or γ-butylide. Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol. The alcohol compound may, for example, be methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether or alkyl lactate. Examples of the amine compound include a primary amine and a secondary amine, and may be any of an aromatic amine, an aliphatic amine, and an alicyclic amine, and examples thereof include aniline, diphenylamine, ethylenimine, and poly Ethyl imine and the like. The active methylene compound may, for example, be diethyl malonate, dimethyl malonate, ethyl acetate or ethyl acetate. The pyrazole compound may, for example, be pyrazole, methylpyrazole or dimethylpyrazole. The thiol compound may, for example, be an alkyl mercaptan or an aryl thiol.

The blocked isocyanate compound can be obtained as a commercial product, and for example, Coronate AP stable M, Coronate 2503, Coronate 2515, g can be preferably used. Coronate 2507, Coronate 2513, Coronate 2555, Millionate MS-50 (above manufactured by Japan Polyurethane Industry), Tuck Knight (Takenate) B-830, Takenate B-815N, Takenate B-820NSU, Takenate B-842N, Takenate B-846N , Takenate B-870N, Takenate B-874N, Takenate B-882N (above manufactured by Mitsui Chemicals Co., Ltd.), Duranate 17B-60PX, Duranate 17B-60P, Duranate TPA-B80X, Duranate TPA-B80E, Duranate MF-B60X, Du Durant MF-B60B, Duranate MF-K60X, Duranate MF-K60B, Dura Duranate E402-B80B, Duranate SBN-70D, Duranate SBB-70P, Duranate K6000 (above, manufactured by Asahi Kasei Chemicals Co., Ltd.) Desmodule BL1100, Desmodule BL1265 MPA/X, Desmodule BL3575/1, Desmodule BL3272MPA, Desmodule BL3370MPA, Desmodule ) BL3475BA/SN, Desmodule BL5375MPA, Desmodule VPLS2078/2, Desmodule BL4265SN, Desmodule PL340, Desmodule PL350, Sumidity (Sumidule) BL3175 (above is manufactured by Bayeramide) and the like.

<<Alkoxymethyl group-containing crosslinking agent>> As the alkoxymethyl group-containing compound, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxy group A are preferable. Alkalized glycoluril and alkoxymethylated urea, and the like. These are obtained by converting a 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, a butoxymethyl group, and the like, and an out gas is used. From the viewpoint of the amount of production, it is particularly preferably a methoxymethyl group. Among these compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are preferred compounds, and from the viewpoint of transparency, it is particularly preferable. It is an alkoxymethylated glycoluril. Regarding the alkoxymethyl group-containing crosslinking agent, a compound having a molecular weight of 1,000 or less is also used for the curable composition. These alkoxymethyl group-containing compounds are commercially available, and for example, CYMEL 300, CYMEL 301, CYMEL 303, and Seime are preferably used. CYMEL 370, CYMEL 325, CYMEL 327, CYMEL 701, CYMEL 266, CYMEL 267, Semel ( CYMEL) 238, CYMEL 1141, CYMEL 272, CYMEL 202, CYMEL 1156, CYMEL 1158, CYMEL 1123, CYMEL 1170, CYMEL 1174, CYMEL UFR65, CYMEL 300 (above manufactured by Mitsui Cyanamid), Nicarak ( Nikalac) MX-750, Nikalac MX-032, Nikalac MX-706, Nikalac MX-708, Nikalac MX-40, Nicarak ( Nikalac) MX-31, Nikalac MX-270, Nikalac MX-280, Nikalac MX-290, Nikalac MS-11, nicardipine la (Nikalac) MW-30HM, nicardipine la (Nikalac) MW-100LM, nicardipine la (Nikalac) MW-390, (more than three and chemical (Unit)) and the like.

In the present invention, as the crosslinking agent B, a crosslinking agent having an epoxy group is preferably used. In addition, the content in the case where the crosslinking agent B is contained in the total amount of the crosslinking agent B, the polymer P, and the polymer A is preferably 30% by mass or less, and more preferably 10% by mass to 30% by mass.

(Organic solvent) The protective layer forming composition preferably contains an organic solvent in addition to the polymer. As the organic solvent, a known organic solvent can be used, and examples thereof include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, and 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, butanediol II Acetate, dipropylene glycol dialkyl ether, dipropylene glycol monoalkyl ether acetate, alcohols, esters, ketones, guanamines, lactones, and the like. As a specific example of such an organic solvent, the paragraph 0062 of Japanese Patent Laid-Open Publication No. 2009-098616 can be referred to.

Preferred specific examples include propylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, and 1,3-butylene glycol. Acetate, methoxypropyl acetate, cyclohexanol acetate, propylene glycol diacetate, tetrahydrofurfuryl alcohol.

The boiling point of the organic solvent is preferably from 100 ° C to 300 ° C, more preferably from 120 ° C to 250 ° C from the viewpoint of coatability. The organic solvent which can be used in the present invention may be used alone or in combination of two or more. It is also preferred to use a solvent having a different boiling point. From the viewpoint of adjusting the viscosity suitable for coating, the content in the case of containing an organic solvent is preferably from 100 parts by mass to 3,000 parts by mass, more preferably 200% by mass based on 100 parts by mass of the total solid content of the composition. The amount is preferably 2,000 parts by mass, and more preferably 250 parts by mass to 1,000 parts by mass. The solid content concentration of the composition is preferably 3% by mass to 50% by mass, and more preferably 20% by mass to 40% by mass.

(Surfactant) The protective layer forming composition may further contain a surfactant. As the surfactant, any of an anionic, cationic, nonionic or amphoteric surfactant can be used, and a preferred surfactant is a nonionic surfactant. The surfactant is preferably a nonionic surfactant, more preferably a fluorine-based surfactant. Examples of the surfactant which can be used in the first aspect include Megafac F142D, Megafac F172, Megafac F173, Megafac F176, and Meijia as commercial products. Method (Megafac) F177, Megafac F183, Megafac F479, Megafac F482, Megafac F554, Megafac F780, Megafac F781, Meijiafa (Megafac) F781-F, Megafac R30, Megafac R08, Megafac F-472SF, Megafac BL20, Megafac R-61, Megafac ) R-90 (made by Dickson (DIC)), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Frode ( Fluorad) FC-431, Novec FC-4430 (made by Sumitomo 3M (share)), Asahi Guard AG7105, Asahi Guard AG7000, Asahi Guard AG950, Xu Jiade (Asahi Guard) AG7600, Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, Surflon SC-105, Surflon SC-106 (made by Asahi Glass Co., Ltd.), Eftop EF351, Eftop EF352, Eftop EF801, Eftop EF802 (Mitsubishi) The material is electronically manufactured (Federal), F. Fentgent 250 (manufactured by NEOS). In addition, in addition to the above, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and Eftop (E-Told) can also be cited. (share) manufacturing), Megafac (made by DiCai (DIC)), Fluorad (made by Sumitomo 3M), Asahi Guard, Surflon ) (made by Asahi Glass Co., Ltd.), PolyFox (made by OMNOVA) and other series.

Further, as the surfactant, a compound described in paragraphs 0151 to 0155 of JP-A-2014-238438 is also preferably used.

The content in the case where the surfactant is contained is preferably 0.001 parts by mass to 5.0 parts by mass, more preferably 0.01 parts by mass to 2.0 parts by mass, per 100 parts by mass of the total solid content of the composition. The surfactant may be contained alone or in combination of two or more. When two or more cases are included, it is preferable that the total amount thereof becomes the above range.

(Adhesive Improver) The protective layer forming composition may further contain a adhesion improving agent. Examples of the adhesion improving agent include alkoxydecane compounds and the like. The alkoxydecane compound is preferably a compound in which an inorganic substance such as ruthenium, ruthenium oxide or ruthenium nitride, or a metal such as gold, copper, molybdenum, titanium or aluminum is improved in adhesion to an insulating film. Specific examples of the adhesion improving agent include γ-aminopropyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-glycidoxypropyltrimethoxydecane, and γ- Glycidoxypropyltriethoxydecane, γ-glycidoxypropylmethyldimethoxydecane, γ-methylpropenyloxypropylmethyldiethoxydecane, γ-methyl Propylene methoxypropyltriethoxy decane, γ-chloropropyltrimethoxydecane, γ-mercaptopropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane , vinyl trimethoxy decane, and the like. Among these, γ-glycidoxypropyltrimethoxydecane, γ-methylpropoxypropyltrimethoxydecane, and more preferably γ-glycidoxypropyltrimethoxydecane are preferred. . These may be used alone or in combination of two or more. The content of the adhesion improving agent is preferably 0.001 parts by mass to 15 parts by mass, more preferably 0.005 parts by mass to 10 parts by mass, per 100 parts by mass of the total solid content of the composition. The adhesion improving agent may be used alone or in combination of two or more. When two or more cases are used, it is preferred that the total amount is the above range.

(Photosensitive Agent) The protective layer forming composition may further contain a photosensitizer. Examples of the photosensitizer include a photoacid generator, a quinonediazide compound, a photoradical initiator, and the like.

<Formation of Protective Layer> The method of forming the protective layer on the substrate is not particularly limited, and examples thereof include a method of applying the protective layer-forming composition onto a substrate.

(Coating) The method of applying the protective layer forming composition to the substrate is not particularly limited, and specific examples thereof include a printing method (for example, a gravure printing method, a screen printing method, a flexographic printing method, and the like). Inkjet printing method, imprint method, etc.), spin coating method, slit coating method, slit and spin coating method, dip coating method, curtain coating method, and the like.

(Solvent Removal) In the present invention, a solvent removal step of removing any solvent contained in the composition for forming a protective layer from the film may be included after the coating and before the alignment treatment step described later. The solvent removal step differs depending on the type or amount of the solvent. For example, when N-methyl pyrrolidone (NMP) is used as the solvent, it is preferably heated at about 80 ° C to 150 ° C. The step of about minute to about 3 minutes is more preferably a step of heating at about 90 to 120 ° C for about 0.5 minutes to 2 minutes.

<Formation of the alignment protective layer (alignment treatment)> Examples of the alignment treatment include a non-contact alignment method such as a rubbing treatment method, a photo alignment treatment, and a magnetic field alignment.

(Photoalignment Treatment) In the case of the present invention, when the alignment group is a photo-alignment group, the alignment 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 for using light having a wavelength of 365 nm or less, and it is preferable to use polarized ultraviolet rays from the viewpoint of obtaining uniform alignment. In this case, the method of irradiating the polarized ultraviolet rays is not particularly limited. In addition, the polarized light is not particularly limited, and examples thereof include linearly polarized light, circularly polarized light, and elliptically polarized light. Among them, linear polarized light is preferable.

Further, as long as the polarized light is substantially obtained, the unpolarized light may be irradiated from the normal line of the film at a constant angle. In other words, non-polarized light can also be irradiated from the oblique direction of the film surface. The "inclined irradiation" is not particularly limited as long as it is inclined in the direction of the normal to the surface of the film by the polar angle θ (0° < θ < 90°), and can be appropriately selected according to the purpose, and θ is preferable. It is 20° to 80°.

Examples of the light source used for the light include a xenon lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, and a metal halide lamp. The wavelength range of the irradiation can be limited by using an interference filter, a color filter or the like for the ultraviolet rays obtained by such a light source. Further, by using a polarizing filter or a polarizing ray for light from the light sources, linearly polarized light can be obtained.

<Heat Treatment> In the present invention, from the viewpoint of improving the reliability of the film transistor, it is preferred that the first step is a step of performing heat treatment before or after the alignment treatment.

As a method of performing the heat treatment, for example, the protective layer or the alignment protective layer subjected to the alignment treatment may be heated at a temperature of from 180 ° C to 350 ° C, preferably from 200 ° C to 300 ° C, for 20 minutes to 60 minutes. Method, etc. Further, the heat treatment is preferably carried out using a heating means such as a hot plate or an oven. Further, the transparency can be further improved by heat treatment in a nitrogen atmosphere.

[Second Step] The second step includes adhering and sealing a second substrate including a substrate, a thin film transistor, a display electrode, and an alignment film to the first substrate, and forming a liquid crystal layer between the first substrate and the second substrate. The step of fabricating a liquid crystal display device. In addition, the second substrate in the second step is the same as the second substrate of the liquid crystal display device of the present invention, and the method for producing the second substrate is not particularly limited.

The method of encapsulating the liquid crystal in the second step is not particularly limited. For example, a method in which a spacer is formed between the first substrate and the second substrate to form a space, and the liquid crystal is sealed in the formed space is exemplified. [Examples]

Hereinafter, the present invention will be further described in detail based on examples. The materials, the amounts used, the ratios, the processing contents, the processing order, and the like shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the invention should not be construed as limited by the embodiments shown below. In addition, "part" and "%" are the quality standards unless otherwise specified.

[Synthesis of a constituent unit having a photo-alignment group (monomer a-1)] Methyl trans-4-hydroxycinnamate (manufactured by Tokyo Chemical Industry Co., Ltd., 12.5 g, 0.07 mol) and triethylamine ( Was prepared by Wako Pure Chemical Industries Co., Ltd., 7.79 g, 0.07 mol) pre-dissolved in 100 mL of tetrahydrofuran (hereinafter referred to as "THF"), and slowly added dropwise methacrylic acid chloride after cooling to 0 °C (Tokyo Chemical Industry Co., Ltd.) (Stock) manufactured, 7.33 g, 0.07 mol). Then, 500 g of water was added to the reaction system which became cloudy, and after stirring for 1 hour, it was filtered, and 14 g of the monomer a-1 which has a cinnamate group as a photo-alignment group was obtained. The structure was confirmed by nuclear magnetic resonance (NMR).

[Synthesis of a constituent unit having a photo-alignment group (monomer a-2)] Ethyl 4-hydroxy-3-methoxycinnamate (manufactured by Tokyo Chemical Industry Co., Ltd., 22.2 g, 0.1 mol) was previously dissolved. Potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd., 30 g, 0.22 mol) was added to 150 mL of dimethyl acetamide, and the temperature was raised to 90 °C. Then, 4-chlorobutanol (manufactured by Wako Pure Chemical Industries, Ltd., 21.6 g, 0.2 mol) was added dropwise, and stirred for 3 hours. Thereafter, the reaction solution was poured into 1 L of water, neutralized with 2 N HCl, extracted with 700 mL of ethyl acetate, washed with saturated brine, and concentrated. Then, fractionation was carried out by silica gel column chromatography to obtain 23 g of an intermediate compound. 15 g (0.05 mol) of this 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. Then, methacrylic acid ruthenium chloride (manufactured by Tokyo Chemical Industry Co., Ltd., 5.8 g, 0.056 mol) was added dropwise, and after stirring for 3 hours, the reaction solution was poured into 500 g of water, extracted with ethyl acetate, and concentrated. . Then, by fractionation by ruthenium column chromatography, 20 g of a monomer a-2 having a cinnamate group as a photo-alignment group was obtained.

[Synthesis of a constituent unit having a photo-alignment group (monomer a-3)] Pre-dissolving hydroquinone (manufactured by Wako Pure Chemical Industries, Ltd., 63.8 g, 0.58 mol) in dimethylacetamide 500 In the mL, potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd., 40 g, 0.29 mol) was added, and the temperature was raised to 90 °C. Then, 4-chlorobutyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., 25.6 g, 0.145 mol) was added dropwise, and stirred for 3 hours. Thereafter, the reaction solution was poured into 1 L of water, neutralized with 2 N HCl, extracted with 700 mL of ethyl acetate, washed with saturated brine, and concentrated. The crude crystals were taken out and fractionated by silica gel column chromatography to obtain 18 g of the intermediate compound. 18 g of the intermediate compound and triethylamine (manufactured by Wako Pure Chemical Industries, Ltd., 7.79 g, 0.07 mol) were dissolved in 100 mL of THF, and cooled to 0 °C. Then, cinnamon chloroform (manufactured by Tokyo Chemical Industry Co., Ltd., 13.1 g, 0.07 mol) was added dropwise, and after stirring for 3 hours, the reaction solution was poured into 500 g of water, extracted with ethyl acetate, and concentrated. Then, fractionation by hydrazine column chromatography gave 22 g of monomer a-3 having a chalcone group as a photo-alignment group.

[Synthesis of a constituent unit having a photo-alignment group (monomer a-4)] Synthesis of an azo in the same manner as "Macromolecules" (2004, Vol. 37, #7, p. 2572) The group is a photo-alignment-based monomer a-4.

[Synthesis of a constituent unit having a photo-alignment group (monomer a-5)] and "Jounal of Polymer Science, Part A: Polymer Chemistry" (2010) , Vol. 48, #19, 4323) In the same manner, a monomer a-5 having a coumarin group as a photo-alignment group was synthesized.

[Synthesis of a constituent unit (monomer e-1) protected by an acid-decomposable group] methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., 86 g, 1 mol) was previously cooled to 15 ° C, and camphor was added. Sulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd., 4.6 g, 0.02 mol). Then, 2-dihydrofuran (manufactured by Kawaken Fine Chemicals Co., Ltd.), 71 g, 1 mol, 1.0 equivalent) was added dropwise to the reaction solution. After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added andEtOAc was evaporated. Then, after drying with magnesium sulfate, the insoluble matter was filtered, and then concentrated under reduced pressure at 40 ° C or lower, and the yellow oil as a residue was distilled under reduced pressure to obtain 125 g as a colorless oil. The boiling point (bp.) of tetrahydro-2H-furan-2-yl methacrylate of 54 ° C to 56 ° C / 3.5 mmHg fraction was taken as monomer e-1 (yield 80%).

[Synthesis of Polymer (P1) Having Structural Unit s1] 22 g of diethylene glycol methyl ethyl ether (hereinafter abbreviated as "HS-EDM") was heated and stirred to 70 ° C under a nitrogen stream. The monomer a-1 (11.1 g, 45 mol%) and hexafluoroisopropyl methacrylate (hereinafter referred to as "HFIP") (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.5 g, were added dropwise over 2 hours. 15 mol%), methacrylic acid (hereinafter referred to as "MAA") (manufactured by Wako Pure Chemical Industries, Ltd., 1.7 g, 20 mol%), glycidyl methacrylate (hereinafter referred to as "GMA") (and Wako Pure Chemical Industries, Ltd., 2.8 g, 20 mol%), free radical polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) 497 mg (2 mol%), and PGMEA (30 g) Mixed solution. After completion of the dropwise addition, the reaction was further carried out at 70 ° C for 4 hours, whereby a PGMEA solution (solid content concentration: 27%) having the polymer P1 constituting the unit s1 was obtained.

[Synthesis of Polymer (P2 to P11) Having Structural Unit s1] The polymer P2 was synthesized in the same manner as the polymer P1 except that the type of the monomer, the initiator, and the solvent were changed according to the first table below. ~ Polymer P11. In addition, the numerical value shown in the column of each singular component of the following Table 1 is the usage amount (mol%) of the total amount of each singular body with respect to the singular component. In addition, the numerical value described in the column of the polymerization initiator is a mol% when the total amount of the monomer components is 100 mol%. In addition, the abbreviation used in the Example is as follows. <Abbreviation> HFIP: Hexafluoroisopropyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) ·6FM: Trifluoroethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) ·KBM-503:3- Methyl propylene methoxy propyl trimethoxy decane (manufactured by Shin-Etsu Chemical Co., Ltd.) · C18MA: octadecyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) · MAA: methacrylic acid (Wako Pure Chemicals) Industrial (stock) manufacturing) ·MMA: Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) ·St: Styrene (manufactured by Wako Pure Chemical Industries, Ltd.) ·AA: Acrylic (Wako Pure Chemical Industries Co., Ltd. )Manufacturing) ·GMA: glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) ·OXE-30: (3-ethyloxetan-3-yl)methyl methacrylate (Osaka Organic Chemistry) Industrial (stock) manufacturing) · Cyclomer M-100: (3,4-epoxycyclohexyl) methacrylate (manufactured by Daicel Chemical Industry Co., Ltd.) ·DCPM: Dicyclopentyl methacrylate Ester (Fancryl FA-513M, manufactured by Hitachi Chemical Co., Ltd.) NBMA: N-butoxymethyl acrylamide (manufactured by Mitsubishi Rayon Co., Ltd.) · V-601: Radical polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd.) · V- 65: Radical polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd.) · PGMEA: methoxypropylene glycol acetate (manufactured by Daicel), HS-EDM: diethylene glycol methyl Ethyl ether (manufactured by Toho Chemical Industry Co., Ltd.)

[Table 1]

[Synthesis of Other Photoalignment Polymer] <Synthesis of Polymer P12> The photo-alignment polymer (A-) described in paragraph [0161] (Preparation Example 1) of JP-A-2013-177561 1) The same method to synthesize the polymer P12. <Synthesis of Polymer P13> The polymer P13 was synthesized in the same manner as the specific copolymer P1 described in the paragraph [0084] (Synthesis Example 1) of WO2010/150748.

[Preparation of Polymer A Having Other Constituent Units] <Synthesis of Polymer A-1 Containing Group A1 Group Having Acid Group Deprotected by Acid-Decomposable Group and Component Unit A2 Having Crosslinkable Group> HS-EDM (82 parts) was heated and stirred to 90 ° C under a nitrogen stream. Then, tetrahydro-2H-furan-2-yl methacrylate synthesized as a monomer e-1 was added dropwise over 2 hours (43 parts (corresponding to 40.5 mol% of all the monomer components)), OXE -30 (48 parts (equivalent to 37.5 mol% of all monomer components)), MAA (6 parts (equivalent to 9.5 mol% of all monomer components)), hydroxyethyl methacrylate (and pure light) Manufactured by the pharmaceutical industry, 11 parts (equivalent to 12.5 mol% of all monomer components), a mixed solution of a radical polymerization initiator V-601 (4.3 parts), and PGMEA (82 parts), The reaction was carried out at 90 ° C for 2 hours, whereby a solution of the polymer A-1 (solid content concentration: 40%) was obtained. Further, the obtained polymer A-1 had a weight average molecular weight of 15,000 as measured by gel permeation chromatography (GPC).

<Synthesis of Polymer A-2 Comprising Structural Unit a1 Having Group Protected with Acid Group by Acid-Decomposable Group> PGMEA (238 g) was heated and stirred to 90 ° C under a nitrogen stream. Then, tetrahydro-2H-furan-2-yl methacrylate synthesized as a monomer e-1 was added dropwise over 2 hours (240 g (corresponding to 61.1 mol% of all the monomer components)), MAA (50.4 g (equivalent to 17.6 mol% of all monomer components)), MMA (27.9 g (equivalent to 21.3 mol% of all monomer components)), and free radical polymerization initiator V-601 (14.7 g) and a mixed solution of PGMEA (238 g) were further reacted at 90 ° C for 2 hours, and after cooling, PGMEA (42 g) was added to obtain a solution of polymer A-2 (solid content concentration: 38%). The weight average molecular weight of the obtained polymer A-2 measured by gel permeation chromatography (GPC) was 15,000.

<Synthesis of Polymer A-3 Comprising Structural Unit a2 Having Crosslinkable Group> HS-EDM (145 g) was heated and stirred to 70 ° C under a nitrogen stream. Then, GMA (144.7 g (67.9 mol%)), MAA (16.7 g (12.9 mol%)), St (28.1 g (18.0 mol%)), and DCPM (3.87 g (1.17 mol%)) were added dropwise over 2 hours. A mixed solution of a radical polymerization initiator V-65 (20.8 g (5.6 mol% monomer conversion)) and HS-EDM (145 g). After completion of the dropwise addition, the reaction was carried out at 70 ° C for 4 hours, whereby a PGMEA solution of polymer A-3 (solid content concentration: 35%) was obtained.

<Polymer A-4 constituting the structural unit a3 having an acid group and the structural unit a2 having a crosslinkable group> PGMEA (268 parts) was heated and stirred to 90 ° C under a nitrogen stream. Then, tetrahydro-2H-furan-2-yl methacrylate synthesized as a monomer e-1 was added dropwise over 2 hours (143.4 parts (corresponding to 40.1 mol% of all monomer components)), Cyclomer M-100 (168.4 parts (equivalent to 37.5 mol% of all monomer components)), MAA (19.5 parts (equivalent to 9.9 mol% of all monomer components)), hydroxyethyl methacrylate (and Manufactured by Wako Pure Chemical Industries Co., Ltd., 37.2 parts (equivalent to 12.5 mol% of all monomer components), a mixture of free radical polymerization initiators V-601 (5.5 parts), and PGMEA (268 parts). Further, the reaction was carried out at 90 ° C for 2 hours, whereby a solution of a polymer A-4 (solid content concentration: 40%) was obtained. Further, the obtained polymer A-4 had a weight average molecular weight of 16,000 as measured by gel permeation chromatography (GPC).

<Polymer A-5 containing structural unit a3 having an acid group and structural unit a2 having a crosslinkable group> After the inside of the flask was purged with nitrogen, 459.0 g of 2,2'-azobisisobutyl was dissolved therein. Nitrile 9.0 g of diethylene glycol dimethyl ether solution. Then, after St (22.5 g), MAA (45.0 g), DCPM (67.5 g), and GMA (90.0 g) were put in, stirring was started slowly. Then, the temperature of the solution was raised to 80 ° C, the temperature was maintained for 5 hours, and then heated at 90 ° C for 1 hour to complete the polymerization. Thereafter, the reaction-forming solution was added dropwise to a large amount of water to solidify the reactant. The coagulum was washed with water, dissolved in THF (200 g), and solidified again with a large amount of water. After the operations of re-dissolution and solidification were carried out three times in total, the obtained coagulum was dried under reduced pressure at 60 ° C for 48 hours to obtain a polymer A-5. Thereafter, diethylene glycol was used to prepare a solution of the polymer A-5 so that the solid content concentration became 25% by mass.

<Polymer A-6> Polymer A was synthesized in the same manner as the non-orthogonal polymer (E-1) described in paragraph [0165] (Preparation Example 5) of JP-A-2013-177561. -6.

[Crosslinking Agent B] The following one was used as the crosslinking agent B. <B-1> 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. <B-2> A polyfunctional epoxy compound (EX-321L, manufactured by Nagase ChemteX Co., Ltd.) was used as the crosslinking agent B-2 having a molecular weight of 5,000 or less. <B-3> A polyfunctional epoxy compound (JER57S65, manufactured by Japan Epoxy Resin Co., Ltd.) was used as the crosslinking agent B-3 having a molecular weight of 5,000 or less.

[Other Ingredients] <F-554> A perfluoroalkyl group-containing nonionic surfactant (F-554, manufactured by Diane (DIC) Co., Ltd.) was used as a surfactant. <KBM-403> γ-glycidoxypropyltrimethoxydecane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as a adhesion improving agent.

[Examples 1 to 24 and Comparative Examples 1 to 6] The respective components shown in the following Table 2 were dissolved and mixed in a solvent (PGMEA) until the solid content concentration was 18% by mass, and the diameter was 0.2 μm. The polytetrafluoroethylene filter was filtered to prepare a resin composition of each of the examples and the comparative examples. In addition, the addition amount in a table shows the addition amount of the solid content of each component, and the unit is a mass part. The obtained resin composition was applied onto a glass substrate by a spin coating method, pre-dried on a hot plate at 80 ° C for 1 minute, and then calcined in a clean oven at 230 ° C for 60 minutes to form a 3 μm outer layer. A cured film of the coating. The formed cured film was obliquely cut by a surface/interface cutting device (DN-20S type, manufactured by Daipla Wintes Co., Ltd.) to expose the cross section. With respect to the exposed cross section, the intensity ELq of the mass spectrum of the fragment derived from the alignment group and the intensity ESub were measured by the measuring device and the conditions, and the intensity ratio (strength ELq/intensity ESub) of the mass spectrum was measured, and the following criteria were used. Evaluation. The results are shown in Table 2 below. Further, the same test was performed on the alignment protective layer after the display device described later was produced, and the results were the same. A: the intensity ratio is 10 times or more or the intensity ESub is below the measurement limit B: the intensity ratio is 8 times or more to less than 10 times C: the intensity ratio is 5 times or more to less than 8 times D: the intensity ratio is 2 times or more to less than 5 Double E: Intensity ratio is less than 2 times F: no fragment peak

[Table 2]

[Evaluation] <Orientation> Each of the prepared resin compositions was applied onto a non-alkali glass substrate by a spin coater (spinner), and then pretreated on a hot plate at 100 ° C for 2 minutes. Baking was carried out to thereby form a coating film having a film thickness of 4.0 μm. Then, using a high-pressure mercury lamp, the exposure amount was set to 1000 J/m ^{2 ,} and the obtained coating film was irradiated with radiation, followed by post-baking in an oven at a hardening temperature of 230 ° C and a hardening time of 30 minutes, thereby forming The protective layer. To the formed protective layer, a polarized light of 750 mJ/cm ^{2 was} irradiated with an ultraviolet polarizing exposure apparatus (HC-2150PUFM, manufactured by LAN TECHNICAL SERVICE), and photoalignment treatment was performed to form an alignment protective layer. Thereafter, the coating was horizontally aligned to the liquid crystal, and the alignment state was observed by a polarizing microscope at a magnification of 20 times. The change site was observed in five fields of view (about 1 square μm) and evaluated by the following criteria. The results are shown in Table 3 below. A: There is no problem. B: I can see the shade, but it is a practical level. C: There is a defect and a bright spot is observed. D: Completely unaligned.

<Retardation (Rth)> On the alkali-free glass substrate, each of the prepared resin compositions was applied by a spin coater, and then prebaked on a hot plate at 100 ° C for 2 minutes to form a film thickness of 4.0. Μm coating film. Then, using a high-pressure mercury lamp, the exposure amount was set to 1000 J/m ^{2 ,} and the obtained coating film was irradiated with radiation, followed by post-baking in an oven at a hardening temperature of 230 ° C and a hardening time of 30 minutes, thereby forming The protective layer. For the protective layer, birefringence was evaluated using a phase difference measuring device KOBRA-WFD (manufactured by Oji Scientific Instruments Co., Ltd.). The results are shown in Table 3. Further, since the birefringence is caused by the angular deviation of the display, as long as it does not exceed 30 nm, there is no problem in practical use, and it is preferable that the value is low.

<Flatness> An L/S pattern having a height of 1 μm and a width of 10 μm (a ratio of L/S width of 1:1) was produced, and a resin composition was applied thereon by a spin coater at 90 ° C / After prebaking in 120 seconds, it was thermally hardened in an oven at 230 ° C / 30 minutes to obtain a 2 μm cured film. The flatness of the obtained cured film was defined and calculated by the following formula. The results are shown in Table 3 below. Further, regarding the flatness, the closer the value is to 100, the higher the flattening ability is, and the practical requirement is 70% or more. Flatness (%) = (1 - Δd / H) × 100 Here, in the above formula, Δd means the difference between the film thickness of the cured film on the upper portion of the L/S pattern and the film thickness (2 μm) of the cured film ( Μm), H means the film thickness (μm) of the L/S pattern of the substrate.

<Display Characteristics> (1) Manufacture of Array Substrate According to the description of Example 42 of the International Publication (WO) 2009/025386, an insulating film in which contact holes are formed is formed on the array substrate. Then, for the substrate on which the insulating film is formed, a transparent conductive layer containing ITO is formed on the insulating film by sputtering. Next, the transparent conductive layer is etched by photolithography to form a common electrode on the insulating film. Thereafter, an insulating layer of SiN was formed using a sputtering method. Next, the SiN layer is etched by photolithography to form a patterned SiN insulating film on the surface of the substrate on which the common electrode is formed. Next, a transparent conductive layer containing ITO was formed on the interlayer insulating film by sputtering. Then, the transparent conductive layer is etched by photolithography to form a comb-shaped pixel electrode on the inorganic insulating film. The array substrate of this embodiment was fabricated as described above. In the obtained array substrate of the present embodiment, a contact hole having 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 device is realized. On the transparent electrode of the array substrate, the liquid crystal alignment agent A-1 described in Example 6 of the International Publication (WO) 2009/025386 is applied as a radiation-inducing line having a photo-alignment group by a spin coater. A liquid crystal alignment agent for polymers. Then, the film was prebaked for 1 minute by a hot plate at 80 ° C, and then heated at 180 ° C for 1 hour in an oven which was internally purged with nitrogen to form a coating film having a film thickness of 80 nm. Then, using a Hg-Xe lamp and Glan Taylor Prism on the surface of the coating film, a polarized ultraviolet ray containing a bright line of 313 nm was irradiated from a direction inclined by 40° with respect to a direction perpendicular to the surface of the substrate. 200 J/m ² to fabricate an array substrate having a liquid crystal alignment film.

(2) Fabrication of Counter Substrate First, a color filter substrate manufactured by a known method is prepared. In the color filter substrate, the micro coloring patterns of the three colors of red, green, and blue are arranged on the transparent substrate in a lattice shape with the black matrix. Next, on the colored pattern of the color filter substrate and the black matrix, the resin compositions of Examples 1 to 24 and Comparative Examples 1 to 6 shown in the second table were used to form a coating film. After prebaking at 90 ° C / 120 seconds, the film was thermally cured at 230 ° C / 30 minutes in an oven to prepare a protective film. Then, with respect to the protective film, an optical alignment treatment of irradiating light of 750 mJ/cm ² was performed using an ultraviolet polarizing exposure apparatus (HC-2150PUFM, manufactured by Lantech Service Co., Ltd.) to form an alignment protective film of 2 μm, thereby manufacturing a pair. To the substrate.

(3) Production of display device A liquid crystal display element was produced by sandwiching a liquid crystal layer with an obtained counter substrate having an alignment protective film and an array substrate. As the liquid crystal layer, a person including a nematic liquid crystal and aligned in parallel with the substrate surface is used. The display characteristics and reliability were evaluated for these liquid crystal display elements.

(4) Evaluation The liquid crystal display element was allowed to stand in an oven at a temperature of 60 ° C / humidity of 90% for one week, and evaluation of re-driving was performed. The results are shown in Table 3 below. A: None of the display defects are generated. B: 1% or more to less than 10% of the pixels have caused display failure, but there is no problem in practical use. C: 10% or more of the pixels produced a poor display. D: Cannot be displayed shortly after manufacturing.

[table 3]

From the results shown in the first to third tables, it is understood that when the alignment protective layer does not have an alignment group, the fragment derived from the alignment group cannot be detected, and even if it is a liquid crystal display element immediately after fabrication, the display is performed. The characteristics were also inferior (Comparative Example 1 to Comparative Example 2). Further, in Comparative Example 3 and Comparative Example 4, the intensity ELq of the segment derived from the alignment group in the alignment protective layer was twice or more the intensity ESub, but the alignment group which was linked to each other via a covalent bond was not provided. Since it has a crosslinked structure, the display characteristics after exposure to high temperature and high humidity are inferior (Comparative Example 3 - Comparative Example 4). Further, it is understood that when a polymer having no bias-existing group for biasing the orientation group is used, the strength of the segment derived from the alignment group formed by the alignment layer is less than twice the intensity ESub. Even in the case of a liquid crystal display element which was just produced, the display characteristics were inferior (Comparative Example 5 to Comparative Example 6).

On the other hand, when a polymer having a constituent unit s1, a constituent unit a2, or the like and a polymer having the constituent unit a3 and the like without the constituent unit s1 are used, it is understood that the formed alignment protective layer has a covalent relationship. The alignment group and the cross-linking structure which are linked to each other by a bond, and the intensity ratio ELq of the mass spectrum of the fragment derived from the alignment group and the intensity ratio E strength (strength ESub) of the intensity ESub satisfy the predetermined conditions, and maintain excellent flatness. The performance was also good when exposed to high temperature and high humidity (Examples 1 to 24). In particular, according to the comparison between Example 1 and Example 24, it was found that when the crosslinking agent B having a molecular weight of 5,000 or less was blended, the flatness was improved and the display performance was further improved.

10‧‧‧Liquid crystal display device
12‧‧‧Backlight unit
14, 15‧‧‧Substrate
16‧‧‧film transistor
17‧‧‧ hardened film
18‧‧‧Contact hole
19‧‧‧ITO transparent electrode
20‧‧‧Liquid layer
21‧‧‧Alignment protective layer
22‧‧‧Color filters
23‧‧‧Alignment film
30‧‧‧1st substrate
40‧‧‧2nd substrate

1 is a schematic cross-sectional view showing an example of an embodiment of a liquid crystal display device of the present invention.

no

Claims (14)

A liquid crystal display device includes a first substrate, a liquid crystal layer, and a second substrate in order from the viewing side, wherein the first substrate includes a substrate and an alignment protective layer, and the second substrate includes a substrate, a thin film transistor, and a display electrode and an alignment film, wherein the alignment protective layer has a surface in contact with the liquid crystal layer, and the alignment protection layer has an alignment group and a crosslinked structure which are connected to each other via a covalent bond, and is related to a second time by flight time a fragment derived from the alignment group detected by ion mass spectrometry, an intensity ELq of a mass spectrum of a fragment derived from the alignment group in a surface of the alignment protective layer in contact with the liquid crystal layer, and The intensity ESub of the mass spectrum of the fragment derived from the alignment group in the surface on the substrate side of the alignment protective layer satisfies the following condition 1 or condition 2, and the crosslinked structure includes the following formula (A-1) Any one of the structures represented by the formula (A-3), Condition 1: The intensity ELq is twice to 20 times the intensity ESub; Condition 2: The intensity ELq is effectively measured, and the intensity ESub is below the measurement limit; Here, in the formula (A-1) to the formula (A-3), * represents a bonding position, and in the formula (A-3), R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. . The liquid crystal display device according to claim 1, wherein the intensity ELq is 5 to 20 times the intensity ESub. The liquid crystal display device according to claim 1 or 2, wherein the alignment group is a group obtained by reacting a photoalignment group. The liquid crystal display device according to claim 1 or 2, wherein the alignment protective layer has a film thickness of 1 μm to 4 μm. The liquid crystal display device according to claim 1 or 2, wherein the liquid crystal constituting the liquid crystal layer is a horizontal alignment liquid crystal. The liquid crystal display device of claim 1, wherein the excipient-derived fragment is derived from at least one selected from the group consisting of a cinnamate group and a chalcone group. A fragment of a photo-alignment group. A method for producing a liquid crystal display device, comprising: in the first step, forming a protective layer on a substrate using a composition for forming an alignment protective layer containing a polymer P and a polymer A, and then performing an alignment treatment on the protective layer Forming an alignment protective layer to form a first substrate, the polymer P comprising a constituent unit having an alignment group, the polymer A does not contain a constituent unit having an alignment group; and the second step, comprising a substrate, The second substrate of the thin film transistor, the display electrode, and the alignment film is adhered to the first substrate to seal the liquid crystal, and a liquid crystal layer is formed between the first substrate and the second substrate to fabricate a liquid crystal display device. The method for producing a liquid crystal display device according to claim 7, wherein the polymer P comprises a constituent unit represented by the following s1 as a constituent unit having the alignment group, and the polymer P and the The polymer A satisfies the following condition 3 or condition 4, and s1: a constituent unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a decane skeleton, and an alkyl group having 10 to 30 carbon atoms, And a constituent unit having a photo-alignment group. Condition 3: the polymer P contains a constituent unit a2 having a crosslinkable group, and the polymer A contains a constituent unit a3 having an acid group; Condition 4: the polymer P contains a constituent unit a3 having an acid group, and the polymer A contains a constituent unit a2 having a crosslinkable group. The method for producing a liquid display device according to claim 8, wherein the crosslinkable group is selected from the group consisting of oxiranyl, 3,4-epoxycyclohexyl, and oxetanyl. At least one of the groups. The method for producing a liquid crystal display device according to any one of claims 7 to 9, wherein a mass ratio of the polymer P to a total mass of the polymer P and the polymer A is Less than 10% by mass. The method for producing a liquid crystal display device according to any one of claims 7 to 9, wherein the composition for forming an alignment protective layer further contains a crosslinking agent B having a molecular weight of 5,000 or less. The method for producing a liquid crystal display device according to claim 11, wherein the crosslinking agent B comprises a crosslinking agent having an epoxy group, and the crosslinking agent B is relative to the crosslinking agent B, The mass ratio of the total mass of the polymer P and the polymer A is 30% by mass or less. The method for producing a liquid crystal display device according to any one of claims 7 to 9, wherein the alignment group is a photo-alignment group, and the alignment treatment uses light having a wavelength of 365 nm or less. Light alignment processing. The method of manufacturing a liquid crystal display device according to any one of claims 7 to 9, wherein the first step includes a step of performing heat treatment before or after the alignment treatment.