WO2017094490A1

WO2017094490A1 - Liquid crystal display apparatus and manufacturing method for liquid crystal display apparatus

Info

Publication number: WO2017094490A1
Application number: PCT/JP2016/083761
Authority: WO
Inventors: 山田　悟; 若彦金子; 秀人田鍋
Original assignee: 富士フイルム株式会社
Priority date: 2015-12-01
Filing date: 2016-11-15
Publication date: 2017-06-08
Also published as: CN108351558A; JP2017102258A; KR102061587B1; TW201728977A; JP6518184B2; KR20180067588A; TWI703373B

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 for manufacturing the liquid crystal display device.

Liquid crystal displays (LCDs) are widely used in monitors and television applications such as personal computers and smartphones because of their various advantages such as low voltage and low power consumption, and enabling miniaturization and thinning.
Such a liquid crystal display device has a liquid crystal cell and two polarizing plates disposed on both sides of the liquid crystal cell, and the liquid crystal cell is disposed to face each other with the liquid crystal layer and the liquid crystal layer interposed therebetween. The two substrates are generally provided with an alignment film for aligning the liquid crystal constituting the liquid crystal layer.

As a material for forming such an alignment film, for example, Patent Document 1 discloses that “a polymer having a silicone group or a fluorine-substituted alkyl group and a photoalignment group as a first component, and methacrylic acid and methacrylic acid as a second component”. "A photoalignable polymer composition comprising a non-photoalignable polymer obtained by polymerizing a monomer containing at least one selected from the group consisting of esters" ([Claim 1]). [Claim 28]).

JP 2013-177561 A

By the way, it is general that a liquid crystal display device is provided with a color filter on the viewing side. In addition, the color filter has a viewpoint of preventing permeation of impurities from the color filter and a viewpoint of flattening a step of the color filter. Therefore, it is known to provide a protective layer (overcoat layer).
Here, the present inventors examined providing an alignment film that does not require a protective layer when a color filter is provided on the viewing side, that is, an alignment protective layer having a function of the protective layer and the alignment film.
In addition, the inventors examined the alignment film described in Patent Document 1 as such an alignment protective layer, and the flatness may be inferior depending on the compounding agent of the photoalignable polymer composition, Also, it has been clarified that there is a problem that the display performance is inferior when the liquid crystal display device is exposed to high temperature and high humidity.
Therefore, the present invention provides a liquid crystal display device that maintains excellent flatness even when a color filter is provided on the viewing side, and has good display performance even when exposed to high temperature and high humidity, and its liquid crystal display device It is an object to provide a manufacturing method.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have provided an orientation protective layer having an orientation group and a cross-linked structure connected to each other through a covalent bond, and the surface in contact with the liquid crystal layer. It is found that even when a color filter is provided on the viewing side, the flatness is maintained even when the color filter is provided on the viewing side, and the display performance is improved even when exposed to high temperatures and high humidity. The present invention has been completed.
That is, it has been found that the above-described problem can be achieved by the following configuration.

[1] A liquid crystal display device having a first substrate, a liquid crystal layer, and a second substrate in this order from the viewing side,
The first substrate comprises a base material and an orientation protective layer,
The second substrate comprises a base material, a thin film transistor, a display electrode, and an alignment film,
The alignment protective layer has a surface in contact with the liquid crystal layer;
The alignment protective layer has an alignment group and a crosslinked structure linked to each other via a covalent bond;
For fragments derived from the orientation group detected by time-of-flight secondary ion mass spectrometry, the intensity ELq of the mass analysis of the fragment derived from the orientation group on the surface in contact with the liquid crystal layer of the orientation protection layer, and the orientation protection layer The strength ESsub of the mass spectrometry of the fragment derived from the orientation group on the surface of the base material side satisfies the following condition 1 or 2:
A liquid crystal display device, wherein the crosslinked structure includes any one of structures represented by formulas (A-1) to (A-3) described later.
Condition 1: The intensity ELq is 2 to 20 times the intensity ESub.
Condition 2: The intensity ELq is significantly measured and the intensity ESub is below the measurement limit.
[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] or [2], wherein the orientation group is a group obtained by photoreaction of 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 1 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 horizontally aligned liquid crystal.
[6] In any one of [1] to [5], the fragment derived from the orientation group is a fragment derived from at least one photoalignment group selected from the group consisting of a cinnamate group and a chalcone group. The liquid crystal display device described.

[7] Protection using a composition for forming an alignment protective layer containing a polymer P containing a structural unit having an orientation group and a polymer A not containing a structural unit having an orientation group on a substrate. A first step of forming a first substrate by forming an orientation protective layer by performing an orientation treatment on the protective layer after forming the layer;
A liquid crystal is sealed by bonding a second substrate having a base material, a thin film transistor, a display electrode, and an alignment film to the first substrate, and a liquid crystal layer is formed between the first substrate and the second substrate. And a second step of manufacturing the liquid crystal display device.
[8] The polymer P includes a structural unit represented by s1 below as a structural unit having an orientation group,
The method for producing a liquid crystal display device according to [7], wherein the polymer P and the polymer A satisfy the following condition 3 or 4.
s1: a structural unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton and an alkyl group having 10 to 30 carbon atoms, and a structural unit having a photoalignment group Condition 3: Heavy The coalescence P includes a structural unit a2 having a crosslinkable group, and the polymer A includes a structural unit a3 having an acid group.
Condition 4: The polymer P includes a structural unit a3 having an acid group, and the polymer A includes a structural unit a2 having a crosslinkable group.
[9] The method for producing a liquid display device according to [8], wherein the crosslinkable group is at least one selected from the group consisting of an oxiranyl group, a 3,4-epoxycyclohexyl group, and an oxetanyl group.
[10] The method for producing a liquid crystal display device according to any one of [7] to [9], wherein the mass ratio of the polymer P to the total mass of the polymer P and the polymer A is less than 10 mass%.
[11] The method for producing a liquid crystal display device according to any one of [7] to [10], wherein the composition for forming an alignment protective layer further contains a crosslinking agent B having a molecular weight of 5000 or less.
[12] The crosslinking agent B includes a crosslinking agent having an epoxy group,
The method for producing a liquid crystal display device according to [11], wherein the mass ratio of the crosslinking agent B to the total mass of the crosslinking agent B, the polymer P, and the polymer A is 30% by mass or less.
[13] The orientation group is a photo-alignment group,
The method for producing a liquid crystal display device according to any one of [7] to [12], wherein the alignment treatment is a photo-alignment treatment using light having a wavelength of 365 nm or less.
[14] The method for manufacturing a liquid crystal display device according to any one of [7] to [13], wherein the first step includes a step of performing a heat treatment before or after the alignment treatment.

According to the present invention, a liquid crystal display device that maintains excellent flatness even when a color filter is provided on the viewing side and has good display performance even when exposed to high temperature and high humidity, and its liquid crystal display device A manufacturing method can be provided.

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

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In this specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. 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 this specification, “(meth) acrylate” is a notation representing “acrylate” or “methacrylate”, “(meth) acryl” is a notation representing “acryl” or “methacryl”, and “(meth) The “) acryloyl” is a notation representing “acryloyl” or “methacryloyl”.

[Liquid Crystal Display]
The liquid crystal display device of the present invention is a liquid crystal display device having a first substrate, a liquid crystal layer, and a second substrate in this order from the viewing side, wherein the first substrate includes a base material and orientation protection. And the second substrate includes a base material, a thin film transistor, a display electrode, and an alignment film.
In the liquid crystal display device of the present invention, the orientation protective layer has a surface in contact with the liquid crystal layer, and any of the orientation groups and formulas (A-1) to (A-3) described later. And a structure in which the orientation group and the crosslinked structure are linked to each other through a covalent bond.
Furthermore, in the liquid crystal display device of the present invention, alignment protection is provided for fragments derived from alignment groups detected by time-of-flight secondary ion mass spectrometry (TOF-SIMS). The intensity ELq of the mass analysis of the fragment derived from the orientation group on the surface in contact with the liquid crystal layer of the layer and the intensity ESub of the mass analysis of the fragment derived from the orientation group on the substrate side surface of the orientation protective layer are as follows: Condition 1 or 2 is satisfied.
Condition 1: The intensity ELq is 2 to 20 times the intensity ESub.
Condition 2: The intensity ELq is significantly measured and the intensity ESub is below the measurement limit.

<TOF-SIMS measurement conditions>
The measurement by TOF-SIMS in the present invention is performed 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 (referring to the surface in contact with the liquid crystal layer; hereinafter the same) and the back surface of the alignment protective layer (base material) Or the surface in contact with the adjacent layer on the substrate side, the same shall apply hereinafter), derived from the orientation group on the surface of the orientation protective layer with the apparatus and conditions shown in (3) below. The mass analysis intensity ELq of the fragment to be analyzed and the mass analysis intensity ESsub of the fragment derived from the orientation group on the back surface of the alignment protective layer are measured.
(2) When the front and back surfaces of the alignment protective layer cannot be exposed, the cutting surface is determined by using the CYCUS method (Surface and Interfacial Cutting Analysis System: SAICAS) for the laminate having the alignment protective layer and the adjacent layer. Cutting is performed in an oblique direction so as to reach the front and back surfaces of the alignment protective layer, and the cross section of the alignment protective layer is exposed.
With respect to the exposed cross section, the intensity of the mass analysis of the fragment derived from the orientation group measured with the apparatus and conditions shown in (3) below in the depth (thickness) direction from the surface of the orientation protective layer is 10 nm. And the intensity of the mass analysis of the fragment derived from the orientation group measured in the depth (thickness) direction from the back surface of the orientation protective layer in the depth (thickness) direction using the apparatus and conditions shown in (3) below is defined as strength ESub.
(3) Measure with the following equipment and conditions.
・ Device: TOF-SIMS IV (made by ION-TOF)
Primary ion: Bi ³⁺ (beam diameter 2 μm)
・ Measurement range: raster scan of 256 points in each direction and orthogonal direction ・ Polarity: posi, negative

When the liquid crystal display device of the present invention is provided with the alignment protective layer described above, it maintains excellent flatness even when a color filter is provided on the viewing side, and when exposed to high temperature and high humidity. In addition, the display performance is good.
Although this is not clear in detail, the present inventors presume as follows.
That is, the alignment protective layer has a crosslinking structure containing an orientation group and any of the structures represented by formulas (A-1) to (A-3) described later. When the structure has a structure linked to each other through a covalent bond, and the strength ELq and the strength ESub by TOF-SIMS measurement satisfy the above condition 1 or 2, the orientation group is unevenly distributed on the surface of the orientation protective layer, And it is thought that the orientation group has couple | bonded firmly with the polymer which comprises an orientation protective layer.
Therefore, even when the orientation group is provided with a color filter on the back side of the orientation protective layer, the flatness is not impaired, and the orientation of the liquid crystal layer is maintained even when exposed to high temperature and high humidity. Therefore, the display performance is considered to be good.

In the present invention, it is preferable that the intensity ELq by the TOF-SIMS measurement is 5 to 20 times the intensity ESub because the display performance is improved even when exposed to high temperature and high humidity.

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

FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of the liquid crystal display device of the present invention.
The liquid crystal display device 10 illustrated in FIG. 1 includes a first substrate 30, a liquid crystal layer 20, and a second substrate 40 in this order from the viewing side.
The first substrate 30 is provided with a base material 15 to which a polarizing film is attached, an RGB color filter 22 on which a black matrix is disposed, and an alignment protective layer 21 having a surface in contact with the liquid crystal layer 20. .
In addition, the second substrate 40 is provided with the base material 14 to which the polarizing film is attached and the element of the thin film transistor 16. Each element formed on the substrate 14 is wired with an ITO transparent electrode 19 that forms a display electrode through 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, white LEDs (light emitting diodes), multicolor LEDs such as blue, red, and green, fluorescent lamps (cold cathode tubes), organic electroluminescence, and the like can be given.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and can be used as the second interphase insulating film (48) of JP 2011-145686A or the interphase insulating film (520) of JP 2009-258758A.

[First substrate]
The 1st board | substrate which the liquid crystal display device of this invention has is a board | substrate provided in the visual recognition side rather than the liquid crystal layer mentioned later, and comprises a base material and an orientation protective layer. Since the alignment protective layer has a surface in contact with a liquid crystal layer described later, the first substrate includes a base material and an alignment protective layer in this order from the viewing side.
When the liquid crystal display device of the present invention is provided with an arbitrary color filter on the viewing side, the first substrate includes a base material, a color filter, and an alignment protective layer in this order.

<Base material>
As the base material, a transparent substrate used in a liquid crystal cell of a conventionally known liquid crystal display device can be used. For example, a glass substrate, a quartz substrate, a transparent resin substrate, or the like can be used. Among these, it is preferable to use a glass substrate.

<Orientation protective layer>
As described above, the alignment protective layer has a surface in contact with a liquid crystal layer described later, and has an alignment group and any structure represented by formulas (A-1) to (A-3) described later. And having a structure in which the orientation group and the crosslinked structure are linked to each other through a covalent bond.

(Orienting group)
The alignment group possessed by the alignment protective layer is not particularly limited as long as it is a group in which a functional group having a function of aligning a liquid crystalline compound is aligned, but in the present invention, the alignment protective layer is brought into contact with the surface when the alignment protective layer is formed. However, it is preferably a group obtained by photoreacting a photoalignable group for the reason that it is possible to prevent deterioration of the surface state.

Here, the photoalignment group refers to a photoreactive group that imparts orientation by any of a photodimerization reaction, a photoisomerization reaction, and a photolysis reaction.
Examples of the group that imparts orientation by a photodimerization reaction include groups introduced from at least one derivative selected from the group consisting of maleimide derivatives, cinnamic acid derivatives, and coumarin derivatives. Preferred examples include cinnamate group and chalcone group.
In addition, as the cinnamate group and the chalcone group, for example, the following structure (in the following formula, * represents a connecting site to a polymer chain, and R represents a hydrogen atom or a monovalent organic group) is introduced. The connecting site to the polymer chain represented by * may be directly connected to the main chain of the polymer or may be bonded via a divalent linking group. The monovalent organic group represented by R is preferably an alkyl group or an aryl group. In addition, the monovalent organic group represented by R preferably has 1 to 10 carbon atoms, and more preferably 1 to 7 carbon atoms.

On the other hand, as the reactive group that isomerizes by the action of light, specifically, for example, a group composed of a skeleton of at least one compound selected from the group consisting of an azobenzene compound, a stilbene compound, and a spiropyran compound is preferable. It is mentioned in.
Specific examples of the reactive group capable of decomposing by the action of light include a group composed of a skeleton of a cyclobutane compound.

Among these, for reasons of irreversibility of the reaction, it is preferably a group that imparts orientation by a photodimerization reaction that reacts with shorter wave light, and is at least one selected from the group consisting of a cinnamate group and a chalcone group. More preferably.

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

In the above formulas (A-1) to (A-3), * represents a bonding position. In the above formula (A-3), each R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. To express.
Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, hexyl group and the like.

Here, examples of the crosslinked structure including the structures represented by the above formulas (A-1) to (A-3) include, for example, a crosslinkable group (for example, epoxy group, oxetanyl group) and an acid group (for example, carboxyl group). And the like, specifically, represented by the following formula (A-1-1), formula (A-2-1) and formula (A-3-1). A crosslinked structure is mentioned.
In the following formulas (A-1-1), (A-2-1), and (A-3-1), * represents a bonding position, and R in the following formula (A-3-1) ¹ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

As described above, the orientation protective layer has a structure in which the orientation group and the crosslinked structure are connected to each other through a covalent bond.
Therefore, in the present invention, a polymer containing a structural unit having a crosslinkable group (for example, an epoxy group, an oxetanyl group, etc.) described later, and / or a structural unit having an acid group (for example, a carboxyl group, etc.) described later. It is preferable that the polymer containing contains further the structural unit which has the said orientation group.

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

<Color filter>
The 1st board | substrate which the liquid crystal display device of this invention has may have comprised the color filter between the base material mentioned above and the alignment protective layer.
The color filter is not particularly limited, and, for example, a commonly known color filter for a liquid crystal display device can be used.
Such a color filter is usually composed of transparent colored patterns of red, green and blue, and each transparent colored pattern is made of a resin composition in which a colorant is dissolved or dispersed, preferably pigment fine particles are dispersed. Composed.
The color filter may be formed by preparing an ink composition colored in a predetermined color and printing it for each colored pattern. However, a paint-type photosensitive material containing a colorant of a predetermined color may be used. It is more preferable to carry out by a photolithography method using a conductive resin composition.

[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 described above and a second substrate described later.
Further, as described above, the liquid crystal layer is provided so as to be in contact with the alignment protective layer included in the first substrate described above.

Driving methods for driving the liquid crystal layer used in the liquid crystal display device of the present invention include TN (Twisted-Nematic) method, VA (Vertical-Alignment) method, IPS (In-Plane-Switching) method, FFS (Fringe-Field). Switching) method, OCB (Optically Compensated Bend) method, etc.

Among these driving methods, the IPS method is preferable.
In the IPS liquid crystal cell, rod-like liquid crystal molecules are aligned substantially parallel to the substrate, and the liquid crystal molecules respond in a planar manner when an electric field parallel to the substrate surface is applied. That is, in the IPS system, the liquid crystal constituting the liquid crystal layer is a horizontally aligned liquid crystal. In the IPS system, black is displayed when no electric field is applied, and the absorption axes of a pair of 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 described above, and includes a base material, a thin film transistor, a display electrode, and an orientation. And a membrane.

<Base material>
As the base material included in the second substrate, a transparent substrate used in a liquid crystal cell of a conventionally known liquid crystal display device can be used, for example, a glass substrate, a quartz substrate, a transparent substrate, as in the first substrate described above. A resin substrate or the like can be used. Among these, it is preferable to use a glass substrate.

<Thin film transistor>
As a thin film transistor (TFT) included in the second substrate, a thin film transistor (TFT) used in a known liquid crystal display device can be used as appropriate, and the configuration is not particularly limited. Or a bottom gate type.
Specific examples of the thin film transistor include an amorphous silicon TFT, a low temperature polysilicon TFT, an oxide semiconductor TFT, and the like.

<Display electrode>
As the display electrodes provided in the second substrate, those used in known liquid crystal display devices can be used as appropriate, and examples of the constituent material thereof include indium tin oxide (ITO) and oxidation. A transparent conductive material such as zinc aluminum (Aluminum doped Zinc Oxide: AZO) or indium zinc oxide (IZO) can be used.

<Alignment film>
As the alignment film provided in the second substrate, generally used as a main component of a polymer, which is used in a known liquid crystal display device, can be appropriately used.
The polymer material for alignment film is described in many documents, and many commercially available products can be obtained.
The polymer material used in the present invention is preferably polyvinyl alcohol or polyimide, and derivatives thereof. In particular, modified or unmodified polyvinyl alcohol is preferred.
With respect to the alignment film that can be used in the present invention, for example, an alignment film described in International Publication No. 01/88574, page 43, line 24 to page 49, line 8; Japanese Patent No. 3907735, paragraphs [0071] to [0095] Modified liquid alcohol described in JP-A-2012-155308, a liquid crystal alignment film formed by a liquid crystal alignment agent described in JP 2012-155308 A, and the like.

For other configurations of the liquid crystal display device (for example, a polarizing plate, a backlight, and the like), the descriptions in JP-A-2007-328210 and JP-A-2014-238438 can be referred to, and the contents thereof are incorporated in this specification. I will do it.

[Method for manufacturing liquid crystal display device]
The method for producing a liquid crystal display device of the present invention comprises an alignment protective layer containing, on a substrate, a polymer P containing a structural unit having an orientation group and a polymer A not containing a structural unit having an orientation group. After forming a protective layer using the composition for formation, the protective layer is subjected to an alignment treatment to form an alignment protective layer, and a first step of producing a first substrate is included.
In addition, the method for manufacturing a liquid crystal display device of the present invention includes a second substrate including a base material, a thin film transistor, a display electrode, and an alignment film, and a first substrate bonded to each other to enclose liquid crystal, A liquid crystal layer is formed between the second substrate and the second step of manufacturing a liquid crystal display device.

[First step]
The first step uses a composition for forming an alignment protective layer containing, on a substrate, a polymer P containing a structural unit having an orientation group and a polymer A not containing a structural unit having an orientation group. In this step, after forming the protective layer, the protective layer is subjected to an alignment treatment to form an alignment protective layer, thereby producing a first substrate.
In addition, the base material in a 1st process is the same as the base material with which the 1st board | substrate of the liquid crystal display device of this invention comprises.

<Orientation protective layer forming composition>
The composition for forming an alignment protective layer lowers the phase difference of the alignment protective layer, increases transparency, and facilitates the formation of the above-described crosslinked structure in the alignment protective layer. It is preferable that the structural unit represented by the following s1 is included as the structural unit having a group, and the polymer P and the polymer A satisfy the following condition 3 or 4.
s1: a structural unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton and an alkyl group having 10 to 30 carbon atoms, and a structural unit having a photoalignment group Condition 3: Heavy The coalescence P includes a structural unit a2 having a crosslinkable group, and the polymer A includes a structural unit a3 having an acid group.
Condition 4: The polymer P includes a structural unit a3 having an acid group, and the polymer A includes a structural unit a2 having a crosslinkable group.

In the present invention, the crosslinkable group possessed by the polymer P and / or the polymer A is an oxiranyl group, a 3,4-epoxycyclohexyl group, because the above-mentioned crosslinked structure is more easily formed in the alignment protective layer. And at least one selected from the group consisting of oxetanyl groups.

Hereinafter, specific examples of the polymer P and the polymer A contained in the composition for forming an alignment protective layer and optional additives will be described in detail.

(Polymer P)
As the polymer P, as described above, a polymer containing a structural unit represented by the following s1 (hereinafter also referred to as “structural unit s1”) is preferably exemplified.
s1: a structural unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton and an alkyl group having 10 to 30 carbon atoms (hereinafter also referred to as “unevenly-distributed group”), and Constituent unit having photo-alignment group

<< Constitutional unit having a partial structure of a fluorine-substituted hydrocarbon group >>
The fluorine-substituted hydrocarbon group may be a hydrocarbon group substituted with at least one fluorine atom, and is at least one of an alkyl group or an alkylene group (hereinafter abbreviated as “alkyl group etc.” in this paragraph). Examples include alkyl groups in which hydrogen atoms are substituted with fluorine atoms, and alkyl groups in which all hydrogen atoms such as alkyl groups are substituted with fluorine atoms are more preferable.

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

In the above formula (I), R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a site connected to a polymer chain. X represents a single bond or a divalent linking group, m represents an integer of 1 to 3, n represents an integer of 1 or more, and r represents 0 or an integer of 1 to 2. When m is 1, the plurality of R ² may be the same or different.

M in the above formula (I) represents an integer of 1 to 3, and is preferably 1 or 2.
N in the above formula (I) represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and particularly preferably 1 or 2.
R in the general formula I represents 0 or an integer of 1 to 2, preferably 1 or 2, and more preferably 2.
Further, the connecting part to the polymer chain represented by * may be directly connected to the main chain of the polymer such as the above-mentioned polymer A1-1, or a polyoxyalkylene group, an alkylene group, an ester group, a urethane group. And may be bonded via a divalent linking group such as a cyclic alkylene group which may contain a hetero atom, poly (caprolactone), or amino group. It is preferable that they are bonded via a polyoxyalkylene group.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ² in the above formula (I) include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and the like. Preferably, they are a hydrogen atom or a methyl group, More preferably, it is a hydrogen atom.
In the above formula (I), when X is a single bond, it means that the polymer main chain and the carbon atom to which R ² is bonded are directly connected.
When X is a divalent linking group, examples of the linking group include —O—, —S—, —N (R ⁴ ) —, —CO—, and the like. Among these, —O— is more preferable. Here, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group, and a hydrogen atom and a methyl group are preferable.

As a method of introducing a fluorine-substituted hydrocarbon group into a polymer, a method of introducing a fluorine-substituted hydrocarbon group into a polymer by a polymer reaction; a monomer having a fluorine-substituted hydrocarbon group (hereinafter referred to as “fluorine-substituted hydrocarbon group-containing” And a method of introducing a structural unit having a fluorine-substituted hydrocarbon group into the polymer.

In the method of copolymerizing a fluorine-substituted hydrocarbon group-containing monomer and introducing a structural unit having a fluorine-substituted hydrocarbon group into the polymer, the fluorine-substituted hydrocarbon group-containing monomer is a monomer represented by the following formula (II) Is preferable.

In the above 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. R ² , X, m, n and r all have the same meaning as R ² , X, m, n and r in formula I, and preferred examples are also the same.
As the halogen atom represented by R ¹ in the above-mentioned formula (II), for example, a fluorine atom, a chlorine atom, a bromine atom.

As for the method for producing such a fluorine-substituted hydrocarbon group-containing monomer, for example, “Synthesis and Function of Fluorine Compound” (Supervision: Nobuo Ishikawa, published by CMC Corporation, 1987), pages 117 to 118, “Chemistry of Organic Fluorine Compounds II” (Monograph 187, Ed by Milos Hudlicky and Attila E.Pavlath, American Chemical Society2), which is described in American 47-Chem.

Specific examples of the monomer represented by the above formula (II) include tetrafluoroisopropyl methacrylate represented by the following formula (IIa), hexafluoroisopropyl methacrylate represented by the following formula (IIb), and the like.
Other specific examples include compounds described in paragraph numbers [0058] to [0061] of JP 2010-18728 A. Of these, a structure in which a fluorine-substituted hydrocarbon group is bonded to a polyoxyalkylene group is preferable.

<< Constitutional Unit Having Partial Structure of 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, from the viewpoint of uneven distribution, the siloxane skeleton is copolymerized with a compound having a (meth) acryloyloxy group and an alkoxysilyl group and introduced into a constituent unit having a partial structure of the siloxane skeleton in the polymer. It is preferable.
Here, as the alkoxysilyl group, for example, a group represented by the following formula (X) is preferable.

In the above 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 is an alkoxy group. * Represents a binding position.

In the above 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, and an alkoxy group having 1 to 8 carbon atoms. It is more preferably a group, more preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably an ethoxy group or a methoxy group.
In the present invention, it is preferable that two of R ³ to R ⁵ are alkoxy groups and one is an alkyl group, or three are alkoxy groups. Among these, an embodiment in which three are alkoxy groups, that is, a trialkoxysilyl group is more preferable.

Specific examples of the compound having such an alkoxysilyl group and a (meth) acryloyloxy group include 3- (meth) acryloxypropylmethyldimethoxysilane and 3- (meth) acryloxypropyltrimethoxysilane. 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, and the like.

In the present invention, from the viewpoint of uneven distribution, the siloxane skeleton is polymerized with a compound represented by the following structural formula (A) (hereinafter also referred to as “specific siloxane compound”), and the siloxane skeleton is converted into a polymer. It is preferable to introduce.

In the structural formula (A), R ⁷ represents a linear or branched alkylene group having 2 to 6 carbon atoms which may have a substituent such as a hydroxyl group, an amine group, or a halogen atom, or the following structural formula (B ) Represents a divalent linking group.

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, two or more R ^{4 s} exist in the structural formula (B), but they may be different or the same.

In the structural formula (A), x1, x2 and x3 are integers whose sum satisfies 1 to 100.
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 alkylene group having 1 to 6 carbon atoms which may have a substituent such as a hydroxyl group, an amine group, or a halogen atom, and Q ¹ , Q ² represents an oxygen atom, a sulfur atom, or —NRB—, and Q ¹ and Q ² may be different from each other or the same. RB represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
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 formulas (D) to (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 y2 represents an integer of 1 to 100, preferably an integer of 1 to 50, more preferably 1 to 20 It is an integer.

Examples of the siloxane skeleton include the structures described in paragraphs [0092] to [0094] of JP 2010-18728 A, as specific examples of the above formula (A), but are not limited thereto. Absent.
Of these, a structure in which a siloxane structure is bonded to a polymer via a polyoxyalkylene group is preferable.

<< Structural unit having a partial structure of an alkyl group having 10 to 30 carbon atoms >>
The alkyl group having 10 to 30 carbon atoms may contain a branched structure or a cyclic structure, but the linear structure portion preferably has a carbon number in the range of 10 to 30, and all have a linear structure. Is more preferable.
In addition, the alkyl group preferably has 10 to 20 carbon atoms.

Specifically, the side chain of the polymer preferably has a group represented by the following general formula (a3-1).

In the general formula (a3-1), n _a3 represents an integer of 10 to 30, and * represents a position linked to the main chain or side chain of the polymer. _na3 is preferably an integer of 10 to 20.

There is no particular limitation on the method for introducing the structure of the general formula (a3-1) into the main chain or side chain of the polymer. For example, a monomer having the structure of (a3-1) is appropriately selected during synthesis and applied. In this case, the structure (a3-1) can be introduced into the repeating unit of the obtained polymer.
As the monomer having the structure of the general formula (a3-1), a commercially available compound can be used, but it is included in (a3-1) with respect to a commercially available monomer having no structure of (a3-1). A desired structure may be introduced as appropriate. There is no limitation on the method of introducing the structure (a3-1) into a commercially available monomer, and a known method may be applied as appropriate.

The monomer having the structure of the general formula (a3-1) can be appropriately selected according to the main chain structure of the polymer. For example, if the polymer has a (meth) acrylic structure in the main chain, the following general It is preferable to use a monomer represented by the formula (a3-2).

In the general 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 alkyleneoxy group. Represents. N _a3 has the same meaning as the general formula (a3-1), including the preferred range.

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

In the general formula (a3-2), examples of the divalent linking group as X ³¹ include —O—, —S—, —N (R ⁴ ) —, and the like. Among these, —O— is more preferable.
Here, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear structure or a branched structure, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group. Preferably, they are a hydrogen atom and a methyl group.

Further, the alkyleneoxy group for R ³³ preferably has 1 to 4 carbon atoms. The alkyleneoxy group may have a branched structure. Moreover, even if it has a substituent, it may be unsubstituted. Examples of the substituent that may have include a halogen atom. Specific examples of the alkyleneoxy group include a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, and the like.

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

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

In the general formula (U-a3-1), n _a3 has the same meaning as that of the general formula (a3-1), including a preferable range, and R ³² , X ³¹ , and R ³³ represent the general formula (a3- It is synonymous including 2) and a preferable range.

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

<< Structural Unit Having Photo-Orienting Group >>
The polymer P has a photoalignable group together with the above-described structural unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton, and an alkyl group having 10 to 30 carbon atoms. A polymer having units.
Here, the photo-alignment group is the same as that described for the orientation group.

The main chain skeleton of the polymer having a structural unit having a photo-alignment group is not particularly limited, but the side chain molecular design is diversified, and the main chain formation by radical polymerization reaction of an ethylenically unsaturated compound is simple. For the reason, a polymer having a repeating unit represented by the following formula (III) is preferable.

Here, in the formula (III), R ¹ represents a hydrogen atom or an alkyl group. X represents an arylene group, — (C═O) —O—, or — (C═O) —NR— (R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). L represents a single bond or a divalent linking group, and P represents a photoalignment group.

In the above formula (III), R ¹ represents a hydrogen atom or an alkyl group, and the alkyl group is an alkyl group having 1 to 4 carbon atoms (for example, methyl group, ethyl group, n-propyl group, isopropyl group, n- Butyl group and the like are preferable. R ¹ is preferably a hydrogen atom or a methyl group.
In the above formula (III), L represents a single bond or a divalent linking group, and the divalent linking group may be —O—, —S—, an alkylene group, an arylene group, or a combination thereof. Is preferred. The alkylene group represented by L may be a linear, branched, or cyclic structure, but is preferably a linear structure. The alkylene group represented by L preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms. Moreover, as an arylene group which L represents, a phenylene group, a tolylene group, a xylylene group etc. are mentioned, A phenylene group is preferable.
In the above formula (III), P represents a photoalignable group, and specific examples thereof include a chalcone group, a cinnamate group, a stilbenyl group, a maleimide group, and an azobenzyl group. Of these, chalcone groups and cinnamate groups are more preferred. In addition, the photoalignable group represented by P may have a substituent as long as the photoalignment is not lost. Specific examples of the substituent include a halogeno group, an alkyl group, and an aryl group, and an alkyl group or an aryl group is preferable. The alkyl group or aryl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 7 carbon atoms.

Hereinafter, preferred specific examples of the polymer having a repeating unit represented by the above formula (III) are shown, but the present invention is not limited thereto.

The polymer having a repeating unit represented by the above formula (I) may be synthesized by (a) a method in which a corresponding monomer is polymerized to directly introduce a photoreactive group, and (b) any functional group. It may be synthesized by a method in which a photoreactive group is introduced into a polymer obtained by polymerizing a monomer having a polymer reaction. Moreover, it can also synthesize | combine combining the method of (a) and (b).
Here, radical polymerization, cation polymerization, anion polymerization, etc. are mentioned as a polymerization reaction which can be utilized in the method of (a) and (b) mentioned above.

The polymer having a repeating unit represented by the above formula (I) may be a copolymer composed of a plurality of types of repeating units represented by the above formula (I). ) May be a copolymer containing a repeating unit other than (for example, a repeating unit not containing an ethylenically unsaturated group).

{Preferred embodiment of the structural unit s1}
The structural unit s1 is preferably 0.01 to 10% by mole, more preferably 0.1 to 10% by mole, still more preferably 0.1 to 5% by mole, based on the structural unit of all polymer components. 1 to 3 mol% is particularly preferred, and 0.5 to 3 mol% is most preferred.
In the structural unit s1, the content of the structural unit having a ubiquitous group is preferably 0.01 to 3% by mole, more preferably 0.1 to 3% by mole, and 0.5 to 3% by mole. Is more preferable.
In the structural unit s1, the content of the structural unit having a photo-alignment group is preferably 0.01 to 5% by mole, more preferably 0.1 to 5% by mole, and 1 to 3% by mole. Further preferred.
In the polymer having the structural unit s1, the content of the structural unit s1 is preferably 20 to 90% by mole, more preferably 20 to 80% by mole, and more preferably 20 to 70% by mole based on all the structural units of the polymer. Is more preferable. In this case, the content of the structural unit having a ubiquitous group is preferably 1 to 50 mol%, more preferably 5 to 30 mol%, and still more preferably 10 to 20 mol%. In addition, the content of the structural unit having a photoalignable group is preferably 1 to 70 mol%, more preferably 10 to 60 mol%, still more preferably 20 to 50 mol%.
In the present invention, when the content of the “structural unit” is defined in terms of molar ratio, the “structural unit” is synonymous with the “monomer unit”. In the present invention, the “monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.

<< Other structural units >>
Examples of the polymer P include, in addition to the structural unit s1 described above, a structural unit a1 having a group in which an acid group is protected by an acid-decomposable group, a structural unit a2 having a crosslinkable group, and a structural unit having an acid group. a3, other structural units a4 may be included.
Among these structural units, as described above, the structural unit a2 having a crosslinkable group and / or the structural unit a3 having an acid group is included for the reason that the above-described crosslinked structure is easily formed in the alignment protective layer. Is preferred.

<<< Structural Unit a1 >>>
The structural unit a1 is a structural unit having an acid group protected with an acid-decomposable group (hereinafter also referred to as the structural unit a1).
The “group in which an acid group is protected with an acid-decomposable group” in the present invention is a group that causes a deprotection reaction using an acid as a catalyst (or an initiator) to generate an acid group, a regenerated acid, and a decomposed structure. Means.
As the “group in which the acid group is protected with an acid-decomposable group” in the present invention, those known as an acid group and an acid-decomposable group can be used, and are not particularly limited.
Preferred examples of the acid group include a carboxyl group and a phenolic hydroxyl group.
In addition, as an acid-decomposable group, a group that is relatively easily decomposed by an acid (for example, an acetal functional group such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group) or an acid-decomposable group is relatively difficult to decompose by an acid. Groups (for example, tertiary alkyl groups such as tert-butyl ester groups and tertiary alkyl carbonate groups such as tert-butyl carbonate groups).

The structural unit a1 having a group in which an acid group is protected with an acid-decomposable group is a structural unit having a protected carboxyl group in which a carboxyl group is protected with an acid-decomposable group (hereinafter referred to as “protection protected with an acid-decomposable group”). Or a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected with an acid-decomposable group (hereinafter referred to as “protected phenolic hydroxyl group protected with an acid-decomposable group”). It is also preferable that it is also referred to as a “structural unit”.
Hereinafter, the structural unit a1-1 having a protected carboxyl group protected with an acid-decomposable group and the structural unit a1-2 having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in order.

{Structural unit a1-1 having a protected carboxyl group protected with an acid-decomposable group}
The structural unit a1-1 having a protected carboxyl group protected with an acid-decomposable group has a carboxyl group in the structural unit having a carboxyl group as a protected carboxyl group protected by an acid-decomposable group described in detail below. It is a structural unit.
The structural unit having a carboxyl group that can be used for the structural unit a1-1 having a protected carboxyl group protected by the acid-decomposable group is not particularly limited, and a known structural unit can be used. For example, the structural unit a1-1-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid; And a structural unit a1-1-2 having both an unsaturated group and a structure derived from an acid anhydride.
Hereinafter, a structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the a1-1-1 molecule used as the structural unit having a carboxyl group, and an a1-1-2 ethylenically unsaturated group And the structural unit having both the structure derived from acid anhydride and the structure derived from acid anhydride will be described in order.

{{Structural unit a1-1-1 derived from unsaturated carboxylic acid having at least one carboxyl group in the molecule}}
Examples of the unsaturated carboxylic acid used in the present invention as the structural unit a1-1-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule include those described in JP-A-2014-238438. And the compounds described in paragraph 0043.
Among these, from the viewpoint of developability, in order to form the structural unit a1-1-1, acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxy are used. It is preferable to use ethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, or an anhydride of an unsaturated polyvalent carboxylic acid. Acrylic acid, methacrylic acid, 2- (meth) acryloyloxy More preferably, ethylhexahydrophthalic acid is used.
The structural unit a1-1-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule may be composed of one kind alone, or may be composed of two or more kinds. Good.

{{Structural unit a1-1-2 having both an ethylenically unsaturated group and a structure derived from an acid anhydride}}
The structural unit a1-1-2 having both an ethylenically unsaturated group and a structure derived from an acid anhydride is obtained by reacting a hydroxyl group present in a structural unit having an ethylenically unsaturated group with an acid anhydride. The unit is preferably derived from a monomer.
As the acid anhydride, known ones can be used, and specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, etc. Dibasic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, and the like. Among these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
The reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol% from the viewpoint of developability.

(Acid-decomposable group that can be used for the structural unit a1-1)
As the acid-decomposable group that can be used for the structural unit a1-1 having a protected carboxyl group protected by the acid-decomposable group, the above-mentioned acid-decomposable groups can be used.
Among these acid-decomposable groups, the carboxyl group is a protected carboxyl group protected in the form of an acetal, so that the basic physical properties of the resin composition, particularly sensitivity and pattern shape, contact hole formation, and storage of the resin composition It is preferable from the viewpoint of stability. Furthermore, among the acid-decomposable groups, the carboxyl group is more preferably a protected carboxyl group protected in the form of an acetal represented by the following formula (a1-10) from the viewpoint of sensitivity. In the case where the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following formula a1-10, the entire protected carboxyl group is — (C═O) —O—CR ¹⁰¹ R ¹⁰² ( OR ¹⁰³ ).

In the above formula (a1-10), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or a hydrocarbon group, except that R ¹⁰¹ and R ¹⁰² are both hydrogen atoms. R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to form a cyclic ether.

In the above formula (a1-10), R ¹⁰¹ and R ¹⁰² each independently represents a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched or cyclic. Here, both R ¹⁰¹ and R ¹⁰² do not represent a hydrogen atom, and at least one of R ¹⁰¹ and R ¹⁰² represents an alkyl group.

In the above formula (a1-10), when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an alkyl group, the alkyl group may be linear, branched or cyclic.
The linear alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. The branched chain preferably has 3 to 6 carbon atoms, and more preferably has 3 or 4 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.

The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When it has a halogen atom as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become a haloalkyl group, and when it has an aryl group as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become an aralkyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Specific examples include a phenyl group, an α-methylphenyl group, a naphthyl group, and the like, and examples of the entire alkyl group substituted with an aryl group, that is, an aralkyl group include a benzyl group, an α-methylbenzyl group, a phenethyl group, A naphthylmethyl group etc. can be illustrated.
The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, and still more preferably a methoxy group or an ethoxy group.
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 is a linear chain. Or a branched alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent.
These substituents may be further substituted with the above substituents.

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

R ¹⁰¹ , R ¹⁰² and R ¹⁰³ can be bonded together to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ¹⁰³ or R ¹⁰² and R ¹⁰³ are bonded include, for example, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.

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

As the radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the above formula (a1-10), a commercially available one may be used, or one synthesized by a known method Can also be used. For example, it can be synthesized by the synthesis method described in paragraphs 0037 to 0040 of JP2011-212494A.

A first preferred embodiment of the structural unit a1-1 having a protected carboxyl group protected by the acid-decomposable group is a structural unit represented by the following formula.

In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least ^one of R ¹ and R ² is an alkyl group or an aryl group, and R ³ is an alkyl group or Represents an aryl group, R ¹ or R ² and R ³ may be linked to form a cyclic ether, R ⁴ represents a hydrogen atom or a methyl group, and X represents a single bond or an arylene group;

When R ¹ and R ² are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are preferably each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
X represents a single bond or an arylene group, and a single bond is preferable.

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

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

As preferred specific examples of the structural unit a1-1 having a protected carboxyl group protected by the acid-decomposable group, the following structural units can be exemplified. R represents a hydrogen atom or a methyl group.

{Structural unit a1-2 having a protected phenolic hydroxyl group protected with an acid-decomposable group}
Examples of the structural unit a1-2 having a protected phenolic hydroxyl group protected with an acid-decomposable group include a structural unit in a hydroxystyrene-based structural unit and a novolac-based resin.
Of these, a structural unit derived from hydroxystyrene or α-methylhydroxystyrene is preferred from the viewpoint of sensitivity.
As the structural unit having a phenolic hydroxyl group, the structural units described in paragraphs 0065 to 0073 of JP-A-2014-238438 are also preferable from the viewpoint of sensitivity.

<<< Structural Unit a2 >>>
The structural unit a2 is a structural unit having a crosslinkable group (hereinafter also referred to as a structural unit a2).
The crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment.
Preferred embodiments of the structural unit having a crosslinkable group include an epoxy group (for example, oxiranyl group, 3,4-epoxycyclohexyl group, etc.), oxetanyl group, —NH—CH ₂ —O—R (R is a hydrogen atom or carbon atom) And a structural unit containing at least one selected from the group consisting of a group represented by formula (1) to (20), an ethylenically unsaturated group, and a blocked isocyanate group, such as an epoxy group and an oxetanyl group. A group represented by the group: —NH—CH ₂ —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms), a (meth) acryloyl group, and a blocked isocyanate group. is preferably a structural unit containing at least one selected, epoxy group, oxetanyl group, _{and, -NH-CH 2 -O-R} (R is a hydrogen atom or a carbon atoms ~ And more preferably a structural unit containing at least one selected from the group consisting of groups represented by.) Represents an alkyl group of 20.

{Structural unit a2-1 having an epoxy group and / or an oxetanyl group}
The polymer component A1 preferably contains a polymer having a structural unit a2-1 having an epoxy group and / or an oxetanyl group. A 3-membered cyclic ether group is also called an epoxy group, and a 4-membered cyclic ether group is also called an oxetanyl group.
The structural unit a2-1 having an epoxy group and / or oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, and may be one or more epoxy groups and one or more oxetanyl groups. Group, two or more epoxy groups, or two or more oxetanyl groups may be included, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups. It is more preferable to have one or two oxetanyl groups in total, and it is even more preferable to have one epoxy group or oxetanyl group.

Specific examples of the radical polymerizable monomer used for forming the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl methacrylate Methyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, described in paragraphs 0031 to 0035 of Japanese Patent No. 4168443 Alicyclic epoch Such compounds may be mentioned containing shea skeleton, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include, for example, a (meth) acryl having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953. Acid esters, and the like, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit a2-1 having the epoxy group and / or oxetanyl group include a monomer having a methacrylic ester structure and an acrylic ester structure. A monomer is preferred.

Among these, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, (3-ethyloxetane-3-yl) methyl acrylate, and methacrylic acid ( 3-ethyloxetane-3-yl) methyl. These structural units can be used individually by 1 type or in combination of 2 or more types.

As preferred specific examples of the structural unit a2-1 having an epoxy group and / or oxetanyl group, the following structural units can be exemplified. R represents a hydrogen atom or a methyl group.

{Structural unit a2-2 having an ethylenically unsaturated group}
Another example of the structural unit a2 having a crosslinkable group includes the structural unit a2-2 having an ethylenically unsaturated group. The structural unit a2-2 having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in the side chain, having an ethylenically unsaturated group at the terminal, and having 3 to 16 carbon atoms. The structural unit having

In addition, regarding the structural unit a2-2 having an ethylenically unsaturated group, refer to the description in paragraphs 0072 to 0090 of JP2011-215580A and the description of paragraphs 0013 to 0031 in JP2008-256974A. The contents of which are incorporated herein by reference.

{Structural unit a2-3 having a group represented by —NH—CH ₂ —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms)}
Another example of the structural unit a2 having a crosslinkable group has a group represented by —NH—CH ₂ —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). The structural unit a2-3 is also preferable. By having the structural unit a2-3, a curing reaction can be caused by a mild heat treatment, and a cured film having excellent 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. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group. The structural unit a2-3 is more preferably a structural unit having a group represented by the following formula (a2-30).

In the above 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. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
Specific examples of R ³² include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl group, n-butyl group and methyl group are preferable.

<<< Structural Unit a3 >>>
The structural unit a3 is a structural unit having an acid group (hereinafter also referred to as a structural unit a3).
The acid group in the present invention means a proton dissociable group having a pKa smaller than 11.
Examples of the acid group used in the present invention include a carboxylic acid group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, a sulfonamide group, a sulfonylimide group, and acid anhydride groups of these acid groups, And the group etc. which neutralized these acid groups and made it into salt structure are illustrated, and a carboxylic acid group and / or a phenolic hydroxyl group are preferable. Although there is no restriction | limiting in particular as said salt, An alkali metal salt, alkaline-earth metal salt, and organic ammonium salt can illustrate preferably.
The structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. . For example, compounds described in paragraphs 0021 to 0023 and paragraphs 0029 to 0044 of JP2012-88459A can be used, the contents of which are incorporated herein. Of these, structural units derived from p-hydroxystyrene, (meth) acrylic acid, maleic acid, and maleic anhydride are preferred.

As the structural unit a3 having an acid group, from the viewpoint of sensitivity, a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group is preferable, and a structural unit having a carboxyl group is more preferable.
Specific examples of the structural unit a3 having an acid group include the structural unit a1-1-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, an ethylenically unsaturated group, and an acid anhydride. Examples thereof include a structural unit a1-1-2 having both a structure derived from a product and a structural unit a1-2-1 having a phenolic hydroxyl group, and preferred embodiments are also the same.
Among them, the structural unit a3 having an acid group is a structural unit derived from a compound selected from the group consisting of methacrylic acid, acrylic acid and p-hydroxystyrene [of the following formulas (a3-1) to (a3-3): A structural unit represented by any of the above formulas, preferably a structural unit derived from methacrylic acid [a structural unit represented by the following formula (a3-1)] or a structural unit derived from acrylic acid [the following formula (a3-2) Is more preferably a structural unit derived from methacrylic acid [a structural unit represented by the following formula (a3-1)].

<<< Structural Unit a4 >>>
There is no restriction | limiting in particular as a monomer used as the structural unit a4 other than the structural unit s1, the structural unit a1, the structural unit a2, and the structural unit a3, for example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic Examples include acid cyclic alkyl esters, (meth) acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, and unsaturated aromatic compounds.
The monomer which forms the other structural unit a4 can be used individually by 1 type or in combination of 2 or more types.

Specific examples of the other structural unit a4 include styrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, 4-hydroxybenzoic acid ( 3-methacryloyloxypropyl) ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth And a structural unit such as 2-hydroxypropyl acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate, and the like. In addition, compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.

As the other structural unit a4, a structural unit derived from a monomer having a styrene or an aliphatic cyclic skeleton is preferable from the viewpoint of electrical characteristics. Specific examples include styrene, methylstyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate.

Furthermore, as other structural unit a4, a structural unit derived from (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable. In all the structural units constituting the polymer, the content of the structural unit a4 is preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less. As a lower limit, although 0 mol% may be sufficient, it is preferable to set it as 1 mol% or more, for example, and it is more preferable to set it as 5 mol% or more. Within the above numerical range, various properties of the cured film obtained from the resin composition are improved.

(Polymer A)
Examples of the polymer A include a polymer that does not include the above-described structural unit s1, but includes any one or more of the above-described structural units a1 to a4. A polymer having a structural unit a2 having a crosslinkable group and / or a structural unit a3 having an acid group is preferable because the above-described crosslinked structure is easily formed in the layer.

<< Molecular weight >>
The molecular weight of the above-mentioned polymer P and polymer A is a polystyrene-converted weight average molecular weight, preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and still more preferably 10,000 to 20,000. 000 range. Various characteristics are favorable in the range of said numerical value. The ratio (dispersity, Mw / Mn) between the number average molecular weight Mn and the weight average molecular weight Mw is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.
In addition, it is preferable to measure the weight average molecular weight and the number average molecular weight in the present invention by a gel permeation chromatography (GPC) method. In the measurement by gel permeation chromatography in the present invention, HLC-8020GPC (manufactured by Tosoh Corporation) is used, and TSKgel Super HZ MH, TSK gel Super HZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation), 4.6 mmID are used as columns. It is preferable to use THF (tetrahydrofuran) as an eluent.

<< Preparation method >>
Various methods for synthesizing the above-described polymer P and polymer A are also known. However, for example, the polymer P and the polymer A include a radical polymerizable monomer used to form each structural unit described above. It can be synthesized by polymerizing a radical polymerizable monomer mixture in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.

In the present invention, in order to keep the retardation (Rth) in the thickness direction low, the mass ratio of the polymer P to the total mass of the polymer P and the polymer A described above is preferably less than 10% by mass. More preferably, the content is 1 to 5% by mass.

(Crosslinking agent B)
In the present invention, the alignment protective layer has a molecular weight of 5000 or less because the flatness when a color filter is provided on the viewing side is improved and the display performance after being exposed to high temperature and high humidity becomes better. It is preferable to contain the crosslinking agent B.
As the crosslinking agent B, any crosslinking agent can be used as long as it causes a crosslinking reaction by heat.
For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, a blocked isocyanate compound (a compound having a protected isocyanato group), an alkoxymethyl group-containing compound, or at least one ethylenic group. It is preferably at least one selected from the group consisting of saturated double bonds (ethylenically unsaturated groups), from a group consisting of compounds having two or more epoxy groups or oxetanyl groups in the molecule, and blocked isocyanate compounds. More preferably, it is at least one selected.
Below, the crosslinking agent B preferably used in this invention is demonstrated.

<< Compound having two or more epoxy groups or oxetanyl groups in the molecule >>
Examples of the crosslinking agent B include polyfunctional small ring cyclic ether compounds.
That is, it means a compound having two or more epoxy groups and / or oxetanyl groups in one molecule.

Specific examples of the compound having two or more epoxy groups in the molecule include aliphatic epoxy compounds.
These are available as commercial products. For example, Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321 , EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX -920, EX-931, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301 DLC-402 (manufactured by Nagase ChemteX Corporation), Celoxide 2021P, 2081, 3000, EHPE31 0, Epolead GT400, Serubinasu B0134, B0177 ((Ltd.) manufactured by Daicel), and the like.
These can be used alone or in combination of two or more.

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

In addition, the compound containing an oxetanyl group is preferably used alone or mixed with a compound containing an epoxy group.

<< Block isocyanate compound >>
As the crosslinking agent B, a blocked isocyanate compound can also be preferably employed.
The blocked isocyanate compound is not particularly limited as long as the isocyanate group has a chemically protected blocked isocyanate group, but is a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability. It is preferable.
In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably. The blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
Further, the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and may be aliphatic, alicyclic or aromatic. Polyisocyanates may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2, '-Diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1, 4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3′-methylene ditolylene-4,4′-diisocyanate, 4,4′-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate, Isocyanate compounds such as hydrogenated 1,3-xylylene diisocyanate and hydrogenated 1,4-xylylene diisocyanate In addition, a prepolymer type skeleton compound derived from these compounds can be preferably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.

Examples of the matrix structure of the blocked isocyanate compound include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.

Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
As said amine compound, a primary amine and a secondary amine are mentioned, Any of an aromatic amine, an aliphatic amine, and an alicyclic amine may be sufficient, An aniline, diphenylamine, ethyleneimine, polyethyleneimine etc. can be illustrated.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like. Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.

The blocked isocyanate compound is available as a commercial product. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (above, manufactured by Nippon Polyurethane Industry Co., Ltd.), Takenate B -830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (manufactured by Mitsui Chemicals, Inc.), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above, manufactured by Asahi Kasei Chemicals Corporation), Death Module BL1100, BL1265 MPA / X BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co.) can be preferably used, and the like.

<< Alkoxymethyl group-containing crosslinking agent >>
As the alkoxymethyl group-containing compound, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferable. These can be obtained by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylolated urea to an alkoxymethyl group, respectively. The type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. From the viewpoint of outgas generation amount, A methyl group is particularly preferred.
Among these compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycoluril are preferable compounds, and alkoxymethylated glycoluril is particularly preferable from the viewpoint of transparency.
As the alkoxymethyl group-containing crosslinking agent, a compound having a molecular weight of 1,000 or less is used for the curable composition.
These alkoxymethyl group-containing compounds are available as commercial products. For example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid), Nicarax MX-750, -032, -706, -708, -40, -31, -270, -280, -290, Nicarak MS-11, Nicarak MW-30HM, -100LM, -390, (manufactured by Sanwa Chemical Co., Ltd.) and the like can be preferably used.

In the present invention, it is preferable to use a crosslinking agent having an epoxy group as the crosslinking agent B.
Further, when the crosslinking agent B is contained, the content is preferably 30% by mass or less, and preferably 10 to 30% by mass with respect to the total mass of the crosslinking agent B, the polymer P and the polymer A. More preferred.

(Organic solvent)
The protective layer-forming composition preferably contains an organic solvent in addition to the polymer described above.
As the organic solvent, known organic solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene. Glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, butylene glycol diacetates, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, alcohol , Esters, ketones, amides, lactones, etc. Kill. As specific examples of these organic solvents, reference can be made to paragraph 0062 of JP-A-2009-098616.

Preferred examples include propylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, 1,3-butylene glycol diacetate, methoxypropyl acetate, cyclohexanol acetate, propylene glycol diacetate, tetrahydroflur Examples include furyl alcohol.

The boiling point of the organic solvent is preferably 100 ° C. to 300 ° C., more preferably 120 ° C. to 250 ° C. from the viewpoint of applicability.
The organic solvent which can be used for this invention can be used individually by 1 type or in combination of 2 or more types. It is also preferred to use solvents having different boiling points in combination.
In the case of containing an organic solvent, the content is preferably from 100 to 3,000 parts by mass, preferably from 200 to 2 parts per 100 parts by mass of the total solid content of the composition, from the viewpoint of adjusting the viscosity to be suitable for coating. More preferably, it is 1,000,000 parts by mass, and even more preferably 250-1,000 parts by mass.
The solid content concentration of the composition is preferably 3 to 50% by mass, and more preferably 20 to 40% by mass.

(Surfactant)
The protective layer forming composition may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. As the surfactant, nonionic surfactants are preferable, and fluorine-based surfactants are more preferable.
As the surfactant that can be used in the first embodiment, for example, commercially available products such as Megafac F142D, F172, F173, F176, F177, F183, F479, F482, F554, F780, F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (manufactured by DIC Corporation), Florard FC-135, FC- 170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC -105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, 802 (manufactured by Mitsubishi Materials Denka Kasei), and Footgent 250 (manufactured by Neos Co., Ltd.) It is done. In addition to the above, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Mitsubishi Materials Denka Kasei Co., Ltd.), MegaFuck (manufactured by DIC Corporation) , FLORARD (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and the like.

As the surfactant, compounds described in paragraphs 0151 to 0155 of JP-A-2014-238438 can also be mentioned as preferred examples.

When the surfactant is contained, the content is preferably 0.001 to 5.0 parts by mass and more preferably 0.01 to 2.0 parts by mass with respect to 100 parts by mass in the total solid content of the composition. .
Only one type of surfactant may be included, or two or more types of surfactants may be included. When two or more types are included, the total amount is preferably within the above range.

(Adhesion improver)
The protective layer forming composition may contain an adhesion improving agent.
Examples of the adhesion improving agent include alkoxysilane compounds.
The alkoxysilane compound is a compound that improves the adhesion between an insulating material and an inorganic material serving as a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum. It is preferable.
Specific examples of the adhesion improver include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycol. Sidoxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, β- (3,4-epoxy (Cyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane and the like. Of these, γ-glycidoxypropyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane are preferred, and γ-glycidoxypropyltrimethoxysilane is more preferred. These can be used alone or in combination of two or more.
The content of the adhesion improving agent is preferably 0.001 to 15 parts by mass, and more preferably 0.005 to 10 parts by mass with respect to 100 parts by mass of the total solid components of the composition. Only one type of adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.

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

<Formation of protective layer>
Although the method in particular of forming a protective layer on a base material is not restrict | limited, For example, the method of apply | coating the said composition for protective layer formation on a base material is mentioned.

(Application)
The method for applying the protective layer-forming composition on the substrate is not particularly limited. Specifically, for example, a printing method (for example, gravure printing method, screen printing method, flexographic printing method, inkjet printing method, imprinting) Method), spin coating method, slit coating method, slit and spin coating method, dip coating method, curtain coating method and the like.

(Solvent removal)
In this invention, it is after the application | coating mentioned above, Comprising: You may have the solvent removal process which removes the arbitrary solvents contained in the composition for protective layer formation from a membrane | film | coat before the orientation process process mentioned later. .
The solvent removal step varies depending on the type and amount of the solvent. For example, when NMP is used as the solvent, it is a step of heating at about 80 to 150 ° C. for about 0.5 to 3 minutes. The step of heating at about 90 to 120 ° C. for about 0.5 to 2 minutes is more preferable.

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

(Photo-alignment treatment)
In the present invention, when the orientation group is a photo-alignment group, the orientation treatment is preferably a photo-alignment treatment using light having a wavelength of 365 nm or less.
The photo-alignment treatment is not particularly limited except that light having a wavelength of 365 nm or less is used, but it is preferable to use polarized ultraviolet rays for obtaining uniform alignment. In this case, the method of irradiating polarized ultraviolet rays is not particularly limited. In addition, there is no restriction | limiting in particular as polarized light, For example, linearly polarized light, circularly polarized light, elliptically polarized light etc. are mentioned, Among these, linearly polarized light is preferable.

Further, it is only necessary to obtain substantially polarized light, and non-polarized light may be irradiated at an angle inclined from the normal line of the thin film. In other words, non-polarized light may be irradiated from an oblique direction on the surface of the thin film. “Inclined irradiation” is not particularly limited as long as it is a direction inclined by a polar angle θ (0 <θ <90 °) with respect to the normal direction of the thin film surface, and can be appropriately selected according to the purpose. However, θ is preferably 20 to 80 °.

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

<Heat treatment>
In the present invention, from the viewpoint of increasing the reliability of the thin film transistor, the first step is preferably a step of performing a heat treatment before or after the alignment treatment.

As a method of performing the heat treatment, for example, a method of heating the protective layer or the alignment protective layer subjected to the alignment treatment at a temperature of 180 to 350 ° C., preferably 200 to 300 ° C., for 20 to 60 minutes is preferable. It is mentioned in.
The heat treatment is preferably performed using a heating device such as a hot plate or an oven. Further, the transparency can be further improved by performing the heat treatment in a nitrogen atmosphere.

[Second step]
In the second step, the liquid crystal is sealed by bonding the second substrate having the base material, the thin film transistor, the display electrode, and the alignment film together with the first substrate, and between the first substrate and the second substrate. Forming a liquid crystal layer and manufacturing a liquid crystal display device;
Note that the second substrate in the second step is similar to the second substrate of the liquid crystal display device of the present invention, and a manufacturing method thereof is not particularly limited.

The method for encapsulating the liquid crystal in the second step is not particularly limited. For example, a method for encapsulating the liquid crystal in the formed space after the spacer is formed between the first substrate and the second substrate described above. Is mentioned.

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples. Unless otherwise specified, “part” and “%” are based on mass.

[Synthesis of a structural 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 (manufactured by Wako Pure Chemical Industries, Ltd., 7.79 g, 0.07 mol) were added to tetrahydrofuran (hereinafter referred to as “tetrahydrofuran”). , And abbreviated as “THF”) After dissolving in 100 mL and cooling to 0 ° C., methacrylic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd., 7.33 g, 0.07 mol) was gradually added dropwise.
Next, 500 g of water was added to the cloudy reaction system and stirred for 1 hour, followed by filtration to obtain 14 g of monomer a-1 having a cinnamate group as a photoaligning group. The structure was confirmed by NMR (nuclear magnetic resonance).

[Synthesis of a structural 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 dissolved in 150 mL of dimethylacetamide, and potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) 30 g, 0.22 mol) was added and the temperature was raised to 90 ° C.
Subsequently, 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 2N HCl, extracted with 700 mL of ethyl acetate, washed with saturated brine, and concentrated.
Subsequently, it fractionated by silica gel column chromatography, and 23g of intermediate compounds were obtained.
15 g (0.05 mol) of the intermediate compound and triethylamine (manufactured by Wako Pure Chemical Industries, Ltd., 5.6 g, 0.056 mol) were dissolved in 100 mL of THF and cooled to 0 ° C.
Next, methacrylic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd., 5.8 g, 0.056 mol) was added dropwise and stirred for 3 hours, and then the reaction solution was poured into 500 g of water, extracted with ethyl acetate, and concentrated.
Subsequently, fractionation was performed by silica gel column chromatography to obtain 20 g of monomer a-2 having a cinnamate group as a photo-alignment group.

[Synthesis of a structural unit having a photo-alignment group (monomer a-3)]
Hydroquinone (Wako Pure Chemical Industries, Ltd., 63.8 g, 0.58 mol) was dissolved in 500 mL of dimethylacetamide, and potassium carbonate (Wako Pure Chemical Industries, Ltd., 40 g, 0.29 mol) was added. The temperature was raised to 90 ° C.
Next, 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 2N HCl, extracted with 700 mL of ethyl acetate, washed with saturated brine, and concentrated. Crude crystals were taken out and fractionated by silica gel column chromatography to obtain 18 g of an intermediate compound.
18 g of the intermediate compound and triethylamine (Wako Pure Chemical Industries, Ltd., 7.79 g, 0.07 mol) were dissolved in 100 mL of THF and cooled to 0 ° C.
Next, cinnamoyl chloride (Tokyo Chemical Industry Co., Ltd., 13.1 g, 0.07 mol) was added dropwise and stirred for 3 hours. The reaction solution was poured into 500 g of water, extracted with ethyl acetate, and concentrated.
Subsequently, fractionation was performed by silica gel column chromatography to obtain 22 g of monomer a-3 having a chalcone group as a photo-alignment group.

[Synthesis of a structural unit having a photo-alignment group (monomer a-4)]
Macromolecules 2004, Vol. 37, # 7, p. In the same manner as in 2572, monomer a-4 having an azo group as a photoalignable group was synthesized.

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

[Synthesis of Structural Unit (Monomer e-1) in which Acid Group is Protected with Acid-Decomposable Group]
Methacrylic acid (Wako Pure Chemical Industries, Ltd., 86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (Tokyo Chemical Industry Co., Ltd., 4.6 g, 0.02 mol) was added.
Subsequently, 2-dihydrofuran (manufactured by Kawaken Fine Chemical Co., Ltd., 71 g, 1 mol, 1.0 equivalent) was added dropwise to the reaction solution.
After stirring for 1 hour, saturated sodium hydrogen carbonate (500 mL) was added, and the mixture was extracted with ethyl acetate (500 mL).
Next, after drying with magnesium sulfate, the insoluble matter was filtered and concentrated under reduced pressure at 40 ° C. or lower, and the yellow oily residue was distilled under reduced pressure to give a boiling point (bp.) Of 54 to 56 as monomer e-1. 125 g of tetrahydro-2H-furan-2-yl methacrylate was obtained as a colorless oil (yield 80%) in the fraction of ℃ / 3.5 mmHg.

[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 at 70 ° C. in a nitrogen stream. Synthesized monomer a-1 (11.1 g, 45 mol%), hexafluoroisopropyl methacrylate (hereinafter abbreviated as “HFIP”) (manufactured by Tokyo Chemical Industry Co., Ltd., 3.5 g, 15 mol%), methacrylic acid (hereinafter referred to as “HFIP”) (Hereinafter abbreviated as “MAA”) (manufactured by Wako Pure Chemical Industries, Ltd., 1.7 g, 20 mol%), glycidyl methacrylate (hereinafter abbreviated as “GMA”) (manufactured by Wako Pure Chemical Industries, Ltd.), 2. 8 g, 20 mol%), a mixed solution of radical polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) 497 mg (2 mol%), and PGMEA (30 g) were added dropwise over 2 hours. After completion of the dropping, the reaction was further performed at 70 ° C. for 4 hours to obtain a PGMEA solution (solid content concentration: 27%) of the polymer P1 having the structural unit s1.

[Synthesis of polymers having structural unit s1 (P2 to P11)]
Polymers P2 to P11 were synthesized in the same manner as the polymer P1, except that the types of the monomer, initiator, and solvent were changed according to Table 1 below. In addition, the numerical value described in the column of each monomer component of the following Table 1 is the usage-amount (mol%) of each monomer with respect to the total amount of a monomer component. Moreover, the numerical value described in the column of a polymerization initiator is mol% when the total amount of monomer components is 100 mol%. Abbreviations used in the examples are 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-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
C18MA: Octadecane methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
・ MMA: Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
・ St: Styrene (Wako Pure Chemical Industries, Ltd.)
AA: Acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
・ GMA: Glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
OXE-30: (3-ethyloxetane-3-yl) methyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
Cyclomer M100: (3,4-epoxycyclohexyl) methyl methacrylate (manufactured by Daicel Chemical Industries, Ltd.)
DCPM: Dicyclopentanyl methacrylate (Fancryl FA-513M, manufactured by Hitachi Chemical Co., Ltd.)
NBMA: N-butoxymethylacrylamide (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 Corporation)
HS-EDM: Diethylene glycol methyl ethyl ether (manufactured by Toho Chemical Industry Co., Ltd.)

[Synthesis of other photo-alignment polymers]
<Synthesis of Polymer P12>
A polymer P12 was synthesized in the same manner as the photoalignable polymer (A-1) described in paragraph [0161] (Preparation Example 1) of JP2013-177561A.
<Synthesis of Polymer P13>
A polymer P13 was synthesized in the same manner as the specific copolymer P1 described in paragraph [0084] (Synthesis Example 1) of WO2010 / 150748.

[Preparation of polymer A having other structural units]
<Synthesis of Polymer A-1 Containing Structural Unit a1 having a Group Protected with Acid-Decomposable Group and Structural Unit a2 Having a Crosslinkable Group>
HS-EDM (82 parts) was heated and stirred at 90 ° C. under a nitrogen stream.
Next, tetrahydro-2H-furan-2-yl methacrylate (43 parts (corresponding to 40.5 mol% of all monomer components)) synthesized as monomer e-1 and OXE-30 (48 parts (total single amount) (Corresponding to 37.5 mol% in body components)), MAA (6 parts (corresponding to 9.5 mol% in all monomer components)), hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., 11 parts ( A mixed solution of radical polymerization initiator V-601 (4.3 parts) and PGMEA (82 parts) over 2 hours. By reacting at 90 ° C. for a time, a solution of polymer A-1 (solid content concentration: 40%) was obtained.
The resulting polymer A-1 had a weight average molecular weight of 15,000 as measured by gel permeation chromatography (GPC).

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

<Synthesis of Polymer A-3 Containing Structural Unit a2 Having a Crosslinkable Group>
HS-EDM (145 g) was heated and stirred at 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%)), DCPM (3.87 g (1.17 mol%)) %), Radical polymerization initiator V-65 (20.8 g (converted to 5.6 mol% monomer amount)), and HS-EDM (145 g) were added dropwise over 2 hours.
After completion of the dropwise addition, a PGMEA solution of polymer A-3 (solid content concentration: 35%) was obtained by reacting at 70 ° C. for 4 hours.

<Polymer A-4 Containing Structural Unit a3 Having Acid Group and Structural Unit a2 Having a Crosslinkable Group>
PGMEA (268 parts) was heated and stirred at 90 ° C. under a nitrogen stream.
Next, tetrahydro-2H-furan-2-yl methacrylate synthesized as monomer e-1 (143.4 parts (corresponding to 40.1 mol% in all monomer components)), cyclomer M100 (168.4 parts) (Corresponding to 37.5 mol% in all monomer components)), MAA (19.5 parts (corresponding to 9.9 mol% in all monomer components)), hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd. ), 37.2 parts (corresponding to 12.5 mol% in all monomer components)), radical polymerization initiator V-601 (5.5 parts), and PGMEA (268 parts) in a mixed solution of 2 The solution was added dropwise over a period of time, and further reacted at 90 ° C. for 2 hours to obtain a solution of polymer A-4 (solid content concentration: 40%).
The resulting 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 Acid Group and Structural Unit a2 Having a Crosslinkable Group>
After the atmosphere in the flask was replaced with nitrogen, 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2′-azobisisobutyronitrile was dissolved was charged.
Next, St (22.5 g), MAA (45.0 g), DCPM (67.5 g), and GMA (90.0 g) were charged, and then gently stirring was started.
Subsequently, the temperature of the solution was raised to 80 ° C., and this temperature was maintained for 5 hours, and then heated at 90 ° C. for 1 hour to complete the polymerization.
Thereafter, the reaction product solution was dropped into a large amount of water to coagulate the reaction product. This coagulated product was washed with water, redissolved in THF (200 g), and coagulated again with a large amount of water.
This re-dissolution and coagulation operation was performed three times in total, and then the obtained coagulated product was dried under reduced pressure at 60 ° C. for 48 hours to obtain a polymer A-5. Thereafter, a polymer A-5 solution was prepared using diethylene glycol so that the solid content concentration was 25% by mass.

<Polymer A-6>
Polymer A-6 was synthesized in the same manner as the non-oriented polymer (E-1) described in paragraph [0165] (Preparation Example 5) of JP2013-177561A.

[Crosslinking agent B]
As the crosslinking agent B, those shown below were used.
<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 Corporation) 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 Resins Co., Ltd.) was used as the crosslinking agent B-3 having a molecular weight of 5,000 or less.

[Other ingredients]
<F-554>
As the surfactant, a perfluoroalkyl group-containing nonionic surfactant (F-554, manufactured by DIC Corporation) was used.
<KBM-403>
As the adhesion improving agent, γ-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

[Examples 1 to 24 and Comparative Examples 1 to 6]
Each component shown in Table 2 below is dissolved and mixed in a solvent (PGMEA) until the solid content is 18% by mass, filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm, and each example and comparative example. A resin composition was prepared. In addition, the addition amount in a table | surface represents the addition amount in solid content of each component, and a unit is a mass part.
The obtained resin composition was applied onto a glass substrate by a spin coat method, pre-dried on a hot plate at 80 ° C. for 1 minute, and then baked in a clean oven at 230 ° C. for 60 minutes to give a 3 μm overcoat. A cured film of layers was formed.
The formed cured film was subjected to oblique cutting with a surface / interface cutting device (DN-20S type, manufactured by Daipura Wintes) to expose the cross section.
For the exposed cross section, the intensity ELq and the intensity ESsub of the mass analysis of the fragment derived from the orientation group were measured using the measurement apparatus and conditions described above, and the intensity ratio (intensity ELq / intensity ESub) was measured. The evaluation was based on the following criteria. The results are shown in Table 2 below. In addition, although the same test was done with respect to the orientation protective layer after producing the display apparatus mentioned later, the result was 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 to less than 10 times. C: The intensity ratio is 5 times to less than 8 times. D: The intensity ratio is 2 times to 5 times. Less than E: Intensity ratio is less than 2 times F: No fragment peak

[Evaluation]
<Orientation>
Each prepared resin composition was applied onto an alkali-free glass substrate by a spin coater (spinner), and then prebaked on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 4.0 μm.
Next, the obtained coating film was irradiated with radiation at an exposure amount of 1000 J / m ² using a high-pressure mercury lamp, and then post-baked in an oven at a curing temperature of 230 ° C. and a curing time of 30 minutes. Formed.
The formed protective layer was irradiated with 750 mJ / cm ² of polarized light using an ultraviolet polarized light exposure apparatus (HC-2150PUFM, manufactured by Run Technical Service Co., Ltd.) to form an alignment protective layer. .
Thereafter, a horizontally aligned liquid crystal was applied, and the alignment state was observed with a polarizing microscope at a magnification of 20 times. The place was changed, and it observed in five visual fields (about 1 square micrometer), and evaluated with the following references | standards. The results are shown in Table 3 below.
A: No problem.
B: A level in which shading is observed but has no practical problem.
C: Defects and bright spots are observed.
D: Not oriented at all.

<Retardation (Rth)>
Each prepared resin composition was applied onto an alkali-free glass substrate by a spin coater, and then prebaked on a hot plate at 100 ° C. for 2 minutes to form a coating film having a thickness of 4.0 μm.
Next, the obtained coating film was irradiated with radiation at an exposure amount of 1000 J / m ² using a high-pressure mercury lamp, and then post-baked in an oven at a curing temperature of 230 ° C. and a curing time of 30 minutes. Formed.
The birefringence of the protective layer was evaluated using a phase difference measuring device KOBRA-WFD (manufactured by Oji Scientific Instruments). The results are shown in Table 3. In addition, since birefringence is caused by a display angle shift, there is no practical problem unless it exceeds 30 nm, but a low numerical value is preferable.

<Flatness>
Create an L / S pattern with a height of 1 μm and a width of 10 μm (L / S width ratio is 1: 1), apply the resin composition on it with a spin coater, pre-bake at 90 ° C./120 seconds, And cured at 230 ° C./30 minutes to obtain a cured film of 2 μm.
The flatness of the obtained cured film was defined by the following formula and calculated. The results are shown in Table 3 below. As the flatness, the closer the value is to 100, the higher the flattening ability, and 70% or more is required for practical use.
Flatness (%) = (1−Δd / H) × 100
Here, in the above formula, Δd means the difference (μm) between the thickness of the cured film above the L / S pattern and the thickness of the cured film (2 μm), and H is the film of the underlying L / S pattern Thickness (μm) is meant.

<Display characteristics>
(1) Manufacture of Array Substrate According to the description of Example 42 of International Publication (WO) 2009/025386, an insulating film having contact holes formed thereon was formed on the array substrate.
Next, a transparent conductive layer made of ITO was formed on the insulating film by sputtering on the substrate on which the insulating film was formed. Next, the transparent conductive layer was etched using a photolithography method to form a common electrode on the insulating film.
Thereafter, a SiN insulating layer was formed by sputtering. Next, the SiN layer was etched using a photolithography method to form a patterned SiN insulating film on the surface of the substrate on which the common electrode was formed.
Next, a transparent conductive layer made of ITO was formed on the interlayer insulating film using a sputtering method. Next, the transparent conductive layer was etched using a photolithography method, and a comb-like pixel electrode was formed on the inorganic insulating film.
As described above, the array substrate of this example was manufactured. In the obtained array substrate of this embodiment, a contact hole of a desired size is formed at a desired position of the insulating film, and electrical connection between the pixel electrode and the source-drain electrode of the active element is realized. It was.
A liquid crystal aligning agent A-1 described in Example 6 of International Publication (WO) 2009/025386 pamphlet as a liquid crystal aligning agent including a radiation-sensitive polymer having a photo-alignable group on the transparent electrode of the array substrate. Is applied with a spinner. Next, after pre-baking for 1 minute on an 80 ° C. hot plate, it was heated at 180 ° C. for 1 hour in an oven in which the inside was replaced with nitrogen to form a coating film having a thickness of 80 nm. Then, the surface of the coating film, polarized ultraviolet rays 200 J / ^{m 2,} including a bright line of 313nm using a Hg-Xe lamp and Gran Taylor prism, irradiated from 40 ° inclined direction with respect to the direction perpendicular to the substrate surface, An array substrate having a liquid crystal alignment film was manufactured.

(2) Production of counter substrate First, a color filter substrate produced by a known method was prepared. In this color filter substrate, fine coloring patterns of three colors of red, green, and blue and a black matrix are arranged in a lattice pattern on a transparent substrate. Next, a coating film was formed on the color pattern of the color filter substrate and the black matrix using the resin compositions of Examples 1 to 24 and Comparative Examples 1 to 6 shown in Table 2 above, and the coating was formed at 90 ° C./120 After pre-baking for 2 seconds, it was thermally cured in an oven at 230 ° C./30 minutes to produce a protective film. Next, the protective film was subjected to a photo-alignment treatment by irradiating polarized light with 750 mJ / cm ² using an ultraviolet polarized light exposure apparatus (HC-2150PUFM, manufactured by Run Technical Service Co., Ltd.), and a 2 μm alignment protective film. The counter substrate was manufactured.

(3) Manufacture of display device A liquid crystal layer was sandwiched between the obtained counter substrate with an alignment protective film and the array substrate to manufacture a color liquid crystal display element. As the liquid crystal layer, a layer made of nematic liquid crystal and aligned parallel to the substrate surface was used. The display characteristics and reliability of these liquid crystal display elements were evaluated.

(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 evaluated to be driven again. The results are shown in Table 3 below.
A: No display failure occurred B: Display failure occurred in 1% to less than 10% of the pixels, but no problem in practical use.
C: Display failure occurred in 10% or more of pixels D: Display failed even immediately after manufacture

From the results shown in Tables 1 to 3, when the alignment protective layer does not have an orientation group, a fragment derived from the orientation group is not detected, It was also found that the display characteristics were inferior (Comparative Examples 1 and 2).
In Comparative Examples 3 and 4, the strength ELq of the fragment derived from the orientation group of the orientation protective layer was twice or more the strength ESsub. However, the orientation group and the crosslinked structure linked to each other through a covalent bond It was found that the display characteristics after exposure to high temperature and high humidity were inferior (Comparative Examples 3 to 4).
Further, when a polymer that does not have an ubiquitous group for unevenly distributing the orientation group is used, the strength ELq of the fragment derived from the orientation group of the formed orientation protective layer is less than twice the strength ESsub. Thus, it was found that even the liquid crystal display element immediately after fabrication was inferior in display characteristics (Comparative Examples 5 to 6).

On the other hand, when the polymer having the structural unit s1, the structural unit a2, and the like, and the polymer having the structural unit s1, but not the structural unit s1, are used, the formed alignment protective layer has a covalent bond. And an intensity ratio (strength ELq / strength ESub) of mass analysis intensity ELq and intensity ESub of the fragment derived from the orientation group satisfies a predetermined condition. As a result, it was found that excellent flatness was maintained and display performance was good even when exposed to high temperature and high humidity (Examples 1 to 24).
In particular, from the comparison between Example 1 and Example 24, it was found that when the crosslinking agent B having a molecular weight of 5000 or less was blended, the flatness was improved and the display performance was also improved.

DESCRIPTION OF SYMBOLS 10: Liquid crystal display device 12: Backlight unit 14,15: Base material 16: Thin film transistor 17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal layer 21: Orientation protective layer 22: Color filter 23: Orientation film 30 : First substrate 40: Second substrate

Claims

A liquid crystal display device having a first substrate, a liquid crystal layer, and a second substrate in this order from the viewing side,
The first substrate comprises a base material and an orientation protective layer,
The second substrate comprises a base material, a thin film transistor, a display electrode, and an alignment film,
The alignment protective layer has a surface in contact with the liquid crystal layer;
The alignment protective layer has an alignment group and a crosslinked structure linked to each other through a covalent bond;
For the fragment derived from the orientation group detected by time-of-flight secondary ion mass spectrometry, the intensity ELq of the mass analysis of the fragment derived from the orientation group on the surface of the orientation protective layer in contact with the liquid crystal layer; The strength ESsub of the mass spectrometry of the fragment derived from the orientation group on the substrate side surface of the orientation protective layer satisfies the following condition 1 or 2:
A liquid crystal display device, wherein the crosslinked structure includes any one of structures represented by the following formulas (A-1) to (A-3).
Condition 1: The intensity ELq is 2 to 20 times the intensity ESub.
Condition 2: The intensity ELq is significantly measured and the intensity ESub is below the measurement limit.

In the formulas (A-1) to (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. To express.
The liquid crystal display device according to claim 1, wherein the intensity ELq is 5 to 20 times the intensity ESsub.
3. The liquid crystal display device according to claim 1, wherein the orientation group is a group obtained by photoreaction of a photo-alignment group.
4. The liquid crystal display device according to claim 1, wherein the thickness of the alignment protective layer is 1 to 4 μm.
The liquid crystal display device according to any one of claims 1 to 4, wherein the liquid crystal constituting the liquid crystal layer is a horizontally aligned liquid crystal.
The fragment derived from the orientation group is a fragment derived from at least one photoalignment group selected from the group consisting of a cinnamate group and a chalcone group. Liquid crystal display device.
A protective layer is formed on a base material using a composition for forming an orientation protective layer containing a polymer P containing a structural unit having an orientation group and a polymer A not containing a structural unit having an orientation group. After that, a first step of performing an alignment treatment on the protective layer to form an alignment protective layer and producing a first substrate;
A liquid crystal is sealed by bonding a second substrate having a base material, a thin film transistor, a display electrode, and an alignment film together with the first substrate, and a liquid crystal layer is interposed between the first substrate and the second substrate. Forming a liquid crystal display device, and manufacturing the liquid crystal display device.
The polymer P includes a structural unit represented by s1 below as a structural unit having the orientation group,
The method for manufacturing a liquid crystal display device according to claim 7, wherein the polymer P and the polymer A satisfy the following condition 3 or 4.
s1: a structural unit having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton and an alkyl group having 10 to 30 carbon atoms, and a structural unit having a photoalignment group Condition 3: The polymer P includes a structural unit a2 having a crosslinkable group, and the polymer A includes a structural unit a3 having an acid group.
Condition 4: The polymer P includes a structural unit a3 having an acid group, and the polymer A includes a structural unit a2 having a crosslinkable group.
The method for producing a liquid display device according to claim 8, wherein the crosslinkable group is at least one selected from the group consisting of an oxiranyl group, a 3,4-epoxycyclohexyl group, and an oxetanyl group.
10. The method for producing a liquid crystal display device according to claim 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.
The method for producing a liquid crystal display device according to any one of claims 7 to 10, wherein the composition for forming an alignment protective layer further contains a crosslinking agent B having a molecular weight of 5000 or less.
The crosslinking agent B includes a crosslinking agent having an epoxy group,
The manufacturing method of the liquid crystal display device of Claim 11 whose mass ratio of the said crosslinking agent B with respect to the total mass of the said crosslinking agent B, the said polymer P, and the said polymer A is 30 mass% or less.
The alignment group is a photo-alignment group;
The method for manufacturing a liquid crystal display device according to any one of claims 7 to 12, wherein the alignment treatment is a photo-alignment treatment using light having a wavelength of 365 nm or less.
The method for manufacturing a liquid crystal display device according to any one of claims 7 to 13, wherein the first step includes a step of performing a heat treatment before or after the alignment treatment.