KR20180067588A - Liquid crystal display device and manufacturing method of liquid crystal display device - Google Patents

Abstract

An object of the present invention is to provide a liquid crystal display device which maintains excellent flatness even in the case where a color filter is provided on the visual side and display performance is good even when exposed under high temperature and high humidity, and a manufacturing method thereof. A liquid crystal display device according to 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 a viewer side, wherein the first substrate comprises a substrate and an orientation protection layer, 2 substrate comprises a substrate, a thin film transistor, a display electrode, and an alignment film, wherein the alignment protection layer has a surface in contact with the liquid crystal layer, the alignment protection layer has an aligning group and a cross- The fragments derived from the orienting group detected by the time-of-flight secondary ion mass spectrometry were measured for the intensity ELq of the fragments on the surface of the orientation-sensitive protective layer in contact with the liquid crystal layer and the fragments And the cross-linking structure is expressed by a predetermined structural formula.

Description

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

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

BACKGROUND ART [0002] Liquid crystal displays (LCDs) are widely used for monitors and televisions in personal computers, smart phones, and the like in various advantages such as miniaturization and thinning with low voltage and low power consumption.

Such a liquid crystal display device has two liquid crystal cells and two polarizing plates arranged on both sides of the liquid crystal cell and the liquid crystal cell has two substrates arranged so as to face each other with the liquid crystal layer and the liquid crystal layer interposed therebetween In these two substrates, an alignment film is generally provided to align the liquid crystal constituting the liquid crystal layer.

As a material for forming such an alignment film, for example, Patent Document 1 discloses a method for producing a liquid crystal display device which comprises a step of forming a liquid crystal layer comprising a polymer having a silicone group or a fluorine-substituted alkyl group and a photo-orientable group as a first component and a polymer comprising a methacrylic acid and a methacrylic acid ester A photo-orientable polymer composition comprising a non-light-orienting polymer obtained by polymerizing a monomer containing at least one member selected from the group consisting of the following [1] to [28].

Patent Document 1: JP-A-2013-177561

However, in the liquid crystal display device, it is common to provide a color filter on the viewer side. From the viewpoints of preventing the penetration of impurities from the color filter and planarizing the step of the color filter, An overcoat layer) is provided.

Here, the present inventors have studied to provide an orientation film in which a protective layer is unnecessary when a color filter is provided on the visual side, that is, an orientation protection layer having a function of a protective layer and an orientation film.

The inventors of the present invention have studied the alignment film described in Patent Document 1 as such an alignment protection layer and found that the flatness may be inferior depending on the compounding agent of the photo-orientable polymer composition and that the liquid crystal display device is exposed to high temperature and high humidity The display performance is inferior.

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a liquid crystal display device which maintains excellent flatness even when a color filter is provided on the visual side, and has good display performance even when exposed under high temperature and high humidity, and a manufacturing method thereof.

The present inventors have intensively studied in order to achieve the above object, and as a result, they have found that an orientation protection layer having an oriented group and a cross-linked structure mutually connected through covalent bonds is provided and the oriented group is localized on the surface side in contact with the liquid crystal layer, The present inventors have found that excellent flatness is maintained even in the case of providing a color filter in a high-temperature and high-humidity environment, and display performance is improved even when exposed under high temperature and high humidity.

That is, it has been found that the above problems can be achieved by the following constitution.

[1] A liquid crystal display device having a first substrate, a liquid crystal layer, and a second substrate in this order from the viewer side,

Wherein the first substrate comprises a substrate and an orientation protection layer,

Wherein the second substrate comprises a substrate, a thin film transistor, a display electrode, and an alignment film,

The orientation protection layer has a surface in contact with the liquid crystal layer,

The orientation-protecting layer has an oriented group and a cross-linked structure connected to each other through a covalent bond,

For the fragment derived from the orienting group detected by the time-of-flight secondary ion mass spectrometry, the intensity ELq of the mass analysis of the fragment derived from the aligning group on the surface in contact with the liquid crystal layer of the orientation protective layer, The intensity ESub of the mass analysis of the fragment derived from the orienting group on the side of the substrate satisfies the following condition 1 or 2,

(A-1) to (A-3) described below, wherein the cross-linking structure comprises at least one of the following structures.

Condition 1: The intensity ELq is 2 to 20 times the intensity ESub.

Condition 2: The intensity ELq is measured significantly 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 oriented group is a group resulting from photo-reacting a photo aligning group.

[4] The liquid crystal display device according to any one of [1] to [3], wherein the thickness of the orientation protection layer is 1 to 4 μm.

[5] The liquid crystal display according to any one of [1] to [4], wherein the liquid crystal constituting the liquid crystal layer is a horizontally aligned liquid crystal.

[6] The liquid crystal display according to any one of [1] to [5], wherein the fragment derived from the orienting group is a fragment derived from at least one photo aligning group selected from the group consisting of a cinnamate group and a chalcone group .

[7] A protective layer is formed on a substrate by using a composition for forming an orientation protection layer containing a polymer P containing a constituent unit having an oriented group and a polymer A containing no constituent unit having an oriented group, A first step of forming an orientation protection layer by performing orientation treatment on the layer,

A liquid crystal display device is manufactured by bonding a first substrate and a second substrate including a substrate, a thin film transistor, a display electrode, and an alignment film to enclose the liquid crystal, and forming a liquid crystal layer between the first substrate and the second substrate And a second step of manufacturing the liquid crystal display device.

[8] The positive resist composition according to any one of [1] to [5], wherein the polymer P comprises a constituent unit represented by s1,

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 from 10 to 30 carbon atoms, and a structural unit having a photo-

Condition 3: 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: Polymer P includes structural unit a3 having an acid group, and polymer A includes structural unit a2 having a crosslinkable group.

[9] The process for producing a liquid crystal display device according to [8], wherein the crosslinkable group is at least one selected from the group consisting of an oxirane group, a 3,4-epoxycyclohexyl group and an oxetanyl group.

[10] The process 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 process 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 5,000 or less.

[12] The method according to any one of [1] to [12], wherein the crosslinking agent B comprises a crosslinking agent having an epoxy group,

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 mass% or less.

[13] The optical recording medium according to [

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

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

Hereinafter, the present invention will be described in detail.

Descriptions of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

In the present specification, the numerical value range indicated by "~" means a range including numerical values written before and after "~" as a lower limit value and an upper limit value.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

As used herein, "(meth) acrylate" is a notation for "acrylate" or "methacrylate", "(meth) acryl" is a notation for "acrylic" The term "(meth) acryloyl" refers to acryloyl or methacryloyl.

[Liquid crystal display device]

A liquid crystal display device according to 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 a viewer side, wherein the first substrate comprises a substrate and an orientation protection layer, 2 substrate includes a substrate, a thin film transistor, a display electrode, and an alignment film.

In the liquid crystal display device of the present invention, the alignment protective layer has a surface in contact with the liquid crystal layer and includes any one of the aligning groups and the structures represented by the following formulas (A-1) to (A-3) And has a structure in which an oriented group and a crosslinked structure are connected to each other via a covalent bond.

Further, in the liquid crystal display device of the present invention, with respect to the fragments derived from the orienting group detected by the time-of-flight secondary ion mass spectrometry (TOF-SIMS) The intensity ELq of the mass analysis of fragments derived from the aligning group on the surface in contact with the liquid crystal layer and the intensity ESub of the mass analysis of fragments derived from the aligning group on the substrate side surface of the orientation protective layer satisfy the following condition 1 Or 2, respectively.

Condition 1: The intensity ELq is 2 to 20 times the intensity ESub.

Condition 2: The intensity ELq is measured significantly and the intensity ESub is below the measurement limit.

<Measurement Conditions of TOF-SIMS>

Measurement by TOF-SIMS in the present invention is performed as follows.

(1) The orientation-protecting layer and the adjacent layer adjacent to the orientation-protecting layer are peeled off, and the surface of the orientation-protecting layer (the surface in contact with the liquid crystal layer, hereinafter the same) and the backside of the orientation- In the case where the same can be exposed in the following description), the intensity and the intensity of the mass analysis of a fragment derived from the orienting group on the surface of the orientation protection layer are measured by the apparatus and conditions shown in the following (3) ELq and the intensity ESub of the mass analysis of fragments derived from the orienting group on the back surface of the orientation protective layer are measured.

(2) When the front surface and the back surface of the orientation protection layer can not be exposed, a laminate having an orientation protection layer and an adjacent layer is subjected to surface and interfacial cutting analysis (SAICAS) And cut in an oblique direction so as to reach the front and back surfaces of the orientation protection layer to expose the end faces of the orientation protection layer.

The intensity of the mass analysis of the fragments derived from the orienting group measured by the apparatus and the conditions shown in the following (3) as the region of 10 nm in the depth (thickness) direction from the surface of the orientation protection layer was determined as the intensity ELq , The intensity of the mass analysis of the fragment derived from the aligning group measured in the device (3) and the condition (2) in the region of 2000 nm in the depth (thickness) direction from the back surface of the orientation protection layer is defined as the intensity ESub.

(3) Measure by the following equipment and conditions.

Device: TOF-SIMS IV (manufactured by ION-TOF)

Primary ion: Bi ³⁺ (beam diameter 2 μm)

· Measuring range: Raster scan in 256 directions in one direction and its orthogonal direction

· Polarity: posi, nega

The liquid crystal display device of the present invention can maintain excellent flatness even when a color filter is provided on the viewer side by providing the above-described alignment protection layer and display performance even when exposed under high temperature and high humidity.

This is not clear in detail, but the present inventors assume as follows.

That is, it is preferable that the orientation-protecting layer has a cross-linking structure including an aligning group and any one of the structures represented by the following formulas (A-1) to (A-3), and the aligning group and the cross- And the intensity ELq and the intensity ESub by the TOF-SIMS measurement satisfies the above-described condition 1 or 2, whereby the orientation group is localized on the surface of the orientation protection layer, and the orientation group is the orientation of the polymer constituting the orientation protection layer It is believed to be tightly coupled.

This makes it possible to maintain the orientation of the liquid crystal layer even when the color filter is provided on the backside of the orientation protection layer without causing any flatness and even under exposure to high temperature and high humidity, and thus 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 for the reason that the display performance becomes better even when exposed under high temperature and high humidity.

Next, the outline of the configuration of the liquid crystal display device of the present invention will be described with reference to Fig. 1, and then 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.

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

In the liquid crystal display device 10 shown in Fig. 1, a first substrate 30, a liquid crystal layer 20, and a second substrate 40 are provided in this order from the viewer side.

The first substrate 30 includes a substrate 15 to which a polarizing film is attached, an RGB color filter 22 having a black matrix disposed thereon, an alignment protection layer 21 having a surface in contact with the liquid crystal layer 20, Respectively.

In the second substrate 40, the base material 14 to which the polarizing film is attached and the elements of the thin film transistor 16 are arranged. Each element formed on the base material 14 is wired with an ITO transparent electrode 19 which forms a display electrode by passing the contact hole 18 formed in the cured film 17 and on the ITO transparent electrode 19 And an alignment film 23 are provided.

The liquid crystal display device 10 shown in Fig. 1 has a backlight unit 12 on its back surface, and a light source of a backlight is not particularly limited and a known light source can be used. For example, a white LED (light emitting diode), a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic electroluminescence.

The liquid crystal display device may be a 3D (three dimensional) type or a touch panel type. It can also be used as a flexible type, and can be used as a second interlayer insulating film 48 of JP-A-2011-145686 or an inter-phase insulating film 520 of JP-A-2009-258758.

[First substrate]

The first substrate of the liquid crystal display device of the present invention is a substrate provided on the viewer side of a later-described liquid crystal layer, and includes a substrate and an orientation protection layer. Further, since the alignment protection layer has a surface in contact with the liquid crystal layer described later, the first substrate is provided with the substrate and the alignment protection layer in this order from the viewing side.

When an arbitrary color filter is provided on the visual side of the liquid crystal display device of the present invention, the first substrate includes a substrate, a color filter, and an alignment protection layer in this order.

<Description>

As the substrate, a transparent substrate used for 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 them, it is preferable to use a glass substrate.

&Lt; Alignment protection layer &

As described above, the above-mentioned orientation protection layer has a cross-linked structure having a surface in contact with the liquid crystal layer, which will be described later, and an orientation unit and any one of the structures represented by the following formulas (A-1) to (A- And has a structure in which an oriented group and a crosslinked structure are connected to each other via a covalent bond.

(Oriented group)

The oriented group of the alignment protection layer is not particularly limited as long as it is a group capable of orienting a functional group having a function of aligning the liquid crystalline compound. In the present invention, the alignment protective layer does not contact the surface at the time of forming the alignment protection layer, It is preferable that the photo-induced group is a group formed by photo-reaction.

Here, the photo-orientable group refers to a photoreactive group which imparts an orientation property by any one of a photo-dimerization reaction, a photo-isomerization reaction and a photo-degradation reaction.

Examples of the group to which the orientation is imparted by the photo-dimerization reaction include groups introduced from at least one kind of derivative selected from the group consisting of maleimide derivatives, cinnamic acid derivatives and coumarin derivatives, Include a cinnamate group and a chalcone group.

Examples of the cinnamate group and the chalcone group may include the following structures (in the following formulas, * represents a connecting site to the polymer chain and R represents a hydrogen atom or a monovalent organic group) The connecting site to the polymer chain represented by * may be directly bonded to the main chain of the polymer or may be bonded via a divalent linking group. As the monovalent organic group represented by R, an alkyl group or an aryl group is preferable. The number of carbon atoms in the monovalent organic group represented by R is preferably 1 to 10, more preferably 1 to 7.

[Chemical Formula 1]

On the other hand, specific examples of the reactive groups which are isomerized by the action of light include a group consisting of a skeleton of at least one compound selected from the group consisting of an azobenzene compound, a stilbene compound and a spiropyran compound .

Specific examples of the reactive group decomposable by the action of light include groups composed of a skeleton of a cyclobutane compound and the like.

Of these, for reasons of irreversibility of the reaction, it is preferable that the group which gives orientation by the light dimerization reaction which reacts in the shortwave light, more preferably at least one selected from the group consisting of a cinnamate group and a chalcone group.

(Crosslinked structure)

The crosslinking structure of the alignment protection layer is a crosslinking structure comprising any one of the structures represented by the following formulas (A-1) to (A-3).

(2)

In the formulas (A-1) to (A-3), * represents a bonding position, and in the formula (A-3), R ¹ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl and hexyl.

Examples of the crosslinking structure including the structure represented by the above formulas (A-1) to (A-3) include a crosslinking group (for example, epoxy group, oxetane- (A-1), (A-2-1) and (A-3-1) represented by the following formulas Structure.

In the following formulas (A-1-1), (A-2-1) and (A-3-1), * represents a bonding position, ¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

(3)

The alignment protection layer has a structure in which the aligning group and the crosslinking structure are linked to each other via a covalent bond, as described above.

Accordingly, in the present invention, a polymer comprising a constituent unit having a crosslinkable group (for example, an epoxy group, an oxetanyl group, etc.) and / or an acid group (for example, a carboxyl group or the like) It is preferable that the polymer containing the structural unit further contains the structural unit having the above-mentioned orientation group.

In the present invention, the thickness of the alignment protection layer is preferably 1 to 4 mu m, more preferably 2 to 3 mu m.

<Color filter>

The first substrate of the liquid crystal display device of the present invention may include a color filter between the substrate and the orientation protection layer.

The color filter is not particularly limited and, for example, a color filter commonly known as a color filter of a liquid crystal display device can be used.

Such a color filter usually comprises transparent coloring patterns of red, green and blue colors, and each transparent coloring pattern thereof is composed of a resin composition in which a coloring agent is dissolved or dispersed, preferably pigment microparticles are dispersed .

The color filter may be formed by preparing an ink composition colored with a predetermined color and printing it on a color pattern basis. However, by using a paint type photosensitive resin composition containing a coloring agent of a predetermined color, It is more preferable to perform it by the method.

[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 above-described first substrate and a second substrate to be described later.

The liquid crystal layer is provided so as to be in contact with the alignment protection layer of the first substrate as described above.

As a driving method for driving the liquid crystal layer used in the liquid crystal display of the present invention, a twisted nematic (TN) method, a VA (Vertical Alignment) method, an IPS (In-Plane-Switching) method, an FFS , An OCB (Optically Compensated Bend) method, and the like.

Among these driving methods, an IPS method is preferable.

In the IPS mode liquid crystal cell, the rod-like liquid crystal molecules are oriented substantially parallel to the substrate, and the liquid crystal molecules respond in a planar manner by applying an electric field parallel to the substrate surface. That is, in the IPS system, the liquid crystal constituting the liquid crystal layer is horizontally aligned liquid crystal. In the IPS system, black display is performed in an electric field-free state, and the absorption axes of the upper and lower pair of polarizing plates are orthogonal.

[Second substrate]

The second substrate of the liquid crystal display of the present invention is a substrate provided on the side opposite to the first substrate (backlight side) of the above-described liquid crystal layer and includes a substrate, a thin film transistor, a display electrode, and an alignment film.

<Description>

As the substrate provided for the second substrate, a transparent substrate used for 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, etc. Can be used. Among them, it is preferable to use a glass substrate.

<Thin Film Transistor>

As a thin film transistor (TFT) provided in the second substrate, those used in known liquid crystal display devices can be suitably used, and the structure thereof is not particularly limited, and may be a top gate type, a bottom gate type do.

Specific examples of the thin film transistor include an amorphous silicon TFT, a low temperature polysilicon TFT, and an oxide semiconductor TFT.

<Display electrode>

As the display electrode included in the second substrate, those used in known liquid crystal display devices can be suitably used. As the constituent material thereof, for example, indium tin oxide (ITO), aluminum doped zinc A transparent conductive material such as indium zinc oxide (AZO) and indium zinc oxide (IZO) can be used.

<Orientation film>

As the alignment film provided by the second substrate, those which are generally used in a known liquid crystal display device containing a polymer as a main component are suitably usable.

As polymer materials for alignment films, there is a description in many documents, and a large number of commercially available products are available.

The polymer material used in the present invention is preferably a polyvinyl alcohol or a polyimide and a derivative thereof. Particularly, modified or unmodified polyvinyl alcohol is preferable.

Examples of the alignment film usable in the present invention include the alignment film described in International Patent Publication No. 01/88574, page 43, line 24 to page 49, line 8; Denatured polyvinyl alcohol described in paragraphs [0071] to [0095] of Japanese Patent Publication No. 3907735; A liquid crystal alignment film formed by the liquid crystal aligning agent described in JP-A-2012-155308; And the like.

With regard to other configurations of the liquid crystal display device (for example, a polarizing plate, a backlight, and the like), reference can be made to Japanese Laid-Open Patent Publication No. 2007-328210 and Japanese Laid-Open Patent Publication No. 2014-238438, .

[Manufacturing Method of Liquid Crystal Display Device]

A method of manufacturing a liquid crystal display device of the present invention is a method of manufacturing a liquid crystal display device using a composition for forming an orientation protection layer containing a polymer P containing a constituent unit having an aligning group and a polymer A containing no constituent unit having an aligning group And a first step of forming an orientation protection layer on the protective layer after the protective layer is formed to manufacture a first substrate.

A method for manufacturing a liquid crystal display device according to the present invention is a method for manufacturing a liquid crystal display device comprising a step of bonding a first substrate with a second substrate provided with a substrate, a thin film transistor, a display electrode and an alignment film to seal the liquid crystal, And a second step of manufacturing a liquid crystal display device.

[First Step]

In the first step, a protective layer is formed on a substrate by using a composition for forming an orientation protection layer containing a polymer P containing a constituent unit having an oriented group and a polymer A containing no constituent unit having an orientation group , And an orientation treatment is applied to the protective layer to form an orientation protection layer, thereby manufacturing a first substrate.

The substrate in the first step is the same as the substrate provided in the first substrate of the liquid crystal display device of the present invention.

&Lt; Composition for forming an alignment protective layer >

The composition for forming an alignment protective layer has a structure in which the polymer P has the structural unit having the above-mentioned orientation-sensitive group, for the reason that the retardation of the alignment protection layer is lowered and the transparency is increased, , And the polymer P and the polymer A satisfy the following condition 3 or 4: &quot; (1) &quot;

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 from 10 to 30 carbon atoms, and a structural unit having a photo-

Condition 3: 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: Polymer P includes structural unit a3 having an acid group, and polymer A includes structural unit a2 having a crosslinkable group.

In the present invention, the reason why the above-mentioned crosslinked structure is more easily formed in the orientation protective layer is that the polymer P and / or the crosslinkable group possessed by the polymer A is an oxirane group, a 3,4-epoxycyclohexyl group , And an oxetanyl group is preferable.

Specific examples of the polymer P and the polymer A contained in the composition for forming an alignment protective layer and optional additives and the like are described below in detail.

(Polymer P)

As the above-mentioned polymer P, a polymer containing a constitutional unit (hereinafter also referred to as "constituent unit s1") shown below in s1 as described above is preferably exemplified.

s1: a structural unit having at least one partial structure (hereinafter also referred to as "ubiquitous group") selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton and an alkyl group having 10 to 30 carbon atoms, unit

&Lt; Structural unit having a partial structure of fluorine-substituted hydrocarbon group &gt; >

The fluorine-substituted hydrocarbon group may be a hydrocarbon group substituted by at least one fluorine atom, and at least one hydrogen atom in an alkyl group or an alkylene group (hereinafter abbreviated as "an alkyl group etc. & An alkyl group substituted with an atom, and the like, and an alkyl group in which all hydrogen atoms such as an alkyl group 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 ellipticity.

[Chemical Formula 4]

In the formula (I), R ² represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * represents a connecting site to the 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, a plurality of R ^{2 s} may be the same or different.

M in the formula (I) represents an integer of 1 to 3, preferably 1 or 2.

N in the formula (I) represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and particularly preferably 1 or 2.

R in the general formula I represents 0 or an integer of 1 to 2, preferably 1 or 2, and more preferably 2.

The connecting site to the polymer chain represented by * may be directly bonded to the main chain of the polymer such as the above-mentioned polymer A1-1 or may be a polyoxyalkylene group, an alkylene group, an ester group, a urethane group, A cyclic alkylene group, a poly (caprolactone), an amino group, or the like. And it is preferable that they are bonded through a polyoxyalkylene group.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ² in the formula (I) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a tert- Is a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

In the 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. Of 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.

Examples of the method of introducing the fluorine-substituted hydrocarbon group into the polymer include a method of introducing the fluorine-substituted hydrocarbon group into the polymer by a polymer reaction; A method of copolymerizing a monomer having a fluorine-substituted hydrocarbon group (hereinafter referred to as a "fluorine-substituted hydrocarbon group-containing monomer") to introduce a structural unit having a fluorine-substituted hydrocarbon group into the polymer; And the like.

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

[Chemical Formula 5]

In the formula (II), R ¹ represents a hydrogen atom, a halogen atom, a methyl group which may have a substituent, or an ethyl group which may have a substituent. In addition, R ^2, all of X, m, n and r, and R ^2, X, m, n, and r and copper in the formula I, preferred examples are the same.

Examples of the halogen atom represented by R ¹ in the formula (II) include a fluorine atom, a chlorine atom and a bromine atom.

The production method of such fluorine-substituted hydrocarbon group-containing monomers is described in, for example, pages 117 to 118 of "Synthesis and function of fluorine compounds" (supervised by Nobu Ishikawa, published by CMC, 1987) &Quot; Chemistry of Organic Fluorine Compounds II "(Monograph 187, Ed. By Milos Hudlicky and Attila E. Pavlath, American Chemical Society 1995), pp. 747-752.

Specific examples of the monomer represented by the formula (II) include tetrafluoroisopropyl methacrylate represented by the following formula (IIa) and hexafluoroisopropyl methacrylate represented by the following formula (IIb) .

As other specific examples, the compounds described in paragraphs [0058] to [0061] of JP-A No. 2010-18728 can be mentioned. Among them, a structure in which a fluorine-substituted hydrocarbon group is bonded to a polyoxyalkylene group is preferable.

[Chemical Formula 6]

<< 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 includes a polyoxyalkylene group.

In the present invention, it is preferable that the siloxane skeleton is introduced into a structural unit having a partial structure of a siloxane skeleton in the polymer by copolymerizing a compound having a (meth) acryloyloxy group and an alkoxysilyl group from the viewpoint of ellipticity .

Here, examples of the alkoxysilyl group include groups represented by the following formula (X).

(7)

In the formula (X), R ³ to R ⁵ each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group or an alkoxy group, and at least one of them is an alkoxy group. * Indicates a bonding position.

In the formula (X), at least one of R ³ to R ⁵ is an alkoxy group, and the alkoxy group is preferably an alkoxy group having 1 to 15 carbon atoms, more preferably an alkoxy group having 1 to 8 carbon atoms, More preferably an alkoxy group of 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 an alkoxy group and one is an alkyl group, or three are alkoxy groups. Among them, it is more preferable that the three are alkoxy groups, that is, a trialkoxysilyl group.

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

In the present invention, the siloxane skeleton is obtained by polymerizing a compound represented by the following structural formula (A) (hereinafter also referred to as "specific siloxane compound") from the viewpoint of ellipticity and introducing a siloxane skeleton into the polymer desirable.

[Chemical Formula 8]

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 a divalent linking group represented by the following structural formula (B) .

[Chemical Formula 9]

In the structural formula (B), R ⁴ represents a hydrogen atom, a methyl group or an ethyl group. n1, n2, and n3 are each independently an integer of 0 to 100; Here, R &lt; ⁴ &gt; is present in two or more of the structural formulas (B), but may be different or may be the same.

In the structural formula (A), x1, x2, and x3 are integers satisfying the sum of 1 to 100.

In addition, 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).

[Chemical formula 10]

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, Q ¹ and Q ^{2 each} represent an oxygen An atom, a sulfur atom, or -NRB-, and Q ¹ and Q ² may be the same or different. 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 formulas (D) to (F).

(11)

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).

[Chemical Formula 12]

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

As the siloxane skeleton, the structure described in paragraphs [0092] to [0094] of Japanese Laid-Open Patent Publication No. 2010-18728 can be given as a concrete example of the above formula (A), but is not limited thereto.

Among them, 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 from 10 to 30 carbon atoms may contain a branched structure or a cyclic structure, but it is preferable that the number of carbon atoms in the straight-chain structure portion is in the range of 10 to 30, more preferably all linear structures.

The number of carbon atoms in the alkyl group is preferably from 10 to 20.

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

[Chemical Formula 13]

In the general formula (a3-1), n _a3 represents an integer of 10 to 30, and * represents a position connecting to the main chain or side chain of the polymer. and n _a3 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, when a monomer having the structure (a3-1) is appropriately selected and applied at the time of synthesis, The structure of (a3-1) can be introduced into the repeating unit of the polymer.

The monomer having the structure of the general formula (a3-1) may be a commercially available compound, but it may be a monomer having a desired structure (a3-1) contained in the monomer (a3-1) May be appropriately introduced and used. The method of introducing the structure of (a3-1) into a commercially available monomer is not limited, and a known method may be appropriately applied.

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, in the case of a polymer having a (meth) acrylic structure in the main chain, the monomer represented by the general formula (a3-2) It is preferable to use an appearing monomer.

[Chemical Formula 14]

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. Also, n _a3 is a synonym including the above general formula (a3-1) and a preferable range.

In the general formula (a3-2), R ³² is a hydrogen atom, a methyl group, an ethyl group or a halogen atom, more preferably a hydrogen atom or a methyl group, and 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. Of 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 straight chain structure or a branched structure and includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a tert-butyl group, Methyl group.

The alkyleneoxy group represented by R ³³ preferably has 1 to 4 carbon atoms. The alkyleneoxy group may have a branched structure. It may have a substituent or may be unsubstituted. Examples of the substituent which may be contained include a halogen atom and the like. Specific examples of the alkyleneoxy group include a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group and the like.

Among them, R ³³ is preferably an unsubstituted straight-chain alkyleneoxy group having 1 to 4 carbon atoms, or a single bond, more preferably a single bond.

By using the monomer represented by the formula (a3-2), a polymer having a repeating unit represented by the following formula (U-a3-1) can be obtained.

Such a polymer is one of preferable forms having a repeating unit represented by the following general formula (U-a3-1).

[Chemical Formula 15]

In the general formula (U-a3-1), n _a3 is the same as the general formula (a3-1) including the preferred range and R ³² , X ³¹ , and R ³³ are the same as those in the general formula (a3- 2) and the preferred scope.

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

[Chemical Formula 16]

<< Constituent Unit Having Photo Orientation Group >>

Polymer P is a polymer having 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, to be.

Here, the photo-orientable group is the same as that described in the above-mentioned oriented group.

The main chain structure of the polymer having a photo-orientable group is not particularly limited. However, since the molecular design of the side chain is varied and the main chain formation by the radical polymerization reaction of the ethylenically unsaturated compound is easy, Is a polymer having a repeating unit represented by the following formula

[Chemical Formula 17]

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 photo-orientable group.

In the formula (III), R ¹ is a hydrogen atom or an alkyl group, an alkyl group, the alkyl group having from 1 to 4 carbon atoms (e.g., methyl group, ethyl group, n- propyl group, isopropyl group, n- view group and the like) . R ¹ is preferably a hydrogen atom or a methyl group.

In the formula (III), L represents a single bond or a divalent linking group, and the divalent linking group is preferably a group formed by -O-, -S-, an alkylene group, an arylene group, or a combination thereof. The alkylene group represented by L may be a straight chain, branched or cyclic structure, but is preferably a straight chain structure. The number of carbon atoms of the alkylene group represented by L is preferably from 1 to 10, more preferably from 1 to 6, still more preferably from 2 to 4. Examples of the arylene group represented by L include a phenylene group, a tolylene group and a xylylene group, and a phenylene group is preferable.

In the formula (III), P represents a photo-orientable group, and specific examples thereof include a chalconic group, a cinnamate group, a stilbenyl group, a maleimide group and an azobenzyl group. Among them, a calcicon group and a cinnamate group are more preferable. The photo-orientable group represented by P may have a substituent unless the photo-alignment property is lost. Specific examples of the substituent include a halogeno group, an alkyl group, an aryl group and the like, preferably an alkyl group or an aryl group. The alkyl group or aryl group preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms.

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

[Chemical Formula 18]

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

&Lt; EMI ID =

(25)

The polymer having a repeating unit represented by the above formula (I) may be synthesized by (a) polymerizing a corresponding monomer to directly introduce a photoreactive group, (b) polymer obtained by polymerizing a monomer having an arbitrary functional group Or may be synthesized by a method in which a photoreactive group is introduced by a polymer reaction. It is also possible to combine the methods (a) and (b).

Examples of the polymerization reaction that can be used in the above-mentioned methods (a) and (b) include radical polymerization, cationic polymerization, and anionic polymerization.

The polymer having a repeating unit represented by the above formula (I) may be a copolymer composed of a plurality of repeating units represented by the above formula (I) and may be a repeating unit other than the above-mentioned formula (I) A repeating unit not containing a sulfonic acid group, or a repeating unit containing no unsaturated group).

{Preferred Embodiment of Constituent Unit s1}

The constituent unit s1 is preferably from 0.01 to 10 mol%, more preferably from 0.1 to 10 mol%, still more preferably from 0.1 to 5 mol%, even more preferably from 0.1 to 3 mol%, based on the total structural units of the polymer component , And most preferably 0.5 to 3 mol%.

The content of the constituent unit having a ubiquitous group in the constituent unit s1 is preferably 0.01 to 3 mol%, more preferably 0.1 to 3 mol%, and still more preferably 0.5 to 3 mol%.

The content of the structural unit having a photo-orientable group in the structural unit s1 is preferably from 0.01 to 5 mol%, more preferably from 0.1 to 5 mol%, still more preferably from 1 to 3 mol%.

In the polymer having the constituent unit s1, the content of the constituent unit s1 is preferably 20 to 90 mol%, more preferably 20 to 80 mol%, and still more preferably 20 to 70 mol%, based on the total constituent units of the polymer. Is more preferable. In this case, the content of the constituent unit having a urethane group is preferably 1 to 50 mol%, more preferably 5 to 30 mol%, and still more preferably 10 to 20 mol%. The content of the photo-alignable group-containing structural unit is preferably from 1 to 70 mol%, more preferably from 10 to 60 mol%, still more preferably from 20 to 50 mol%.

In the present invention, when the content of the "constituent unit" is defined as a molar ratio, "constituent unit" In the present invention, the "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same goes for the following.

<< Other building blocks >>

Examples of the polymer P include, in addition to the aforementioned constituent unit s1, a constituent unit a1 having an acid group protected with an acid-decomposable group, a constituent unit a2 having a crosslinkable group, a constituent unit a3 having an acid group, .

Among these structural units, as described above, it is preferable that the structural unit a2 having a crosslinkable group and / or the structural unit a3 having an acid group are contained in the orientation protection layer for the reason that the above-mentioned crosslinked structure is easily formed.

<<< Configuration unit a1 >>>

The structural unit a1 is a structural unit having an acid group protected by an acid-decomposable group (hereinafter also referred to as structural unit a1).

The term "a group protected with an acid-decomposable group" in the present invention means a group which causes a deprotection reaction with an acid as a catalyst (or an initiator) to generate a structure decomposed by an acid group and a regenerated acid.

The "group in which the acid group is protected with an acid-decomposable group" in the present invention may be any of those known as an acid group and an acid decomposable group, and is not particularly limited.

As the acid group, for example, a carboxyl group, a phenolic hydroxyl group and the like are preferably exemplified.

Examples of the acid decomposable group include groups which are relatively easily decomposed by an acid (for example, an ester structure, an acetal functional group such as a tetrahydropyranyl ester group or a tetrahydrofuranyl ester group) (For example, a tertiary alkyl group such as a tert-butyl ester group, a tertiary alkylcarbonate group such as a tert-butylcarbonate group), and the like.

The constituent unit a1 having a group protected by an acid-decomposable group is a constituent unit in which a carboxyl group is protected by an acid-decomposable group (hereinafter also referred to as " constituent unit having a protected carboxyl group protected with an acid-decomposable group & (Hereinafter, also referred to as " a structural unit having a protective phenolic hydroxyl group protected with an acid-decomposable group ") protected with an acid-decomposable group.

Hereinafter, the structural unit a1-1 having a protected carboxyl group protected with an acid-decomposable group and the constituent 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 is a structural unit having a carboxyl group of the structural unit having a carboxyl group and having a protected carboxyl group protected by an acid-decomposable group described in detail below.

The structural unit having a carboxyl group which can be used for the structural unit a1-1 having a protected carboxyl group protected with an acid-decomposable group is not particularly limited and a known structural unit can be used. Examples of the constitutional 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 and an unsaturated tricarboxylic acid, or a structure derived from an ethylenic unsaturated group and an acid anhydride Containing structural units a1-1-2.

Hereinafter, structural units derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule a1-1-1 used as the structural unit having a carboxyl group, and structural units derived from a1-1-2 ethylenically unsaturated group and acid anhydride- Constituent units will be described in order.

{(Structural unit a1-1-1 derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule)

Examples of the unsaturated carboxylic acid used in the present invention as the constituent unit a1-1-1 derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule include the compounds described in paragraph 0043 of JP-A No. 2014-238438 have.

Among them, from the viewpoint of developability, in order to form the aforementioned structural unit a1-1-1, acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxy (Meth) acryloyloxyethylphthalic acid, or an anhydride of an unsaturated polycarboxylic acid, and the like, and acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, It is more preferable to use them.

The constituent unit a1-1-1 derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule may be composed of one kind alone or two or more kinds.

{{Structural units a1-1-2 having an ethylenic unsaturated group and a structure derived from an acid anhydride together}}

The constituent unit a1-1-2 having both the ethylenically unsaturated group and the structure derived from an acid anhydride is preferably a unit derived from a monomer obtained by reacting a hydroxyl group and an acid anhydride which are present in the constituent unit having an ethylenic unsaturated group.

As the acid anhydride, known dicarboxylic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and anhydrous chloric anhydride; Acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride are 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.

(An acid-decomposable group usable in the structural unit a1-1)

As the acid decomposable group usable in the structural unit a1-1 having a protected carboxyl group protected with the acid decomposable group, the acid decomposable group described above can be used.

Among these acid decomposable groups, the carboxyl group is preferably a protected carboxyl group protected in the form of an acetal from the viewpoints of the basic physical properties of the resin composition, particularly from the viewpoints of sensitivity and pattern shape, the formation of contact holes, and the storage stability of the resin composition. Among the acid decomposable groups, from the viewpoint of sensitivity, it is more preferable that the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following formula (a1-10). Further, as the whole of the carboxyl group, if the formula protected carboxyl group protected in the form of an acetal represented by a1-10, protected carboxyl group, - a structure of a (C = O) -O-CR 101 R 102 (OR 103) have.

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In the formula (a1-10), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or a hydrocarbon group, provided that R ¹⁰¹ and R ¹⁰² are not hydrogen atoms at the same time. R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be connected to form a cyclic ether.

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

When R ¹⁰¹ , R ¹⁰² and R ^{103 in} the formula (a1-10) represent an alkyl group, the alkyl group may be any of linear, branched or cyclic.

The straight-chain alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. The branched chain is more preferably 3 to 6 carbon atoms, and more preferably 3 or 4 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a tert- 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 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 isobonyl 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 R ¹⁰¹ , R ¹⁰² and R ¹⁰³ are a haloalkyl group and have an aryl group as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ are an aralkyl group when they have a halogen atom as a substituent.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, 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 thereof include a phenyl group, an? -Methylphenyl group and a naphthyl group. Examples of the alkyl group substituted with an aryl group, that is, an aralkyl group include a benzyl group, an? -Methylbenzyl group, a phenethyl group, For example.

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 more preferably a methoxy group or an ethoxy group.

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. When the alkyl group is a straight chain or branched chain alkyl group, To 12 cycloalkyl groups.

These substituents may be further substituted by the substituents described above.

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

Further, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ may combine with each other to form a ring together with the carbon atoms to which they are bonded. Examples of the ring structure in the case where R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ^103, or R ¹⁰² and R ¹⁰³ are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, A t-butyl group and a tetrahydropyranyl group.

In the formula (a1-10), it is preferable that either R ¹⁰¹ or R ¹⁰² is a hydrogen atom or a methyl group.

As the radically polymerizable monomer used for forming the constituent unit having a protective carboxyl group represented by the above formula (a1-10), commercially available ones may be used, or those synthesized by known methods may be used. For example, it can be synthesized by a synthesis method described in paragraphs 0037 to 0040 of Japanese Patent Laid-Open Publication No. 2011-221494.

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

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Wherein R ¹ and R ² are each independently 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, R ³ is an alkyl group or an aryl group, and R ¹ Or R ² and R ³ may be connected 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, an alkyl group having 1 to 10 carbon atoms is preferable. When R ¹ and R ² are aryl groups, a phenyl group is preferred. R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R ³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

X represents a single bond or an arylene group, preferably a single bond.

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

(28)

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 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and preferably a hydrogen atom.

Preferable specific examples of the structural unit a1-1 having a protected carboxyl group protected with an acid-decomposable group include the following structural units. R represents a hydrogen atom or a methyl group.

[Chemical Formula 29]

{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 by the acid-decomposable group include a constituent unit in a hydroxystyrene-based structural unit and a novolac-based resin.

Of these, a structural unit derived from hydroxystyrene or? -Methylhydroxystyrene is preferable from the viewpoint of sensitivity.

As the constituent unit having a phenolic hydroxyl group, a constituent unit described in paragraphs 0065 to 0073 of JP-A No. 2014-238438 is also preferable from the viewpoint of sensitivity.

<<< Configuration 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 so long as it is a group which generates a curing reaction by a heat treatment.

Preferred examples of the structural unit having a crosslinkable group include an epoxy group (e.g., an oxiranyl group, a 3,4-epoxycyclohexyl group, etc.), an oxetanyl group, -NH-CH ₂ -OR (R is a hydrogen atom, An ethylenically unsaturated group, and a block isocyanate group, and examples thereof include an epoxy group, an oxetanyl group, an -NH- CH ₂ -OR a structural unit containing at least one member selected from the group, a (meth) acryloyl group and a block isocyanate group represented by the group consisting of (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) is preferred, an epoxy group, an oxetane group, and a -NH-CH ₂ -OR configuration, including at least one member selected from the group consisting of a group represented by (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) unit It is more preferable.

{Structural unit a2-1 having an epoxy group and / or oxetanyl group}

The polymer component A1 preferably contains a polymer having the structural unit a2-1 having an epoxy group and / or an oxetanyl group. The cyclic group of a three-membered ring is also referred to as an epoxy group, and the cyclic group of a four-membered ring is also referred to as an oxetanyl group.

The structural unit a2-1 having an epoxy group and / or an oxetanyl group may have at least one epoxy group or oxetanyl group in one structural unit, and may contain at least one epoxy group and at least one oxetanyl group, An epoxy group or two or more oxetanyl groups, and it is not particularly limited, but it is preferable that a total of 1 to 3 epoxy groups and / or oxetanyl groups are contained, and a total of 1 or 2 epoxy groups and / or oxetanyl groups More preferably one having an epoxy group or oxetanyl group.

Specific examples of the radical polymerizable monomer used for forming the structural unit having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -N-propyl acrylate Dicumyl acrylate, glycidyl alpha-n-butyl acrylate, 3,4-epoxycutyl acrylate, methacrylic acid-3,4-epoxybutyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, -Epoxy cyclohexylmethyl,? -Ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, Compounds containing an alicyclic epoxy skeleton described in paragraphs 0031 to 0035 of Japanese Patent Publication No. 4168443, and the like, and these contents are incorporated herein by reference.

Specific examples of the radical polymerizable monomer used for forming the constituent unit having an oxetanyl group include (meth) acrylate ester having an oxetanyl group described in paragraphs 0011 to 0016 of JP-A No. 2001-330953 , The contents of which are incorporated herein by reference.

Specific examples of the radically polymerizable monomer used for forming the structural unit a2-1 having an epoxy group and / or an oxetanyl group are monomers containing a methacrylic acid ester structure and monomers containing an acrylic acid ester structure .

Among these, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, methyl (3-ethyloxetan-3-yl) (3-ethyloxetan-3-yl) methyl. These constituent units may be used alone or in combination of two or more.

Preferable specific examples of the structural unit a2-1 having an epoxy group and / or an oxetanyl group include the following structural units. R represents a hydrogen atom or a methyl group.

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{Structural unit a2-2 having an ethylenically unsaturated group}

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

In addition, for the structural unit a2-2 having an ethylenic unsaturated group, reference can be made to the description of paragraphs 0072 to 0090 of Japanese Laid-Open Patent Publication No. 2011-215580 and the description of paragraphs 0013 to 0031 of Japanese Laid-Open Patent Publication No. 2008-256974 , The contents of which are incorporated herein by reference.

{-NH-CH ₂ -OR configuration having represented by (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms)} unit a2-3

Another example of the structural unit a2 having a crosslinkable group is also a structural unit a2-3 having a group represented by -NH-CH ₂ -OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). By having the constituent unit a2-3, a curing reaction can be caused by a gentle heat treatment, and a cured film excellent in all properties 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 more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be any of linear, branched or cyclic alkyl groups, 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).

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In the formula (a2-30), R ³¹ represents a hydrogen atom or a methyl group, and R ³² represents an alkyl group having 1 to 20 carbon atoms.

R ³² is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be any of linear, branched or cyclic alkyl groups, but is preferably a straight chain 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, an i-butyl group, an n-butyl group and a methyl group are preferable.

<<< Configuration unit a3 >>>

The constituent unit a3 is a constituent unit having an acid group (hereinafter also referred to as a constituent unit a3).

The acid group in the present invention means a proton dissociable group having a pKa of less than 11.

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, an acid anhydride group of these acid groups, And the like, and a carboxylic acid group and / or a phenolic hydroxyl group are preferable. The salt is not particularly limited, but an alkali metal salt, an alkaline earth metal salt, and an organic ammonium salt can be preferably exemplified.

The constituent unit containing an acid group used in the present invention is more preferably a constituent unit derived from styrene, a constituent unit derived from a vinyl compound, or a constituent unit derived from (meth) acrylic acid and / or an ester thereof. For example, compounds described in paragraphs 0021 to 0023 and paragraphs 0029 to 0044 of JP-A-2012-88459 can be used, the contents of which are incorporated herein by reference. Among them, a constituent unit derived from p-hydroxystyrene, (meth) acrylic acid, maleic acid and maleic anhydride is preferable.

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 a structural unit a1-1-1 derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the above-mentioned molecule, a structural unit a1-1-1 having an ethylenic unsaturated group and a structure derived from an acid anhydride, 1-2, and a structural unit a1-2-1 having a phenolic hydroxyl group, and preferred embodiments thereof are also the same.

Among them, the structural unit a3 having an acid group is preferably a structural unit derived from a compound selected from the group consisting of methacrylic acid, acrylic acid and p-hydroxystyrene [any of the following formulas (a3-1) to (a3-3) Is a constitutional unit derived from methacrylic acid [constitutional unit represented by the following formula (a3-1)] or an acrylic acid-derived constitutional unit [constitutional unit represented by the following formula (a3-2)] , More preferably a structural unit derived from methacrylic acid (structural unit represented by the following formula (a3-1)).

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<<< Configuration unit a4 >>>

Examples of the monomer to be the constituent unit a4 other than the above-mentioned constituent unit s1, constituent unit a1, constituent unit a2 and constituent unit a3 include, but not limited to, styrene, alkyl (meth) acrylate, Alkyl esters, (meth) acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, bicyclo unsaturated compounds, maleimide compounds, and unsaturated aromatic compounds.

The monomers forming the other constituent unit a4 may be used singly or in combination of two or more.

Specific examples of the other structural unit a4 include styrene, methylstyrene,? -Methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbearate, vinyl vinyl benzoate (Meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, isobutyl (meth) acrylate, (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile and ethylene glycol monoacetate mono Unit. In addition, compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623 can be mentioned.

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

As the other structural unit a4, a structural unit derived from a (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. More preferred is methyl (meth) acrylate. The content of the structural unit a4 in the total structural units constituting the polymer is preferably 60 mol% or less, more preferably 50 mol% or less, further preferably 40 mol% or less. The lower limit value may be 0 mol%, but is preferably 1 mol% or more, for example, and is more preferably 5 mol% or more. Within the range of the above-mentioned numerical values, all the properties of the cured film obtained from the resin composition become good.

(Polymer A)

As the polymer A, for example, there can be mentioned a polymer containing at least any one of the above-mentioned constituent units a1 to a4, which does not include the constituent unit s1 described above. Among them, It is preferable that the polymer is a polymer having a structural unit a2 having a crosslinkable group and / or a structural unit a3 having an acid group for the reason that the above-mentioned crosslinked structure is easily formed in the protective layer.

<< MOLECULAR >>

The above-mentioned polymer P and polymer A have a molecular weight in terms of polystyrene equivalent 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. If it is within the range of the above-mentioned numerical values, all characteristics are good. The ratio (dispersion degree, Mw / Mn) of the number average molecular weight Mn to the weight average molecular weight Mw is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.

The measurement of the weight average molecular weight and the number average molecular weight in the present invention is preferably carried out by gel permeation chromatography (GPC). TSK gel Super HZM-H, TSK gel Super HZ4000, and TSKgel Super HZ200 (manufactured by TOSOH CORPORATION) were used as the columns by using gel permeation chromatography method in the present invention using HLC-8020GPC (manufactured by TOSOH CORPORATION) 4.6 mm ID x 15 cm), and THF (tetrahydrofuran) is preferably used as the eluent.

<< Preparation Method >>

Various methods are also known for the synthesis of the polymer P and the polymer A described above. For example, a method in which a radically polymerizable monomer mixture containing a radically polymerizable monomer used for forming the respective constituent units described above is dissolved in an organic solvent, Can be synthesized by polymerization using a radical polymerization initiator. It is also possible to synthesize by a so-called polymer reaction.

In the present invention, the mass ratio of the polymer P to the total mass of the polymer P and the polymer A is preferably less than 10 mass%, more preferably 0.1 to 5 mass% % Is more preferable.

(Crosslinking agent B)

In the present invention, for the reason that the flatness when the color filter is provided on the visual side is improved and the display performance after exposure under high temperature and high humidity becomes better, the orientation protection layer contains the crosslinking agent B having a molecular weight of 5,000 or less .

The crosslinking agent B can be used without limitation as long as it causes a crosslinking reaction by heat.

For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule, a block isocyanate compound (compound having a protected isocyanate group), an alkoxymethyl group-containing compound, or at least one ethylene At least one member selected from the group consisting of an unsaturated double bond (ethylenic unsaturated group), a compound having at least two epoxy groups or an oxetanyl group in the molecule, and at least one member selected from the group consisting of a block isocyanate compound Is more preferable.

Hereinafter, the crosslinking agent B preferably used in the present invention will be described.

&Lt; Compounds having two or more epoxy groups or oxetanyl groups in the molecule &gt;

As the crosslinking agent B, there can be mentioned, for example, a multifunctional ring-shaped cyclic ether compound.

That is, 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 and the like.

These are available as commercial products. For example, Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX- EX-810, EX-821, EX-821, EX-832, EX-841, EX- DLC-204, DLC-204, DLC-204, EX-920, EX-931, EX-212L, EX-214L, EX-216L, EX- DLC-301, DLC-402 (manufactured by Nagase ChemteX Corporation), Celloxide 2021P, 2081, 3000, EHPE3150, EPOLED GT400, Cell Venus B0134, B0177 have.

These may be used alone or in combination of two or more.

As specific examples of the compound having two or more oxetane groups in the molecule, AOXTENE OXT-121, OXT-221, OX-SQ and PNOX (manufactured by DOA Corporation) can be used.

The oxetanyl group-containing compound is preferably used alone or in combination with a compound containing an epoxy group.

<< Block isocyanate compound >>

As the crosslinking agent B, a block isocyanate-based compound can also be preferably employed.

The block isocyanate compound is not particularly limited so long as the isocyanate group is a compound having a block isocyanate group chemically protected. From the viewpoint of curability, a compound having two or more block isocyanate groups in one molecule .

In addition, the block isocyanate group in the present invention is a group capable of generating an isocyanate group by heat, and for example, a group in which a block agent and an isocyanate group are reacted to protect an isocyanate group is preferable . The block isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C to 250 ° C.

The skeleton of the block isocyanate compound is not particularly limited and may be any of those having two isocyanate groups in one molecule and may be an aliphatic, alicyclic or aromatic polyisocyanate, For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophoronediisocyanate, 1,6-hexamethylene diisocyanate, 1,3 -Trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Hexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2,2'-diethyl ether diisocyanate Cyanate, da Phenylmethane-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'-methyleneditholylene-4,4'-diisocyanate, 4,4'-diphenyl ether isocyanate, tetrachlorophenylene diisocyanate Isocyanate compounds such as cyanate, norbornane diisocyanate, hydrogenated 1,3-xylylene diisocyanate and hydrogenated 1,4-xylylene diisocyanate, and compounds derived from these compounds The compound of the prepolymer type skeleton Can be used together. Among them, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI) and isophoronediisocyanate (IPDI) Particularly preferred.

Examples of the parent structure (mother structure) of the block isocyanate compound include buret type, isocyanurate type, adduct type, bifunctional prepolymer type and the like.

Examples of the block agent for forming the block structure of the block isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, And the like. Among them, a block agent selected from an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, and a pyrazole compound is particularly preferable.

Examples of the oxime compounds include oxime and ketoxime. Specific examples thereof include acetoxime, formaldehyde, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime. .

Examples of the lactam compound include? -Caprolactam,? -Butyrolactam, and the like.

Examples of the phenol compound include phenol, naphthol, cresol, xylenol, halogen-substituted phenol, and the like.

Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, alkyl lactate and the like.

Examples of the amine compound include a primary amine and a secondary amine, and may be an aromatic amine, an aliphatic amine, or an alicyclic amine, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.

Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, and methyl acetoacetate. Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole, and the like.

Examples of mercaptan compounds include alkyl mercaptans, aryl mercaptans, and the like.

The block isocyanate compound is commercially available, for example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 B-872N, B-874N, and B-882N (all manufactured by Mitsui Chemicals, Inc.), B-815N, B-820NSU, B- B40B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (Manufactured by Asahi Kasei Chemicals Co., Ltd.), desmodule BL1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, , Manufactured by Sumika Bayer Co., Ltd.), and the like can be preferably used.

<< Crosslinking agent containing alkoxymethyl group >>

As the alkoxymethyl group-containing compound, alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril and alkoxymethylated urea are preferable. These are obtained by converting the methylol group of methylol melamine, methylol benzoguanamine, methylol glycolluryl or methylol group into 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 the amount of generated outgas, a methoxymethyl group is particularly preferable Do.

Of these compounds, alkoxymethylated melamine, alkoxymethylated benzoguanamine and alkoxymethylated glycoluril are preferable compounds, and from the viewpoint of transparency, alkoxymethylated glycoluril is particularly preferable.

A compound having an alkoxymethyl group-containing crosslinking agent whose molecular weight is 1,000 or less is used in the curable composition.

These alkoxymethyl group-containing compounds are commercially available and are commercially available, for example, from Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (manufactured by Mitsui Cyanamid), NIKARAK MX-750, -032, -706, -708, -40, -31, -270, -280, -290, -11, NIKARAK MW-30HM, -100 LM, -390 (manufactured by SANWA CHEMICAL CO., LTD.) And the like can be preferably used.

In the present invention, as the crosslinking agent B, it is preferable to use a crosslinking agent having an epoxy group.

The content of the crosslinking agent B in the case of containing the crosslinking agent B is preferably 30 mass% or less, more preferably 10 to 30 mass%, based on the total mass of the crosslinking agent B, the polymer P and the polymer A.

(Organic solvent)

The composition for forming the protective layer preferably contains an organic solvent in addition to the above-mentioned polymer.

As the organic solvent, a known organic solvent can be used. Examples of the organic solvent include 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 Propylene glycol diacetate, dipropylene glycol monoalkyl ether acetate, alcohols, esters, ketones, amides, lactones and the like can be exemplified . As specific examples of these organic solvents, reference can be made to paragraph 0062 of Japanese Laid-Open Patent Publication No. 2009-098616.

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

The boiling point of the organic solvent is preferably 100 占 폚 to 300 占 폚, and more preferably 120 占 폚 to 250 占 폚, from the viewpoint of coatability.

The organic solvents usable in the present invention may be used alone or in combination of two or more. It is also preferable to use a solvent having a different boiling point.

The content of the organic solvent is preferably from 100 to 3,000 parts by mass, more preferably from 200 to 2,000 parts by mass, more preferably from 250 to 1,000 parts by mass, per 100 parts by mass of the total solid content of the composition, More preferably, it is in the mass part.

The solid content concentration of the composition is preferably from 3 to 50 mass%, and more preferably from 20 to 40 mass%.

(Surfactants)

The composition for forming the protective layer may contain a surfactant.

As the surfactant, any of anionic, cationic, nonionic or amphoteric surfactants can be used, but preferred surfactants are nonionic surfactants. As the surfactant, a nonionic surfactant is preferable, and a fluorinated surfactant is more preferable.

Examples of the surfactant that can be used in the first embodiment include Megapak F142D, Dong F172, Dong F173, Dong F176, Dong F177, Dong F183, Dong F479, Dong F482, Dong F554, Dong F780, Dong F781 (F), FC-135, FC-170C, FC (FC), FC-170, FC (FC) S-113, S-131, S-131, S-131, S-131, S- 141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105 and SC-106 (manufactured by Asahi Glass Co., (Available from Mitsubishi Material Denshi Kasei Co., Ltd.) and Fotogen 250 (manufactured by Neos Co., Ltd.). In addition to the above, other materials such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyfluor (manufactured by Kyoeisha Chemical Co., Ltd.), Epson (manufactured by Mitsubishi Material Denshi Kasei Co., (Manufactured by Sumitomo 3M Ltd.), Asahi Guard, Surfron (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and the like.

As the surfactant, the compounds described in paragraphs 0151 to 0155 of Japanese Patent Laid-Open Publication No. 2014-238438 are also preferable.

The content of the surfactant is preferably 0.001 to 5.0 parts by mass, more preferably 0.01 to 2.0 parts by mass, per 100 parts by mass of the total solid content of the composition.

The surfactant may be contained only in one kind or in two or more kinds. When two or more kinds are included, the total amount is preferably in the above range.

(Adhesion improving agent)

The composition for forming the protective layer may contain an adhesion improver.

Examples of the adhesion improver include alkoxysilane compounds and the like.

The alkoxysilane compound is a compound which improves the adhesion of an inorganic material to be a substrate such as a silicon compound such as silicon, silicon oxide, or silicon nitride, a metal such as gold, copper, molybdenum, titanium, desirable.

Specific examples of the adhesion improver include, for example,? -Aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxy Silane,? -Glycidoxypropylmethyldimethoxysilane,? -Methacryloxypropylmethyldiethoxysilane,? -Methacryloxypropyltriethoxysilane,? -Chloropropyltrimethoxysilane ,? -mercaptopropyltrimethoxysilane,? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, and the like. Of these,? -Glycidoxypropyltrimethoxysilane and? -Methacryloxypropyltrimethoxysilane are preferable, and? -Glycidoxypropyltrimethoxysilane is more preferable. These may be used alone or in combination of two or more.

The content of the adhesion improver is preferably 0.001 to 15 parts by mass, more preferably 0.005 to 10 parts by mass, per 100 parts by mass of the total solid component of the composition. The adhesion improver may be used alone or in combination of two or more. When two or more kinds are used, it is preferable that the total amount is in the above range.

(Photosensitive agent)

The composition for forming the protective layer may contain a photosensitizer.

Examples of the photosensitizer include photoacid generators, quinone diazide compounds, photo radical initiators, and the like.

<Formation of Protective Layer>

The method for forming the protective layer on the substrate is not particularly limited. For example, a method of applying the composition for forming the protective layer onto the substrate can be mentioned.

(apply)

The method of applying the composition for forming a protective layer on a substrate is not particularly limited and specific examples include a printing method (for example, a gravure printing method, a screen printing method, a flexographic printing method, an inkjet printing method, A spin coating method, a slit coating method, a slit and spin coating method, a dip coating method, and a curtain coating method.

(Solvent removal)

In the present invention, after the above-described application, a solvent removing step for removing any solvent contained in the protective layer forming composition from the coating film may be provided before the orientation treatment step described later.

For example, when NMP is used as a solvent, the solvent removal step is preferably a step of heating at about 80 to 150 DEG C for about 0.5 to 3 minutes, More preferably about 120 deg. C for 0.5 to 2 minutes.

&Lt; Formation of alignment protection layer (alignment treatment) >

As the alignment treatment, for example, a non-contact alignment method such as a rubbing treatment method, a photo alignment treatment, and a magnetic alignment can be given.

(Photo-alignment treatment)

In the present invention, when the aligning group is a photo aligning group, the aligning treatment is preferably a photo aligning 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 to obtain a uniform orientation. In this case, a method of irradiating polarized ultraviolet rays is not particularly limited. The polarized light is not particularly limited, and examples thereof include linearly polarized light, circularly polarized light, elliptically polarized light and the like, among which linearly polarized light is preferable.

In addition, as long as substantially polarized light can be obtained, non-polarized light may be irradiated at a predetermined angle from the normal to the thin film. In other words, unpolarized light may be irradiated from the oblique direction of the thin film surface. Is not particularly limited as long as it is in a direction in which the polar angle? (0 &lt;? &Lt; 90 °) is inclined with respect to the normal direction of the surface of the thin film, Deg.].

Examples of the light source for the light to be used include a xenon lamp, a high-pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp.

The wavelength range to be irradiated can be limited by using an interference filter, a color filter, or the like for ultraviolet rays obtained from such a light source. Linearly polarized light can be obtained by using a polarization filter or a polarization prism for the light from these light sources.

<Heat treatment>

In the present invention, from the viewpoint of enhancing the reliability of the thin film transistor, it is preferable that the first step is a step of performing heat treatment before or after the alignment treatment.

As the method of performing the heat treatment, for example, a method of heating the protective layer or the orientation protection layer subjected to the orientation treatment at a temperature of 180 to 350 占 폚, preferably 200 to 300 占 폚 for 20 to 60 minutes Can be suitably selected.

The heat treatment is preferably performed using a heating apparatus such as a hot plate or an oven. In addition, transparency can be further improved by performing the heat treatment in a nitrogen atmosphere.

[Second Step]

A second step is a step of forming a liquid crystal layer between a first substrate and a second substrate by bonding a second substrate comprising a substrate, a thin film transistor, a display electrode and an alignment film to a first substrate, And a step of manufacturing a display device.

The second substrate in the second step is the same as the second substrate in the liquid crystal display device of the present invention, and the manufacturing method thereof is not particularly limited.

The method of encapsulating the liquid crystal in the second step is not particularly limited. For example, after a space is formed by interposing a spacer between the first substrate and the second substrate, liquid crystal is sealed in the formed space Method.

Example

Hereinafter, the present invention will be described in more detail based on examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed to be limited by the following embodiments. Unless otherwise stated, "part" and "%" are based on mass.

[Synthesis of structural unit (monomer a-1) having photo aligning group]

(7.79 g, 0.07 mol) of methyl trans-4-hydroxycinnamate (12.5 g, 0.07 mol, manufactured by Tokyo Kasei Kogyo K.K.) and triethylamine (Wako Pure Chemical Industries, Ltd.) were dissolved in tetrahydrofuran , Hereinafter abbreviated as "THF"). After cooling to 0 占 폚, methacrylic acid chloride (7.33 g, 0.07 mol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was gradually added dropwise.

Subsequently, 500 g of water was added to a cloudy reaction system (reaction system), stirred for 1 hour, and then filtered to obtain 14 g of a monomer a-1 having a cinnamate group as a photo-aligning group. The structure was confirmed by NMR (nuclear magnetic resonance).

[Synthesis of constituent unit (monomer a-2) having photo aligning group]

(22.2 g, 0.1 mol) of ethyl 4-hydroxy-3-methoxycinnamate (manufactured by Tokyo Kasei Kogyo K.K.) was dissolved in 150 mL of dimethylacetamide, and potassium carbonate (manufactured by Wako Pure Chemical Industries, 30 g, 0.22 mol) was added and the temperature was raised to 90 占 폚.

Then, 4-chlorobutanol (21.6 g, 0.2 mol, manufactured by Wako Pure Chemical Industries, Ltd.) 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.

Then, the product was collected by silica gel column chromatography to obtain 23 g of an intermediate compound.

15 g (0.05 mol) of the intermediate compound and 5.6 g (0.056 mol) of triethylamine (Wako Pure Chemical Industries, Ltd.) were dissolved in 100 mL of THF and cooled to 0 占 폚.

Subsequently, methacrylic acid chloride (5.8 g, 0.056 mol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise and stirred for 3 hours. The reaction solution was extracted with ethyl acetate (500 g), and then concentrated.

Subsequently, this was fractionated by silica gel column chromatography to obtain 20 g of monomer a-2 having a cinnamate group as a photo-aligning group.

[Synthesis of constituent unit (monomer a-3) having photo aligning group]

Hydroquinone (63.8 g, 0.58 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 500 mL of dimethylacetamide and potassium carbonate (40 g, 0.29 mol, manufactured by Wako Pure Chemical Industries, Ltd.) The temperature was raised to 90 占 폚.

Subsequently, 4-chlorobutyl methacrylate (25.6 g, 0.145 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise and stirred for 3 hours.

Thereafter, the reaction solution was neutralized with 2N HCl in 1 L of water, extracted with ethyl acetate (700 mL), washed with saturated brine, and concentrated. Crude crystals (crude crystals) were collected and collected by silica gel column chromatography to obtain 18 g of an intermediate compound.

18 g of the intermediate compound and 7.79 g (0.07 mol) of triethylamine (Wako Pure Chemical Industries, Ltd.) were dissolved in 100 mL of THF and cooled to 0 占 폚.

Then, cinnamoyl chloride (13.1 g, 0.07 mol, manufactured by Tokyo Kasei Kogyo Co., Ltd.) 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, this was fractionated by silica gel column chromatography to obtain 22 g of a monomer a-3 having a chalcone group as a photo-aligning group.

[Synthesis of constituent unit (monomer a-4) having photo aligning group]

Macromolecules 2004, Vol. 37, # 7, and p.2572, a monomer a-4 having an azo group as a photo-alignable group was synthesized.

[Synthesis of constituent unit (monomer a-5) having photo aligning group]

Jounal of Polymer Science, Part A: Polymer Chemistry, 2010, Vol. 48, # 19, and 4323, a monomer a-5 having a coumarin group was synthesized as a photo-alignable group.

[Synthesis of constituent unit (monomer e-1) protected with an acid-decomposable group at an acid]

Methacrylic acid (86 g, 1 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was cooled to 15 캜, and camphorsulfonic acid (4.6 g, 0.02 mol, manufactured by Tokyo Kasei Kogyo K.K.) was added.

Then, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) made by Kawaken Fine Chemicals Co., Ltd. was added dropwise to the reaction solution.

After stirring for 1 hour, saturated sodium hydrogencarbonate (500 mL) was added, and the mixture was extracted with ethyl acetate (500 mL).

Subsequently, after drying with magnesium sulfate, the insoluble material was filtered and concentrated under reduced pressure at 40 ° C or lower, and the yellow oily matter of the residue was subjected to vacuum distillation to obtain a monomers e-1 having a boiling point (bp) of 54 125 g of methacrylic acid tetrahydro-2H-furan-2-yl in 56 ° C / 3.5 mmHg fraction (yield) was obtained (yield 80%) as a colorless oil.

[Synthesis of polymer (P1) having constituent unit s1]

22 g of diethylene glycol methyl ethyl ether (hereinafter abbreviated as "HS-EDM") was heated and stirred at 70 ° C. in a stream of nitrogen. (11 g, 45 mol%), hexafluoroisopropyl methacrylate (hereinafter abbreviated as "HFIP") (3.5 g, 15 mol%, manufactured by TOKYO KASEI KOGYO CO., LTD.), Methacrylic (Hereinafter abbreviated as "MAA") (Wako Pure Chemical Industries, Ltd., 1.7 g, 20 mol%), glycidyl methacrylate (hereinafter abbreviated as "GMA" (2 mol%) of a radical polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) and PGMEA (30 g) was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was further reacted at 70 DEG C for 4 hours to obtain a PGMEA solution (solid content concentration: 27%) of the polymer P1 having the constituent unit s1.

[Synthesis of polymer (P2-P11) having constituent unit s1]

Polymers P2 to P11 were synthesized in the same manner as Polymer P1, except that the kind of monomer, initiator and solvent was changed according to Table 1 below. In the column of each monomer component in the following Table 1, the numerical value is the amount (mol%) of each monomer relative to the total amount of the monomer components. The numerical values described in the column of the polymerization initiator are mol% when the total amount of the monomer components is 100 mol%. The abbreviations used in the examples are as follows.

<Abbreviation>

HFIP: Hexafluoroisopropyl methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

6FM: Trifluoroethyl methacrylate (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.)

KBM-503: 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

C18MA: octadecane methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

MAA: methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)

MMA: Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)

St: Styrene (manufactured by Wako Pure Chemical Industries, Ltd.)

AA: Acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)

GMA: glycidyl methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.)

OXE-30: (3-ethyloxetan-3-yl) methyl methacrylate (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.)

Cyclomer M100: (3,4-epoxycyclohexyl) methyl methacrylate (manufactured by Daicel Chemical Industries, Ltd.)

DCPM: Dicyclopentanyl methacrylate (Pancuril FA-513M, manufactured by Hitachi Kasei Corporation)

NBMA: N-Butoxymethylacrylamide (manufactured by Mitsubishi Rayon Co., Ltd.)

V-601: Radical polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd.)

V-65: Radical polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd.)

PGMEA: Methoxypropylene glycol acetate (Daicel Co., Ltd.)

· HS-EDM: Diethylene glycol methyl ethyl ether (manufactured by Tohoku Kagaku Kogyo Co., Ltd.)

[Table 1]

[Synthesis of other photo-orientable polymer]

&Lt; Synthesis of Polymer P12 >

Polymer P12 was synthesized in the same manner as the photo-orientable polymer (A-1) described in [0161] (Preparation Example 1) of JP-A-2013-177561.

&Lt; Synthesis of Polymer P13 >

A polymer P13 was synthesized in the same manner as the specific copolymer P1 described in the paragraph (Synthesis Example 1) of WO2010 / 150748.

[Preparation of polymer A having another constituent unit]

&Lt; Synthesis of polymer A-1 comprising a structural unit a1 having a group protected by an acid-decomposable group and a structural unit a2 having a crosslinkable group >

HS-EDM (82 parts) was heated and stirred in a nitrogen stream at 90 占 폚.

Then, 43 parts (corresponding to 40.5 mol% in total monomer components) of methacrylic acid tetrahydro-2H-furan-2-yl methacrylate synthesized as monomer e-1, 48 parts of OXE-30 (corresponding to 9.5 mol% of the total monomer components), 11 parts of hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd., 12.5 mol% , A solution of Polymer A-1 (corresponding to a solid content (hereinafter referred to as &quot; Polymer A-1 &quot;)), a mixed solution of a radical polymerization initiator V-601 (4.3 parts) and PGMEA (82 parts) Concentration: 40%).

The polymer A-1 thus obtained had a weight average molecular weight of 15,000 as measured by gel permeation chromatography (GPC).

&Lt; Synthesis of polymer A-2 containing structural unit a1 having a group protected with an acid-decomposable group &

PGMEA (238 g) was heated and stirred in a nitrogen stream at 90 占 폚.

Subsequently, 240 g (corresponding to 61.1 mol% of the total monomer components) of methacrylic acid tetrahydro-2H-furan-2-yl methacrylate synthesized as the monomer e-1, 50.4 g (MA of 17.6 mol% ), MMA (27.9 g, corresponding to 21.3 mol% of the total monomer components), radical polymerization initiator V-601 (14.7 g) and PGMEA (238 g) The reaction was carried out at 90 占 폚 for a time, and after cooling, PGMEA (42 g) was added to obtain a solution of polymer A-2 (solid concentration: 38%).

The polymer A-2 thus obtained had a weight average molecular weight measured by gel permeation chromatography (GPC) of 15,000.

&Lt; Synthesis of polymer A-3 containing the structural unit a2 having a crosslinkable group >

The HS-EDM (145 g) was heated and stirred in a nitrogen stream at 70 占 폚.

Subsequently, 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 65 (20.8 g (5.6 mol% in terms of monomer amount)) and HS-EDM (145 g) was added dropwise over 2 hours.

After completion of the dropwise addition, the mixture was reacted at 70 DEG C for 4 hours to obtain a PGMEA solution (solid content concentration: 35%) of Polymer A-3.

<Polymer A-4 comprising the constituent unit a3 having an acid group and the constituent unit a2 having a crosslinkable group>

PGMEA (268 parts) was heated and stirred in a nitrogen stream at 90 占 폚.

Then, 143.4 parts (corresponding to 40.1 mol% in total monomer components) of methacrylic acid tetrahydro-2H-furan-2-yl methacrylate synthesized as monomer e-1, 168.4 parts of Cyclomer M100 (37.5 (corresponding to 9.9 mol% of the total monomer components), 37.2 parts (12.5 mol% of all monomer components) of hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) , A mixed solution of a radical polymerization initiator V-601 (5.5 parts) and PGMEA (268 parts) was added dropwise over 2 hours, and the mixture was further reacted at 90 DEG C for 2 hours to obtain a solution of the polymer A- Concentration: 40%).

The polymer A-4 thus obtained had a weight average molecular weight of 16,000 as measured by gel permeation chromatography (GPC).

&Lt; Polymer A-5 comprising structural unit a3 having an acid group and structural unit a2 having a crosslinkable group >

After the inside of the flask was purged with nitrogen, 459.0 g of a diethylene glycol dimethyl ether solution in which 9.0 g of 2,2'-azobisisobutyronitrile was dissolved was introduced.

Subsequently, St (22.5 g), MAA (45.0 g), DCPM (67.5 g), and GMA (90.0 g) were introduced and stirring was started slowly.

Subsequently, the temperature of the solution was raised to 80 DEG C, the temperature was maintained for 5 hours, and the polymerization was terminated by heating at 90 DEG C for 1 hour.

Thereafter, the reaction product solution was added dropwise to a large amount of water to solidify the reaction product. After washing the solidified product with water, the solidified product was redissolved in THF (200 g) and solidified again with a large amount of water.

This redissolving and coagulation operation was carried out three times in total, and the resulting coagulum was dried under reduced pressure at 60 DEG C for 48 hours to obtain polymer A-5. Thereafter, a polymer A-5 solution was prepared by using diethylene glycol so that the solid concentration became 25 mass%.

<Polymer A-6>

Polymer A-6 was synthesized in the same manner as in the non-oriented polymer (E-1) described in [0165] (Preparation Example 5) of Japanese Patent Application Laid-Open No. 2013-177561.

[Crosslinking agent B]

The following crosslinking agent B was used.

<B-1>

As the crosslinking agent B-1 having a molecular weight of 5,000 or less, a polyfunctional epoxy compound (Oxol EG, manufactured by Osaka Gas Co., Ltd.) was used.

<B-2>

As the crosslinking agent B-2 having a molecular weight of 5,000 or less, a polyfunctional epoxy compound (EX-321L, manufactured by Nagase ChemteX Corporation) was used.

<B-3>

As the crosslinking agent B-3 having a molecular weight of 5,000 or less, a polyfunctional epoxy compound (JER57S65, manufactured by Japan Epoxy Resin Co., Ltd.) was used.

[Other components]

<F-554>

As the surfactant, a perfluoroalkyl group-containing nonionic surfactant (F-554, manufactured by DIC) was used.

<KBM-403>

As the adhesion improver,? -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 was dissolved and mixed in a solvent (PGMEA) until the solid content concentration reached 18 mass%, and the solution was filtered with a polytetrafluoroethylene filter having a pore size of 0.2 m to obtain a resin A composition was prepared. The addition amount in the table indicates the amount added by the solid content of each component, and the unit is parts by mass.

The obtained resin composition was applied on a glass substrate by a spin coat method, preliminarily dried on a hot plate at 80 DEG C for 1 minute, and then fired in a clean oven at 230 DEG C for 60 minutes to form a cured film of an overcoat layer of 3 mu m .

The formed cured film was subjected to oblique cutting by a surface and interfacial cutting apparatus (DN-20S type, made by Dypler &amp; Wints) to expose a cross section.

The intensity ratio ELq and the intensity ESub of the mass analysis of fragments derived from the aligning group were measured and the intensity ratio (intensity ELq / intensity ESub) of the exposed cross section was measured by the above-mentioned measuring apparatus and conditions, . The results are shown in Table 2 below. Further, the same test was performed on the alignment protection layer after the display device described later was fabricated, but the results were the same.

A: When the intensity ratio is 10 times or more, or the intensity Esub is below the measurement limit

B: Intensity ratio is more than 8 times to less than 10 times

C: Intensity ratio is more than 5 times to less than 8 times

D: intensity ratio more than 2 times to less than 5 times

E: intensity ratio less than 2 times

F: No fragment peak

[Table 2]

〔evaluation〕

<Orientation>

Each of the prepared resin compositions was coated on a non-alkali glass substrate by a spin coater (spinner), and then prebaked on a hot plate at 100 캜 for 2 minutes to form a coating film having a film thickness of 4.0 탆.

Subsequently, the resulting coating film was irradiated with a high-pressure mercury lamp at an exposure dose of 1000 J / m ² , and then post-baked at a curing temperature of 230 캜 and a curing time of 30 minutes in an oven to form a protective layer.

The formed protective layer was irradiated with deflected light at 750 mJ / cm ² and photo-alignment treatment using an ultraviolet ray polarizing exposure apparatus (HC-2150PUFM, manufactured by Lan Technical Service Co., Ltd.) to form an alignment protection layer .

Thereafter, horizontally aligned liquid crystal was applied, and the alignment state was observed with a polarization microscope at a magnification of 20 times. The place was changed and observed with five fields of view (about 1 square m), and evaluated according to the following criteria. The results are shown in Table 3 below.

A: No problem

B: Level where there is no problem in practice although the joke is confirmed.

C: Defective, bright spot observed

D: Not aligned at all

&Lt; Retardation (Rth) >

Each of the prepared resin compositions was coated on a non-alkali glass substrate by a spin coater and then pre-baked on a hot plate at 100 캜 for 2 minutes to form a coating film having a film thickness of 4.0 탆.

Subsequently, the resulting coating film was irradiated with a high-pressure mercury lamp at an exposure dose of 1000 J / m ² , and then post-baked at a curing temperature of 230 캜 and a curing time of 30 minutes in an oven to form a protective layer.

The birefringence of the protective layer was evaluated using a phase difference measuring apparatus KOBRA-WFD (manufactured by Oji Scientific Co., Ltd.). The results are shown in Table 3. Further, the birefringence is caused by the angle deviation of the display, and therefore, there is no practical problem if it is not more than 30 nm, but a low value is preferable.

<Flatness>

(L / S width ratio of 1: 1) having a height of 1 mu m and a width of 10 mu m was prepared. The resin composition was applied thereon with a spin coater and pre-baked at 90 DEG C for 120 seconds. And then thermally cured for 30 minutes to obtain a cured film of 2 m.

The flatness of the obtained cured film was defined and calculated. The results are shown in Table 3 below. In addition, the planarity is higher as the value is closer to 100, the planarization capability is higher, and the practical value is required to be 70% or more.

Flatness (%) = (1 -? D / H) x 100

Here,? D means the difference (μm) between the film thickness of the cured film on the L / S pattern and the film thickness (2 μm) of the cured film, and H denotes the difference Means the film thickness (μm).

<Display characteristics>

(1) Fabrication of array substrate

According to the description of Example 42 of International Publication No. WO 2009/025386, an insulating film having a contact hole formed on an array substrate was formed.

Subsequently, a transparent conductive layer made of ITO was formed on the insulating film by sputtering on the substrate having the insulating film formed thereon. Next, the transparent conductive layer was etched by photolithography, and a common electrode was formed on the insulating film.

Thereafter, an insulating layer of SiN was formed by sputtering. Next, the SiN layer was etched by photolithography 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 by sputtering. Subsequently, the transparent conductive layer was etched by photolithography to form a comb-shaped pixel electrode on the inorganic insulating film.

Thus, the array substrate of this embodiment was manufactured. In the obtained array substrate of the present embodiment, a contact hole of a desired size was formed at a desired position of the insulating film, and electrical connection was made between the pixel electrode and the source-drain electrode of the active element.

As a liquid crystal aligning agent containing a radiation-sensitive polymer having a photo-orientable group, a liquid crystal aligning agent A-1 described in Example 6 of International Publication No. WO 2009/025386 was coated on a transparent electrode of an array substrate by a spinner do. Subsequently, pre-baking was performed with a hot plate at 80 DEG C for 1 minute, and then the coated film was heated at 180 DEG C for 1 hour in an oven where the inside was replaced with nitrogen to form a coating film having a thickness of 80 nm. Subsequently, a polarizing ultraviolet ray ²⁰⁰ J / m ² containing a bright line of 313 nm was irradiated onto the surface of the coating film from a direction inclined by 40 ° with respect to a direction perpendicular to the substrate surface using an Hg-Xe lamp and a Glane Taylor prism, An array substrate having an orientation film was produced.

(2) Fabrication of counter substrate

First, a color filter substrate manufactured by a known method was prepared. In this color filter substrate, a minute colored pattern 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 coloring 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, and prebaked at 90 DEG C / 120 seconds And then thermally cured in an oven at 230 DEG C for 30 minutes to prepare a protective film. Subsequently, the protective film was subjected to photo alignment treatment for irradiating deflected light at 750 mJ / cm ² using an ultraviolet ray polarizing exposure apparatus (HC-2150PUFM, manufactured by Lan Technical Service Co., Ltd.) to form an orientation protective film of 2 μm To prepare a counter substrate.

(3) Manufacturing of display devices

A color liquid crystal display element was produced by sandwiching the liquid crystal layer by the obtained alignment substrate with an alignment protective film and an array substrate. As the liquid crystal layer, those made of nematic liquid crystal and aligned in parallel to the substrate surface were used. The display characteristics and reliability of these liquid crystal display devices were evaluated.

(4) Evaluation

The liquid crystal display device was allowed to stand in an oven at a temperature of 60 占 폚 / humidity of 90% for 1 week, and evaluated again for driving. The results are shown in Table 3 below.

A: No display defect occurred at all

B: Display failure occurred at 1% or more and less than 10% of the pixels, but there was no problem in practical use

C: A display failure occurred at 10% or more of the pixels

D: What could not be displayed immediately after manufacturing

[Table 3]

From the results shown in Tables 1 to 3, when the alignment protection layer does not have an orientation group, fragments derived from the aligning group are not detected, and the display characteristics are poor even after the liquid crystal display element immediately after preparation (Comparative Examples 1 and 2).

In addition, in Comparative Examples 3 and 4, the strength ELq of the fragment derived from the aligning group of the orientation protection layer was at least twice the strength ESub, but since it did not have an orienting group and a crosslinking structure connected to each other via covalent bonds, And the display characteristics after exposure were inferior (Comparative Examples 3 to 4).

When a polymer having no ubiquitous group for localizing an oriented group is used, the strength ELq of the fragment derived from the aligning group of the orientation-protective layer to be formed becomes less than twice the intensity ESub, (Comparative Examples 5 to 6).

On the other hand, when a polymer having a constituent unit s1 and a constituent unit a2 or the like and a polymer having no constituent unit s1 and having a constituent unit a3 or the like is used, it is preferable that the formed orientation- It is possible to maintain excellent flatness while maintaining a good flatness even under a high temperature and high humidity if the strength ratio ELq of the fragment analysis derived from the orienting group and the intensity ratio (intensity ELq / intensity ESub) It was found that the display performance was good even when exposed (Examples 1 to 24).

In particular, from the comparison of Example 1 and Example 24, it was found that blending of the cross-linking agent B having a molecular weight of 5,000 or less improves the flatness and the display performance becomes better.

10: Liquid crystal display
12: Backlight unit
14, 15: substrate
16: Thin film transistor
17:
18: Contact hole
19: ITO transparent electrode
20: liquid crystal layer
21: orientation protection layer
22: Color filter
23:
30: first substrate
40: second substrate

Claims (14)

A liquid crystal display device having a first substrate, a liquid crystal layer, and a second substrate in this order from the viewer side,
Wherein the first substrate comprises a substrate and an alignment protection layer,
Wherein the second substrate includes a substrate, a thin film transistor, a display electrode, and an alignment film,
Wherein the alignment protection layer has a surface in contact with the liquid crystal layer,
Wherein the alignment protection layer has an oriented group and a cross-linked structure connected to each other via a covalent bond,
The intensity ELq of the mass analysis of the fragment derived from the orienting group on the surface of the orientation-protective layer which is in contact with the liquid crystal layer, and the intensity ELq of the mass spectrum of the fragment derived from the orienting group, The intensity ESub of the mass analysis of the fragment derived from the orienting group on the substrate side of the orientation protection layer satisfies the following condition 1 or 2,
Wherein the cross-linking structure comprises 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 measured significantly and the intensity ESub is below the measurement limit.
[Chemical Formula 1]

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. The method according to claim 1,
And the intensity ELq is 5 to 20 times the intensity ESub. The method according to claim 1 or 2,
Wherein the orienting group is a group formed by photo-reacting a photo aligning group. The method according to any one of claims 1 to 3,
And the thickness of the orientation protection layer is 1 to 4 占 퐉. The method 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 method according to any one of claims 1 to 5,
Wherein the fragment derived from the aligning group is a fragment derived from at least one photo aligning group selected from the group consisting of a cinnamate group and a chalcone group. After forming a protective layer on a substrate using a composition P for forming an orientation protection layer containing a polymer P containing a constituent unit having an oriented group and a polymer A containing no constituent unit having an oriented group, A first step of forming an alignment protection layer by performing alignment treatment on the first substrate,
A liquid crystal display device comprising: a first substrate; a second substrate provided with a substrate, a thin film transistor, a display electrode and an alignment film; and a liquid crystal sealed between the first substrate and the second substrate, And a second step of manufacturing the liquid crystal display device. The method of claim 7,
Wherein the polymer P comprises a constituent unit having the above-mentioned orientation group,
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 from 10 to 30 carbon atoms, and a structural unit having a photo-
Condition 3: the polymer P comprises a structural unit a2 having a crosslinkable group, and the polymer A comprises a structural unit a3 having an acid group.
Condition 4: the polymer P comprises the constituent unit a3 having an acid group, and the polymer A comprises the constituent unit a2 having a crosslinkable group. The method of 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. The method according to any one of claims 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%. The method 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 5,000 or less. The method of claim 11,
Wherein the crosslinking agent B comprises a crosslinking agent having an epoxy group,
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 mass% or less. The method according to any one of claims 7 to 12,
Wherein the orienting group is a photo aligning group,
Wherein the alignment treatment is an optical alignment treatment using light having a wavelength of 365 nm or less. The method 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.

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