JP6470204B2 - Manufacturing method of liquid crystal display panel - Google Patents

Description

  The present invention relates to a method for manufacturing a liquid crystal display panel.

  Liquid crystal display panels are widely used for monitors and television applications such as personal computers and smartphones because of their various advantages, such as low voltage and low power consumption, and enabling miniaturization and thinning.

  In general, a liquid crystal display panel includes a pair of substrates, a sealing material for bonding the pair of substrates, and a liquid crystal layer formed in a space surrounded by the pair of substrates and the sealing material. An alignment film for controlling the initial alignment of liquid crystal molecules is formed on the substrate. Conventionally, alignment films that have been subjected to rubbing treatment have been used in many cases, but static electricity and dust generated by rubbing treatment may lead to problems, so they are manufactured without using rubbing treatment such as photo-alignment treatment. Alignment films have also been developed. In this specification, the alignment film manufactured by the photo-alignment treatment is also referred to as “photo-alignment film”.

  By the way, when the alignment film is formed in a region where the sealing material is formed (hereinafter also referred to as “sealing material forming region”), there is a problem that the adhesive strength of the sealing material is lowered. In order to avoid such a problem, for example, in the method of manufacturing a liquid crystal display panel disclosed in Patent Document 1, the sealing material is formed on the substrate after the photo-alignment film formed in the sealing material forming region is removed. .

JP 2015-36721 A

  However, in the method of Patent Document 1, in the step of removing the photo-alignment film formed in the sealing material forming region, a resist mask is separately formed using a resist solution, and etching is performed. There was a problem of being big.

  In view of the above circumstances, an object of the present invention is to provide a simpler method for manufacturing a liquid crystal display panel.

  As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by providing the alignment film material with not only photo-alignment properties but also photo-patterning properties.

(1) preparing a pair of substrates in which a photo-alignment film is formed in a region other than the sealing material forming region;
Forming a sealing material in the sealing material forming region of any one of the pair of substrates; and a sealing material forming step;
A bonding step of bonding the pair of substrates together with the sealing material;
A liquid crystal layer forming step of forming a liquid crystal layer in a space surrounded by the pair of substrates and the sealing material,
The substrate preparation step
A coating film forming step of forming a coating film made of an alignment film material having a photopatterning property and a photoalignment property and containing a thermosetting component on a pair of substrates having a sealing material forming region;
Removing and removing the coating film formed in the sealing material formation region of the coating film by exposing and developing the coating film;
Thermosetting the coating film remaining after the removing step, and forming a thermosetting film in a region other than the sealing material forming region of the pair of substrates;
A method of manufacturing a liquid crystal display panel, comprising: a photo-alignment treatment step, wherein the thermosetting film is subjected to a photo-alignment treatment, and a photo-alignment film is formed in a region other than the sealing material formation region of the pair of substrates.
(2) Of the thermosetting film, an angle between a side end surface of the thermosetting film formed in the liquid crystal layer forming region and in contact with the sealing material forming region and a surface of the thermosetting film in contact with the substrate is 30. The manufacturing method of the liquid crystal display panel as described in said (1) which is -90 degree | times.
(3) The method for producing a liquid crystal display panel according to (1) or (2), wherein the alignment film material is a positive type in which an exposed portion of a coating film to be formed is dissolved.
(4) When the softening temperature of the coating film is Tm [° C.] and the curing start temperature of the thermosetting component in the coating film is Tc [° C.]
The manufacturing method of the liquid crystal display panel in any one of said (1)-(3) with which said Tm and Tc satisfy | fill following formula (1) and (2).
Tm = 80 to 200 (1)
Tc ≦ Tm + 20 (2)
(5) Of the coating film remaining after the removing step, an angle between a side end surface of the coating film formed in the liquid crystal layer forming region and the surface of the coating film in contact with the substrate is 70 to 90. The manufacturing method of the liquid crystal display panel in any one of said (1)-(4) which is degree.
(6) The manufacturing method of the liquid crystal display panel in any one of said (1)-(5) whose wavelength of the light used by the said exposure is longer than the wavelength of the light used by the said photo-alignment process.
(7) The manufacturing method of the liquid crystal display panel in any one of said (1)-(6) whose light used by the said photo-alignment process is a linearly polarized light.

  As described below, according to the present invention, a simpler method for manufacturing a liquid crystal display panel can be provided.

FIG. 1 is a cross-sectional view of a pair of substrates 10 used in an embodiment of the manufacturing method of the present invention. FIG. 2 is a plan view of a pair of substrates 10 used in an embodiment of the manufacturing method of the present invention. FIG. 3 is a cross-sectional view after the coating film forming step in one embodiment of the production method of the present invention. FIG. 4 is a cross-sectional view after the removal step in one embodiment of the production method of the present invention. FIG. 5 is a cross-sectional view after the thermosetting step in one embodiment of the production method of the present invention. FIG. 6 is a cross-sectional view after the photo-alignment treatment step in one embodiment of the production method of the present invention. FIG. 7 is a plan view after the photo-alignment treatment step in one embodiment of the manufacturing method of the present invention. FIG. 8 is a cross-sectional view after the sealing material forming step in one embodiment of the manufacturing method of the present invention. FIG. 9 is a plan view after the sealing material forming step in one embodiment of the manufacturing method of the present invention. FIG. 10 is a cross-sectional view after the bonding step and the liquid crystal layer forming step in one embodiment of the manufacturing method of the present invention. FIG. 11 is a partial cross-sectional view after the removal step in one embodiment of the production method of the present invention. FIG. 12 is a partial cross-sectional view after the thermosetting step in one embodiment of the production method of the present invention.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, “(meth) acrylate” is a notation representing “acrylate” or “methacrylate”, “(meth) acryl” is a notation representing “acryl” or “methacryl”, and “(meth) “) Acryloyl” is a notation representing “acryloyl” or “methacryloyl”, and “(meth) acryloyloxy” is a notation representing “acryloyloxy” or “methacryloyloxy”.

  The manufacturing method of the liquid crystal display panel (liquid crystal display device) of the present invention includes the following steps (1) to (4). Hereinafter, the method for manufacturing a liquid crystal display panel of the present invention is also referred to as “the manufacturing method of the present invention”.

Step (1): Substrate preparation step Step of preparing a pair of substrates in which a photo-alignment film is formed in a region other than the sealing material formation region Step (2): Sealing material formation step Any one of the pair of substrates Step / step (3) of forming a sealing material in the sealing material formation region: bonding step Step / step (4) of bonding the pair of substrates together with the sealing material: liquid crystal layer forming step The pair of substrates and the above A process of forming a liquid crystal layer in a space surrounded by a sealing material

Here, the substrate preparation step includes the following steps (1-1) to (1-4).
-Process (1-1): Coating film formation process The coating film which consists of alignment film material which has photo-patterning property and photo-alignment property on a pair of board | substrate which has a sealing material formation area | region, and contains a thermosetting component. Step / Step (1-2): Forming Step The step / step (1) of exposing and developing the coating film to remove the coating film formed in the sealing material formation region of the coating film. -3): Thermosetting step Step / step (1-4): light for thermosetting the coating film remaining after the removing step and forming a thermosetting film in a region other than the sealing material forming region of the pair of substrates. Alignment treatment step A step of applying a photo-alignment treatment to the thermosetting film and forming a photo-alignment film in a region other than the sealing material formation region of the pair of substrates

First, the manufacturing method of the present invention will be described with reference to the drawings.
1-10 is a schematic diagram which shows one embodiment of the manufacturing method of this invention in order of a process.

First, in the substrate preparation step, a pair of substrates in which the photo-alignment film 26 is formed in a region other than the sealing material formation region b is prepared. Specifically, it is as follows.
FIG. 1 is a cross-sectional view of a pair of substrates 10 used in an embodiment of the manufacturing method of the present invention. FIG. 2 is a plan view of the pair of substrates 10. Only one of the pair of substrates is shown. A liquid crystal layer forming region a exists near the center of the main surface of the pair of substrates 10, a sealing material forming region b exists around the liquid crystal layer forming region, and an end region around the sealing material forming region b c exists.
First, in the coating film forming step, an alignment film material (hereinafter also referred to as “specific alignment film material”) having a photo-patterning property and a photo-alignment property and containing a thermosetting component is formed on the pair of substrates 10. A coating film 20 is formed (FIG. 3).
Next, in the removing step, the coating film 20 is exposed and developed, and the coating film formed in the sealing material forming region b is removed from the coating film 20 (FIG. 4).
Further, in the thermosetting step, the coating film 22 (22a, 22c) remaining after the removing step is thermoset, and regions other than the sealing material forming region b of the pair of substrates 10 (liquid crystal layer forming region a, end region c). Then, the thermosetting film 24 (24a, 24c) is formed (FIG. 5).
Thereafter, in the photo-alignment processing step, the thermosetting film 24 is subjected to photo-alignment processing, and the photo-alignment films 26 (26a, 26c) are formed in regions other than the sealing material forming region b of the pair of substrates 10 (FIGS. 6 and 7). ).
In this manner, a pair of substrates (a pair of substrates 12 with a photo-alignment film) in which the photo-alignment film 26 is formed in a region other than the sealing material formation region b is prepared.

Next, in the sealing material forming step, the sealing material 30 is formed in any one sealing material forming region b of the pair of substrates 12 with the photo-alignment film (FIGS. 8 and 9).
Thereafter, in the bonding step, the sealing material 30 of the substrate 12 with the photo-alignment film on which the sealing material 30 is formed is aligned with the sealing material formation region b of the substrate 12 with the photo-alignment film on which the sealing material is not formed. A pair of substrate 12 with a photo-alignment film is bonded by the sealing material 30.
Before or after the bonding step, a liquid crystal layer forming composition is sandwiched between a pair of substrates 12 with a photo-alignment film, and liquid crystal is formed in a space surrounded by the pair of substrates 12 with a photo-alignment film and the sealing material 30. Layer 40 is formed. In this way, the liquid crystal display panel 100 is obtained (FIG. 10).

  Hereinafter, materials and procedures used for each step will be described in detail.

[Step (1): Substrate preparation step]
The substrate preparation step is a step of preparing a pair of substrates in which a photo-alignment film is formed in a region other than the sealing material formation region, and includes steps (1-1) to (1-4) described later.

[Step (1-1): Coating film forming step]
The coating film forming step is a coating film comprising an alignment film material (specific alignment film material) having a photo-patterning property and a photo-alignment property and containing a thermosetting component on a pair of substrates having a sealing material forming region. Is a step of forming. Hereinafter, the materials and procedures used will be described in detail. The specific alignment film material will be described in detail after the description of all steps.

<Board>
In the manufacturing method of the present invention, a pair of substrates is used. One of the pair of substrates is a substrate (hereinafter also referred to as “first substrate”) provided on the viewing side with respect to a liquid crystal layer to be described later, and the other is a side opposite to the first substrate of the liquid crystal layer to be described later (usually, A substrate (hereinafter also referred to as a “second substrate”) provided on the backlight side.

  The substrate has a region where a sealing material is formed (a sealing material forming region). Note that the substrate on which the sealing material is formed in the sealing material forming step is only one of the pair of substrates, but in the subsequent bonding step, the sealing material formed on one substrate is the other substrate. Since it is bonded to the sealing material forming region, as a result, the sealing material is also formed in the sealing material forming region of the other substrate. Therefore, usually, when a pair of substrates are opposed to each other, the sealing material forming regions of both coincide in the main surface direction.

  Although the shape of the sealing material forming region is not particularly limited, it is preferably a band shape surrounding the region where the liquid crystal layer is formed (liquid crystal layer forming region) as shown in FIG.

(First substrate)
The first substrate preferably includes a base material and a color filter (color filter substrate).

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

(2) Color filter The color filter is not particularly limited. For example, a color filter generally used for a liquid crystal display panel can be used.
Such a color filter is usually composed of transparent colored patterns of red, green and blue, and each transparent colored pattern is made of a resin composition in which a colorant is dissolved or dispersed, preferably pigment fine particles are dispersed. Composed.
The color filter may be formed by preparing an ink composition colored in a predetermined color and printing it for each colored pattern. However, a paint type photosensitive material containing a colorant of a predetermined color may be used. It is more preferable to carry out by a photolithography method using a conductive resin composition.

(Second substrate)
The second substrate preferably includes a base material, a thin film transistor, and a display electrode.

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

(2) Thin Film Transistor As the thin film transistor (TFT), those used in known liquid crystal display panels can be used as appropriate, and the configuration is not particularly limited, and is a top gate type. There may be a bottom gate type.
Specific examples of the thin film transistor include amorphous silicon-TFT, low-temperature polysilicon-TFT, and oxide semiconductor TFT.

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

<Formation method of coating film>
Although the method in particular of forming a coating film is not restrict | limited, The method etc. which apply | coat the specific alignment film material mentioned later on a pair of board | substrate are mentioned.

  The coating method is not particularly limited. Specifically, for example, a printing method (for example, gravure printing method, screen printing method, flexographic printing method, inkjet printing method, imprinting method, etc.), spin coating method, slit coating method, etc. , Slit and spin coating method, curtain coating method and the like.

When the specific alignment film material contains a solvent, a solvent removal step of removing the solvent contained in the coating film may be provided before the removal step.
In the solvent removal step, the processing conditions differ depending on the type and amount of the solvent. For example, when NMP (N-methylpyrrolidone) is used as the solvent, the temperature is about 80 to 150 ° C. and about 0.5 to 3 minutes. The step of heating is preferable, and the step of heating at about 90 to 120 ° C. for about 0.5 to 2 minutes is more preferable.

<Thickness of coating film>
The thickness of the coating film is not particularly limited, but is preferably 0.1 to 5 μm.

<Softening temperature Tm of coating film, curing start temperature Tc of thermosetting component in coating film>
When the softening temperature of the coating film is Tm [° C.] and the curing start temperature of the thermosetting component in the coating film is Tc [° C.], the above Tm and Tc satisfy the following formulas (1) and (2). preferable. When Tm and Tc satisfy the following formulas (1) and (2), the angle d2 of the thermosetting film formed by the thermosetting process described later becomes large, and a liquid crystal display panel with a narrower frame can be obtained. The thermosetting component is as described later.
Tm = 80 to 200 (1)
Tc ≦ Tm + 20 (2)

The softening temperature Tm [° C] of the coating is measured by measuring the displacement at each temperature by pushing the coating into a hardness machine, applying a load (100 mN), increasing the temperature from 90 ° C to 350 ° C in 5 ° C increments. Calculated. Specifically, the temperature at which the displacement changed by 10% or more was defined as the softening temperature Tm.
Further, the curing start temperature Tc [° C.] of the thermosetting component in the coating film was calculated by measuring IR (infrared spectroscopy) while increasing the temperature of the coating film by 5 ° C. per minute. Specifically, the temperature at which the change amount of the IR spectrum of the reactive group in the curing reaction in each thermosetting component becomes a value of 10% or more with respect to the final change amount of the IR spectrum is the curing start temperature Tc. It was.

[Step (1-2): Removal step]
A removal process is a process of exposing and developing with respect to the coating film formed at the coating-film formation process, and removing the coating film formed in the sealing material formation area among the said coating films.

<Exposure>
As a light source for exposure, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generator, etc. can be used. Actinic rays having a wavelength of 300 nm to 450 nm such as a line (436 nm) can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed. The exposure amount is preferably 1 to 500 mJ / cm ² .
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, and a laser exposure can be used. In addition, exposure using a so-called super-resolution technique can be performed. Examples of the super-resolution technique include multiple exposure in which exposure is performed a plurality of times, a method using a phase shift mask, and an annular illumination method. By using these super-resolution techniques, it is possible to form a higher definition pattern, which is preferable.

  In addition, it is preferable that the wavelength of the light used by exposure is longer than the wavelength of the light used by the photo-alignment process mentioned later.

<Development>
The developer used for development preferably contains an aqueous solution of a basic compound. Examples of the basic compound include compounds described in paragraph 0171 of International Publication No. 2015/0887829, such as sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetra Butylammonium hydroxide and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferred. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dipping method, and the like.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.

<Angle d1 of coating film>
Of the coating film remaining after the removal step, the angle d1 between the side end surface of the coating film formed in the liquid crystal layer formation region and the surface of the coating film that contacts the substrate is not particularly limited, but is narrower. From the reason that a liquid crystal display panel with a frame can be obtained, the angle is preferably 50 degrees or more, more preferably 70 degrees or more, and further preferably 70 to 90 degrees. Among them, a larger angle is preferable. That is, 90 degrees is most preferable. In the present specification, a large angle for an angle up to 90 degrees is also simply referred to as “a large angle”.
As shown in FIG. 11 (partial cross-sectional view after the removing step in one embodiment of the manufacturing method of the present invention), the coating film angle d1 is in the liquid crystal layer forming region a of the coating film remaining after the removing step. This is the angle between the side end face 22p of the formed coating film 22a in contact with the sealing material forming region b and the surface 22q of the coating film 22a in contact with the substrate 10.

[Step (1-3): Thermosetting step]
The thermosetting step is a step of thermosetting the coating film remaining after the removing step and forming a thermosetting film in a region other than the sealing material forming region of the pair of substrates.

<Heat curing>
The heating temperature for thermosetting is preferably 180 to 400 ° C, and more preferably 220 ° C to 350 ° C. The heating time is preferably 15 to 120 minutes. This heating can be performed using a heating device such as a hot plate or an oven. Further, the transparency can be further improved by performing the heat treatment in a nitrogen atmosphere.
It is also possible to perform post-baking after baking at a relatively low temperature before thermosetting (post-baking) (addition of a middle baking step). When performing middle baking, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages.

In addition, when a coating film contains a photo-acid generator, the film hardening reaction can be accelerated | stimulated by post-baking, after carrying out full re-exposure (post-exposure) prior to post-baking. As a preferable exposure amount when the post-exposure step is included, 100 to 3,000 mJ / cm ² is preferable, and 100 to 500 mJ / cm ² is particularly preferable.

<The thickness of the thermosetting film>
The thickness of the thermosetting film is not particularly limited, but is preferably 0.1 to 5 μm.

<Angle d2 of thermosetting film>
Of the thermosetting film, the angle d2 between the side end face of the thermosetting film formed in the liquid crystal layer forming region and the surface of the thermosetting film in contact with the substrate is not particularly limited. A larger angle is preferable because a liquid crystal display panel with a narrow frame can be obtained. That is, 90 degrees is most preferable. Specifically, it is preferably 30 to 90 degrees, more preferably 50 to 90 degrees, and further preferably 70 to 90 degrees.
The angle d2 of the coating film was formed in the liquid crystal layer forming region a in the thermosetting film, as shown in FIG. 12 (partial sectional view after the thermosetting step in one embodiment of the manufacturing method of the present invention). This is the angle between the side end surface 24p of the coating film 24a that contacts the sealing material forming region b and the surface 24q of the coating film 24a that contacts the substrate 10.

[Step (1-4): Photo-alignment treatment step]
The photo-alignment processing step is a step of performing photo-alignment processing on the thermosetting film and forming the photo-alignment film in a region other than the sealing material formation region of the pair of substrates.

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

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

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

[Step (2): Sealing material forming step]
The sealing material forming step is a step of forming a sealing material in any one sealing material forming region of the pair of substrates obtained in the substrate preparing step.
A method for forming the sealing material is not particularly limited, but a method of applying the sealing material forming composition to the sealing material forming region is preferable. As the composition for forming a sealing material, conventionally known ones can be used, and examples thereof include an acrylic resin type, an epoxy resin type, a composition containing both an acrylic resin and an epoxy resin.

[Step (3): Bonding step]
The bonding process is a process of bonding a pair of substrates together with a sealing material. That is, a pair of photo-alignment films is formed by aligning the seal material of the substrate with a photo-alignment film on which the seal material is formed in the seal material forming step with the seal material forming region of the substrate with the photo-alignment film on which the seal material is not formed In this step, the attached substrate is bonded by the sealing material 30.

[Step (4): Liquid crystal layer forming step]
The liquid crystal layer forming step is a step of forming a liquid crystal layer in a space surrounded by the pair of substrates and the sealing material. In the bonding step, the liquid crystal layer forming composition is sandwiched between a pair of substrates with a photo-alignment film (a seal material is formed on one side), and the pair of substrates with the photo-alignment film and the seal material The liquid crystal layer is preferably formed in a space surrounded by 30.

As a driving method for driving the liquid crystal layer, a TN (Twisted Nematic) method, a VA (Vertical Alignment) method, an IPS (In-Plane-Switching) method, an FFS (Fringe Field Switching) method, an OCB (Optical Fully Coated) method. Examples include methods. Among these driving methods, the IPS method is preferable.
In the IPS liquid crystal cell, rod-like liquid crystal molecules are aligned substantially parallel to the substrate, and the liquid crystal molecules respond in a planar manner when an electric field parallel to the substrate surface is applied. That is, in the IPS system, the liquid crystal constituting the liquid crystal layer is a horizontally aligned liquid crystal. In the IPS system, black is displayed when no electric field is applied, and the absorption axes of a pair of upper and lower polarizing plates are orthogonal.

[Alignment film material]
The alignment film material (specific alignment film material) used in the present invention has photo-patterning properties and photo-alignment properties. Further, it contains a thermosetting component. That is, the alignment film material used in the present invention has photo-patterning properties, photo-alignment properties, and thermosetting properties.
The alignment film material contains a single compound having all three properties (photo-patterning property, photo-alignment property, and thermosetting property), so that it has three properties (photo-patterning property, photo-alignment property, and thermosetting property). ) May contain a plurality of compounds having each of the above. When the alignment film material contains a plurality of compounds, any of the plurality of compounds may have two or more of the three characteristics (photo patterning property, photo alignment property, thermosetting property). .

Further, the polymers p1 (photo-patterning property), p2 (photo-alignment property), p3 (photo-alignment property) and p4 (thermosetting component), which will be described later, may be contained as separate polymers. It may be contained as a polymer. That is, one polymer may be contained as a plurality of polymers among the polymers p1 to p4.
For example, P4 and P5 used in Examples described later are a structural unit having a group in which an acid group is protected by an acid-decomposable group, a structural unit having a photoalignable group, and a structural unit having a crosslinkable group. Therefore, it corresponds to all of the polymer p1 (photo-patterning property), the polymer p2 (photo-alignment property), and the polymer p4 (thermosetting component).

[Optical patterning]
As described above, the alignment film material used in the present invention has photo-patterning properties. That is, when the coating film formed from the alignment film material used in the present invention is exposed and developed, the exposed portion (exposed portion) is dissolved (positive type) or not exposed. A pattern is formed by dissolving a part (non-exposed part) (negative type). The alignment film material used in the present invention is preferably a positive type in which the exposed portion of the coating film to be formed dissolves because the angle d2 described above becomes large.

Examples of preferred embodiments for the alignment film material used in the present invention to have photo-patterning properties include the following preferred embodiments 1 to 3.
(1) Preferred embodiment 1: positive type (chemical amplification type)
A polymer containing a structural unit having a group in which an acid group is protected with an acid-decomposable group and a photoacid generator are contained.
(2) Preferred embodiment 2: Positive type (quinonediazide compound)
Contains quinonediazide compounds.
(3) Preferred embodiment 3: Negative type A compound (polymerizable compound) having two or more groups having an ethylenically unsaturated bond and a photopolymerization initiator are contained.
Hereinafter, each aspect is explained in full detail.

<Preferred embodiment 1: positive type (chemical amplification type)>
In preferred embodiment 1, the alignment film material generates a polymer p1 including a structural unit having a group in which an acid group is protected by an acid-decomposable group, and a photoacid generator (preferably, an acid having a pKa of 3 or less is generated. This is an embodiment containing a photoacid generator).
In the case of the preferred embodiment 1, when the coating film formed from the alignment film material is exposed, the acid-decomposable group is decomposed in the exposed portion and an acid group is generated, so that the exposed portion is dissolved by development, A positive pattern is formed. A preferred embodiment 1 is a so-called chemical amplification type.
Incidentally, the polyimide precursor p3 to be described later, when X ¹ or X ² in the formula (p3) to be described later is an acid-decomposable group, corresponding to the polymer p1.

(Polymer p1 containing a structural unit having an acid group protected by an acid-decomposable group)
In this specification, “a group in which an acid group is protected by an acid-decomposable group” causes a deprotection reaction using an acid as a catalyst (or an initiator), thereby generating an acid group, a regenerated acid, and a decomposed structure. Means group. As the group in which the acid group is protected with an acid-decomposable group, those known as an acid group and an acid-decomposable group can be used and are not particularly limited.
Preferred examples of the acid group include a carboxyl group and a phenolic hydroxyl group.
In addition, as an acid-decomposable group, a group that is relatively easily decomposed by an acid (for example, an acetal functional group such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group) or an acid-decomposable group is relatively difficult to decompose by an acid. Group (for example, tertiary alkyl group such as tert-butyl ester group, tertiary alkyl carbonate group such as tert-butyl carbonate group) and the like.

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

(1) Structural unit having a protected carboxyl group protected with an acid-decomposable group The structural unit having a protected carboxyl group protected with an acid-decomposable group is described in detail below. And a structural unit having a protected carboxyl group protected by an acid-decomposable group.
There is no restriction | limiting in particular as a structural unit which has the said carboxyl group which can be used for the structural unit which has the protected carboxyl group protected by the said acid-decomposable group, A well-known structural unit can be used. For example, a structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, or unsaturated tricarboxylic acid, or an ethylenically unsaturated group and an acid. And a structural unit having both an anhydride-derived structure.
Hereinafter, a structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and a structural unit having both an ethylenically unsaturated group and a structure derived from an acid anhydride will be described in order.

(1-1) Structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, etc. As a structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule As unsaturated carboxylic acid used by invention, the compound of Paragraph 0043 of JP, 2014-238438, A is mentioned, for example.
Among them, from the viewpoint of developability, acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid are used to form the above structural unit. 2- (meth) acryloyloxyethyl-phthalic acid or an anhydride of an unsaturated polyvalent carboxylic acid is preferably used. Acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid It is more preferable to use
The structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule may be composed of one kind alone, or may be composed of two or more kinds.

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

A known acid-decomposable group can be used as the acid-decomposable group that can be used in the structural unit having a protected carboxyl group protected by the acid-decomposable group.
In the present invention, the acid-decomposable group is preferably a protected carboxyl group in which the carboxyl group is protected in the form of an acetal. Furthermore, among the acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following formula a1-10. In addition, when the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following formula a1-10, the entire protected carboxyl group is-(C = O) -O-CR ¹⁰¹ R ¹⁰² ( OR ¹⁰³ ).

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

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

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

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

The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When it has a halogen atom as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become a haloalkyl group, and when it has an aryl group as a substituent, R ¹⁰¹ , R ¹⁰² and R ¹⁰³ become an aralkyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
Moreover, as said aryl group, a C6-C20 aryl group is preferable and a C6-C12 aryl group is more preferable. Specifically, a phenyl group, an α-methylphenyl group, a naphthyl group and the like can be exemplified, and as an entire alkyl group substituted with an aryl group, that is, as an aralkyl group, a benzyl group, an α-methylbenzyl group, a phenethyl group, A naphthylmethyl group etc. can be illustrated.
As said alkoxy group, a C1-C6 alkoxy group is preferable, a C1-C4 alkoxy group is more preferable, and a methoxy group or an ethoxy group is still more preferable.
Further, when the alkyl group is a cycloalkyl group, the cycloalkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is linear Or a branched alkyl group, it may have a cycloalkyl group having 3 to 12 carbon atoms as a substituent.
These substituents may be further substituted with the above substituents.

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

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

In the above formula a1-10, it is preferable that any one of R ¹⁰¹ and R ¹⁰² is a hydrogen atom or a methyl group.

  As the radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the formula a1-10, a commercially available one may be used, or one synthesized by a known method may be used. You can also. For example, it can be synthesized by a synthesis method described in paragraphs 0037 to 0040 of JP2011-221494A.

  The 1st preferable aspect of the structural unit which has the protected carboxyl group protected by the said acid-decomposable group is a structural unit represented by a following formula.

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

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

  The 2nd preferable aspect of the structural unit which has the protected carboxyl group protected by the said acid-decomposable group is a structural unit represented by a following formula.

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

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

(2) Structural unit having protected phenolic hydroxyl group protected with acid-decomposable group As the structural unit having protected phenolic hydroxyl group protected with acid-decomposable group, hydroxystyrene-based structural unit or novolac resin A structural unit is mentioned.
Among these, a structural unit derived from hydroxystyrene or α-methylhydroxystyrene is preferable from the viewpoint of sensitivity.
Moreover, as a structural unit having a phenolic hydroxyl group, the structural units described in paragraphs 0065 to 0073 of JP-A-2014-238438 are also preferable from the viewpoint of sensitivity.

  The molar ratio of the structural unit having a group in which the acid group is protected with an acid-decomposable group with respect to all the structural units constituting the polymer p1 is not particularly limited, but is preferably 10 to 100 mol%, and preferably 20 to 90%. More preferably, it is mol%.

The content of the polymer p1 in the alignment film material is not particularly limited, but is preferably 0.1 to 99.9 parts by mass with respect to 100 parts by mass of the total solid components. For example, the lower limit is more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more. For example, the upper limit is more preferably 90 parts by mass or less, and still more preferably 80 parts by mass or less.
The polymer p1 may be used alone or in combination of two or more.

(Photoacid generator)
The photoacid generator is not particularly limited.
The photoacid generator is preferably a compound that reacts with an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm and generates an acid, but is not limited to its chemical structure. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.

The photoacid generator used in the present invention is preferably a photoacid generator that generates an acid having a pKa of 3 or less, and more preferably a photoacid generator that generates an acid having a pKa of 2 or less.
Here, pKa basically refers to pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured after changing to a solvent suitable for measurement. Specifically, the pKa described in the chemical handbook can be referred to.
The acid having a pKa of 3 or less is preferably sulfonic acid or phosphonic acid, and more preferably sulfonic acid.
The photoacid generator is preferably one that generates an acid having a pKa of 2 or less.

  Examples of photoacid generators include onium salt compounds, trichloromethyl-s-triazines, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. . Among these, onium salt compounds, imide sulfonate compounds, and oxime sulfonate compounds are preferable, and onium salt compounds and oxime sulfonate compounds are particularly preferable. A photo-acid generator can be used individually by 1 type or in combination of 2 or more types.

Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane compounds include the compounds described in paragraph numbers 0083 to 0088 of JP2011-221494A; And compounds described in paragraph numbers 0013 to 0049 of JP-A-2011-105645, and the contents thereof are incorporated in the present specification.
Specific examples of the imide sulfonate compound include the compounds described in paragraphs 0065 to 0075 of WO2011 / 087011, and the contents thereof are incorporated herein.

It is also preferable to use triarylsulfonium salts having the following structure.

  Preferred examples of the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following general formula (B1-1).

General formula (B1-1)
In General Formula (B1-1), R ²¹ represents an alkyl group or an aryl group. Wavy lines represent bonds with other groups.

In general formula (B1-1), any group may be substituted, and the alkyl group in R ²¹ may be linear, branched or cyclic. Acceptable substituents are described below.
As the alkyl group for R ^21, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group for R ²¹ is a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group, etc.). It may be substituted with a bridged alicyclic group, preferably a bicycloalkyl group or the like.
As the aryl group for R ^21, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.

  The compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound described in paragraph numbers 0108 to 0133 of JP 2014-238438 A.

  As an imide sulfonate type compound, a naphthalene imide type compound is preferable, the description of international publication WO11 / 087011 pamphlet can be referred to, These content is integrated in this-application specification.

In the present invention, the content of the photoacid generator is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the alignment film material. For example, the lower limit is more preferably 0.2 parts by mass or more, and further preferably 0.5 parts by mass or more. For example, the upper limit is more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.
In addition, only 1 type may be used for a photo-acid generator, and it can also use 2 or more types together. When using 2 or more types of photo-acid generators, it is preferable that the total amount becomes the said range.

<Preferred embodiment 2: Positive type (quinonediazide compound))
A preferred embodiment 2 is an embodiment in which the alignment film material contains a quinonediazide compound.
In the case of the preferred embodiment 2, when the coating film formed from the alignment film material is exposed, a carboxy group is usually generated from the quinonediazide compound in the exposed portion. A pattern is formed. In the preferred embodiment 2, the alignment film material preferably contains a polymer containing a structural unit having a crosslinkable group described later.

(Quinonediazide compound)
As said quinonediazide compound, the 1, 2- quinonediazide compound which generate | occur | produces carboxylic acid by irradiation of actinic light can be used. As the 1,2-quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used. As specific examples of these compounds, for example, the description in paragraphs 0075 to 0078 of JP2012-088459A can be referred to, and the contents thereof are incorporated in the present specification.

  In the condensation reaction of the phenolic compound or alcoholic compound (mother nucleus) and 1,2-naphthoquinonediazidesulfonic acid halide, preferably 30 to 85 moles relative to the number of OH groups in the phenolic compound or alcoholic compound. %, More preferably 1,2-naphthoquinonediazidesulfonic acid halide corresponding to 50 to 70 mol% can be used. The condensation reaction can be carried out by a known method.

  Examples of the 1,2-quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, for example, 2,3,4-triaminobenzophenone-1,2. -Naphthoquinonediazide-4-sulfonic acid amide etc. are also used suitably. Further, 4,4 ′-{1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene} bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfone Condensate with acid chloride (3.0 mol), 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.0 mol) Mol)), 2,3,4,4′-tetrahydroxybenzophenone (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid ester (2.44 mol), etc. It may be used.

These quinonediazide compounds can be used singly or in combination of two or more.
The content of the quinonediazide compound in the alignment film material is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, and still more preferably 10 to 30 parts by mass with respect to 100 parts by mass of the total solid content. By setting the blending amount of the quinonediazide compound within the above range, the difference in solubility between the irradiated portion of the actinic ray and the unirradiated portion with respect to the alkaline aqueous solution as the developer is large, the patterning performance is improved, and the resistance of the cured film obtained is improved Good solvent properties.

<Preferable aspect 3: negative type>
A preferred embodiment 3 is an embodiment in which the alignment film material contains a compound having two or more groups having an ethylenically unsaturated bond (polymerizable compound) and a photopolymerization initiator.
In the case of the preferred embodiment 3, when the coating film formed from the alignment film material is exposed, the exposed portion is usually crosslinked, so that the unexposed portion is dissolved by development and a negative pattern is formed. . In the preferred embodiment 3, the alignment film material preferably contains a polymer containing a constituent unit having a crosslinkable group described later.

(Polymerizable compound)
Examples of the group having an ethylenically unsaturated bond that the polymerizable compound has include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group, and a (meth) acryloyl group is preferable.

  The polymerizable compound may be in any chemical form such as a monomer, a prepolymer, an oligomer, or a polymer. Monomers and / or polymers are preferred. The monomer type polymerizable compound preferably has a molecular weight of 100 to 3,000. The polymer type polymerizable compound preferably has a weight average molecular weight of 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 4,000 or more, and more preferably 5,000 or more.

  The polymerizable compound is preferably a (meth) acrylate compound. The (meth) acrylate compound is preferably a compound having 2 or more (meth) acryloyl groups in one molecule, and more preferably a compound having 3 or more (meth) acryloyl groups. The upper limit of the number of (meth) acryloyl groups is preferably 15 or less, more preferably 10 or less, still more preferably 8 or less, and particularly preferably 6 or less. Specific examples of these compounds include compounds described in paragraphs 0095 to 0108 of JP2009-288705A, paragraph 0227 of JP2013-29760A, and paragraph numbers 0254 to 0257 of JP2008-292970A. Which is incorporated herein by reference.

  Polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (As a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth) acryloyl groups contain ethylene glycol and propylene glycol residues. Through Structure (e.g., commercially available from Sartomer Company, SR454, SR499) is preferred. These oligomer types can also be used. Moreover, KAYARAD RP-1040, DPCA-20 (Nippon Kayaku Co., Ltd. product), and M-321 (Toagosei Co., Ltd. product) can also be used.

  The polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. A preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the developability is good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent. As a commercial item of the polymeric compound which has an acid group, M-305, M-510, M-520 etc. are mentioned as a polybasic acid modified acrylic oligomer by Toagosei Co., Ltd., for example.

  The polymerizable compound is also preferably a compound having a caprolactone structure. Polymerizable compounds having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.

  As the polymerizable compound, a polymerizable compound having an alkyleneoxy group can also be used. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and 4 to 20 ethyleneoxy groups (meta ) Acrylate compounds are more preferred. Examples of commercially available polymerizable compounds having an alkyleneoxy group include SR-494, a tetrafunctional acrylate having four ethyleneoxy groups manufactured by Sartomer, and six pentyleneoxy groups manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy groups.

  Polymerizable compounds include urethane acrylates such as those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), U-15HA, U-6LPA, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Japan) Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

  The polymerizable compound is also preferably a polymer having a group having an ethylenically unsaturated bond in the side chain (hereinafter also referred to as a polymerizable polymer). In the polymerizable polymer, the content of the structural unit having a group having an ethylenically unsaturated bond in the side chain is preferably 5 to 100% by mass of the total structural unit. The lower limit is more preferably 10% by mass or more, and still more preferably 15% by mass or more. The upper limit is more preferably 95% by mass or less, and still more preferably 90% by mass or less.

  The polymerizable polymer may contain other structural unit positions in addition to the structural unit having a group having an ethylenically unsaturated bond in the side chain. The other structural unit may contain a functional group such as an acid group or may not contain a functional group. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Only one type of acid group may be included, or two or more types of acid groups may be included. Other functional groups include development promoting groups such as lactones, acid anhydrides, amides, cyano groups, long chain and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups, hydroxyl groups, maleimide groups, amino groups, etc. Can be introduced as appropriate.

  The polymerizable polymer preferably contains a structural unit having an acid group. It is preferable that the ratio of the structural unit which has an acid group is 1-50 mass% of all the structural units which comprise a polymerizable polymer. The lower limit is more preferably 2% by mass or more, and further preferably 3% by mass or more. The upper limit is more preferably 35% by mass or less, and still more preferably 30% by mass or less. When the polymerizable polymer includes a structural unit having an acid group, the acid value of the polymerizable polymer is preferably 10 to 150 mgKOH / g. The lower limit is preferably 20 mgKOH / g or more, more preferably 30 mgKOH / g or more. The upper limit is preferably 140 mgKOH / g or less, and more preferably 130 mgKOH / g or less.

  Examples of commercially available polymerizable polymers include: NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (produced by COOH containing polyurethane acrylic oligomer. Diamond Shamrock Co., Ltd.), Biscoat R-264, KS resist 106 Also manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (both manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), Acrycure-RD-F8 ( Nippon Shokubai Co., Ltd.).

  As for content of the polymeric compound in alignment film material, 10 mass parts or more are preferable with respect to 100 mass parts of all the solid components, 20 mass parts or more are more preferable, and 30 mass parts or more are still more preferable. The upper limit is more preferably 99 parts by mass or less, for example. The alignment film material may contain only one type of polymerizable compound or two or more types. When two or more types are included, the total amount is preferably within the above range.

(Photopolymerization initiator)
As described above, in the preferred embodiment 3, the alignment film material contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

  Examples of the photopolymerization initiator include acylphosphine compounds, alkylphenone compounds, α-aminoketone compounds, benzophenone compounds, benzoin ether compounds, ketal derivative compounds, thioxanthone compounds, oxime compounds, hexaarylbiimidazole compounds, trihalomethyls. Examples thereof include compounds, azo compounds, organic peroxides, diazonium compounds, iodonium compounds, sulfonium compounds, azinium compounds, metallocene compounds, organic boron salt compounds, disulfone compounds, and thiol compounds. From the viewpoint of sensitivity, oxime compounds and alkylphenone compounds are preferred. As a photoinitiator, description of paragraph number 0061-0073 of Unexamined-Japanese-Patent No. 2011-186398 can be referred, for example, The content is integrated in this-application specification.

  As oxime compounds, IRGACURE OX-01 (manufactured by BASF), IRGACURE OXE-02 (manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arcles NCI -831 (manufactured by ADEKA), Adeka Arcles NCI-930 (manufactured by ADEKA), and the like can be used.

  In the present invention, an oxime compound having a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and compounds described in JP 2013-164471 A ( C-3). This content is incorporated herein.

  Examples of the alkylphenone compounds include hydroxyalkylphenone compounds and aminoalkylphenone compounds. As the hydroxyalkylphenone compound, commercially available products such as IRGACURE 184, DAROCUR 1173, IRGACURE 500, IRGACURE 2959, IRGACURE 127 (trade names: all manufactured by BASF) can be used. As the aminoalkylphenone compounds, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379EG (trade names: all manufactured by BASF) can be used.

  As the acylphosphine compound, commercially available products such as IRGACURE 819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

  As for content of a photoinitiator, 0.1-50 mass parts is preferable with respect to 100 mass parts of a polymeric compound, More preferably, it is 0.5-30 mass parts, More preferably, it is 1-20 mass parts. is there. Within this range, better sensitivity and pattern formability can be obtained. The alignment film material may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.

(Photo orientation)
As described above, the alignment film material used in the present invention has photo-alignment properties.
As a preferable aspect for alignment film material having photo-alignment property, the following suitable aspects 1-2 are mentioned, for example.
(1) Preferred embodiment 1: An embodiment containing a polymer p2 containing a structural unit having a photo-alignment group (2) Preferred embodiment 2: A polyimide precursor p3 represented by the formula (p3) described later is contained. Aspects Each aspect will be described in detail below.

<Preferred embodiment 1: an embodiment containing a polymer p2 containing a structural unit having a photoalignment group>
A preferred embodiment 1 includes an embodiment in which the alignment film material contains a polymer p2 including a structural unit having a photoalignable group.
Here, the photoalignment group refers to a photoreactive group that imparts orientation by any of a photodimerization reaction, a photoisomerization reaction, and a photolysis reaction. Especially, the photoreactive group which provides orientation by photodimerization reaction is preferable.
Examples of the group that imparts orientation by a photodimerization reaction include groups introduced from at least one derivative selected from the group consisting of maleimide derivatives, cinnamic acid derivatives, and coumarin derivatives. Preferred examples include cinnamate group and chalcone group. Of these, a cinnamate group is preferable.
In addition, as the cinnamate group and the chalcone group, for example, the following structure (in the following formula, * represents a connecting site to a polymer chain, and R represents a hydrogen atom or a monovalent organic group) is introduced. The connecting site to the polymer chain represented by * may be directly connected to the main chain of the polymer or may be bonded via a divalent linking group. The monovalent organic group represented by R is preferably an alkyl group or an aryl group. Moreover, 1-10 are preferable and, as for carbon number of the monovalent organic group which R represents, 1-7 are more preferable.

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

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

  The main chain skeleton of the polymer p2 having a structural unit having a photo-alignment group is not particularly limited, but the side chain molecular design is diversified, and the main chain formation by radical polymerization reaction of an ethylenically unsaturated compound is simple. For a certain reason, a polymer (polymer) having a repeating unit (structural unit) represented by the following general formula (III) is preferable.

(In General 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 Represents an alkyl group having 1 to 4 carbon atoms, L represents a single bond or a divalent linking group, and P represents a photo-alignment group.)

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

  Although the preferable specific example of the polymer which has a repeating unit represented by general formula (III) below is shown, this invention is not limited to these.

  The molar ratio of the structural unit having a photoalignable group to the total structural units constituting the polymer p2 is not particularly limited, but is preferably 10 to 100% by mole, and more preferably 20 to 90% by mole. .

The content of the polymer p2 in the alignment film material is not particularly limited, but is preferably 0.1 to 99.9 parts by mass with respect to 100 parts by mass of the total solid components. For example, the lower limit is more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more. For example, the upper limit is more preferably 90 parts by mass or less, and still more preferably 80 parts by mass or less.
The polymer p2 may be used alone or in combination of two or more.

(Preferable embodiment 1a: an embodiment in which the polymer p2 further includes a structural unit having a ubiquitous group)
As a preferable embodiment of the polymer p2, for example, at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton, and an alkyl group having 10 to 30 carbon atoms (hereinafter referred to as “unevenly-distributed group”). Polymer p2a containing a structural unit having a. Since the orientation group is unevenly distributed on the surface of the film by including the structural unit having the uneven distribution group, the content of the polymer p2 can be suppressed.
Hereinafter, each ubiquitous group will be described in detail.

(1) Structural unit having a partial structure of a fluorine-substituted hydrocarbon group The fluorine-substituted hydrocarbon group may be a hydrocarbon group substituted by at least one fluorine atom, and may be an alkyl group or an alkylene group (hereinafter, this paragraph). The alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and an alkyl group in which all hydrogen atoms such as an alkyl group are substituted with fluorine atoms is more preferable. .

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

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

M in the general formula I represents an integer of 1 to 3, and is preferably 1 or 2.
N in the general 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.
In addition, the connecting portion to the polymer chain represented by * may be directly connected to the main chain of the polymer, or may contain a polyoxyalkylene group, an alkylene group, an ester group, a urethane group, or a hetero atom. You may couple | bond together through bivalent coupling groups, such as an alkylene group, poly (caprolactone), and an amino group. It is preferable that they are bonded via a polyoxyalkylene group.

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

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

  In the method of copolymerizing a fluorine-substituted hydrocarbon group-containing monomer and introducing a structural unit having a fluorine-substituted hydrocarbon group into the polymer, the fluorine-substituted hydrocarbon group-containing monomer is a monomer represented by the following general formula II: It is mentioned as preferable.

In General Formula II, R ¹ represents a hydrogen atom, a halogen atom, a methyl group that may have a substituent, or an ethyl group that may have a substituent. R ² , X, m, n and r all have the same meaning as R ² , X, m, n and r in formula I, and preferred examples are also the same.
In addition, as a halogen atom represented by R < ¹ > in General formula II, a fluorine atom, a chlorine atom, a bromine atom is mentioned, for example.

  In addition, regarding the method for producing such a fluorine-substituted hydrocarbon group-containing monomer, for example, “Synthesis and function of fluorine compound” (supervision: Nobuo Ishikawa, published by CMC Co., 1987), pages 117 to 118, “Chemistry of Organic Fluorine Compounds II” (Monograph 187, Ed by Milos Hudricky and Attila E. Pavlath, pages 747-75 of American Chemical Society, 1995).

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

(2) Structural Unit Having Partial Structure of Siloxane Skeleton The siloxane skeleton is not particularly limited as long as it has “—Si—O—Si—”, and preferably contains a polyoxyalkylene group.

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

In said formula (X), R < ³ > -R < ⁵ > represents a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl group, or an alkoxy group each independently, and at least 1 is an alkoxy group. * Represents a binding 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, and an alkoxy group having 1 to 8 carbon atoms. It is more preferably a group, more preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably an ethoxy group or a methoxy group.
In the present invention, it is preferable that two of R ^{3 to} R ⁵ are alkoxy groups and one is an alkyl group, or three are alkoxy groups. Among these, an embodiment in which three are alkoxy groups, that is, a trialkoxysilyl group is more preferable.

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

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

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

In the structural formula (B), R ⁴ represents a hydrogen atom, a methyl group, or an ethyl group. n1, n2, and n3 are each independently an integer of 0 to 100. Here, two or more R ^{4 s} exist in the structural formula (B), but they may be different or the same.

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

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

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

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

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

In the structural formula (G), R ⁶ represents an unsubstituted alkyl group having 1 to 4 carbon atoms, and y2 represents an integer of 1 to 100, preferably an integer of 1 to 50, more preferably 1 to 20. It is an integer.

Examples of the siloxane skeleton include structures described in paragraph numbers [0092] to [0094] of JP 2010-18728 A, but are not limited thereto. Absent.
Of these, a structure in which a siloxane structure is bonded to a polymer via a polyoxyalkylene group is preferable.

(3) Structural unit having a partial structure of an alkyl group having 10 to 30 carbon atoms The alkyl group having 10 to 30 carbon atoms may include a branched structure or a cyclic structure, but the carbon number of the linear structure portion is It is preferable that it exists in the range of 10-30, and it is more preferable that all are linear structures.
Moreover, it is preferable that carbon number of an alkyl group is 10-20.

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

In formula _{(a3-1), n a3} represents an integer of 10 to 30, * represents a position for coupling to the main chain or side chain of the polymer. It is preferable that _na3 is an integer of 10-20.

Although there is no particular limitation on the method for introducing the structure of the general formula (a3-1) into the main chain or side chain of the polymer, for example, a monomer having the structure of (a3-1) is appropriately selected and applied at the time of synthesis. Then, the structure of (a3-1) can be introduced into the repeating unit of the obtained polymer.
Moreover, although the commercially available compound can be used for the monomer which has the structure of the said general formula (a3-1), it is contained in (a3-1) with respect to the commercially available monomer which does not have the structure of (a3-1). A desired structure may be introduced as appropriate. There is no limitation on the method of introducing the structure (a3-1) into a commercially available monomer, and a known method may be applied as appropriate.

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

In the general formula (a3-2), R ³² represents a hydrogen atom, a methyl group, an ethyl group, or a halogen atom, X ³¹ represents a divalent linking group, and R ³³ represents a single bond or an alkyleneoxy group. Represents. Moreover, _na3 is synonymous also including the said general formula (a3-1) and a preferable range.

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

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

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

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

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

In formula _{(U-a3-1), n a3} are synonymous, including the preferred ranges as in the general formula ^{(a3-1), R 32, X} 31, and ^{R 33,} the above general formula (A3- It is synonymous including 2) and a preferable range.

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

  Although the molar ratio of the structural unit having a ubiquitous group to the total structural units constituting the polymer p2a is not particularly limited, it is preferably 1 to 50% by mole, and more preferably 10 to 30% by mole.

Although content in particular of polymer p2a in alignment film material is not restrict | limited, 0.1-99.9 mass parts is preferable with respect to 100 mass parts of all the solid components. For example, the lower limit is more preferably 1 part by mass or more. For example, the upper limit is more preferably 20 parts by mass or less, and still more preferably 10 parts by mass or less.
The polymer p2a may be used alone or in combination of two or more.

<Preferable Aspect 2: Aspect Containing Polyimide Precursor p3 Represented by Formula (p3)>
A preferred embodiment 2 includes an embodiment in which the alignment film material contains a polyimide precursor p3 (polymer p3) represented by the formula (p3).
The polyimide precursor p3 is ring-closed (cyclized) by the thermosetting process described above to become a polyimide, and is further assumed to be decomposed and aligned at the portion A in the formula (p3) by the above-described photo-alignment treatment. Is done.
As above-mentioned, since the polyimide precursor p3 is cyclized by a thermosetting process, it shows thermosetting. That is, the polyimide precursor p3 has photo-alignment properties and also corresponds to a thermosetting component described later.
Hereinafter, the polyimide precursor p3 will be described.

Formula (p3)

In the above formula (p3), A represents a tetravalent organic group, and B represents a divalent organic group. X ¹ and X ² are a hydrogen atom or an acid-decomposable group.

  In the formula (p3), A preferably has at least one structure selected from the following formulas (A-1) to (A-5). Especially, it is preferable that it is a structure of Formula (A-1) from a viewpoint which shows the more outstanding photo-alignment property.

In said formula (A-1), R < ¹¹ >, R <^12> , R <^13> and R < ¹⁴ > represent a hydrogen atom, a fluorine atom, or a C1-C4 organic group each independently.

A in the above formula (p3) can contain a tetravalent aromatic hydrocarbon group and / or a tetravalent chain hydrocarbon group. Specific examples of the tetravalent aromatic hydrocarbon group include a tetravalent group in which four hydrogens in the mother skeleton of the aromatic hydrocarbon are substituted.
Examples of the chain hydrocarbon of the tetravalent chain hydrocarbon group include ethane, n-propane, n-butane, n-pentane, n-hexane, n-octane, n-decane, n-dodecane, and the like. it can. These tetravalent chain hydrocarbon groups may contain an aromatic ring in at least a part of the structure.

  In the formula (p3), B is preferably a divalent aromatic hydrocarbon group or a divalent alicyclic group, and the following formula (B-1) to the following formula (B-10) and the following formula ( It is more preferable that it is at least one structure selected from 4) to (5).

In the formula (B-1) ~ the formula (B-8), ^{R 5} each independently represent a hydrogen atom, an alkyl group or a hydroxyl group having 1 to 6 carbon atoms.

In the above formula (5), Z ¹ is a single bond, an ester bond, an amide bond, a thioester bond, or a divalent organic group having 2 to 10 carbon atoms.
Specific examples and preferred embodiments of the acid-decomposable group represented by X ¹ and X ² in the formula (p3) are the same as the acid-decomposable group that the polymer p1 has.
Incidentally, when X ¹ or X ² in the formula (p3) is an acid-decomposable group, the polyimide precursor p3 in order to fall in polymer p1 described above, the alignment layer material also exhibit optical patterning properties become.

Although content in particular of the polyimide precursor p3 in alignment film material is not restrict | limited, 0.1-99.9 mass parts is preferable with respect to 100 mass parts of all the solid components. For example, the lower limit is more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more. For example, the upper limit is more preferably 90 parts by mass or less, and still more preferably 80 parts by mass or less.
The polyimide precursor p3 may be used alone or in combination of two or more.

(Thermosetting component)
As described above, the alignment film material used in the present invention contains a thermosetting component. The thermosetting component is cured (crosslinked, cyclized, etc.) in the above-described thermosetting step.

As a suitable aspect of a thermosetting component, the polymer p4 containing the structural unit which has a crosslinkable group is mentioned, for example. Moreover, the polyimide precursor p3 mentioned above is also mentioned as a suitable aspect of a thermosetting component.
Hereinafter, the structural unit which has a crosslinkable group is explained in full detail.

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

(Constitutional unit having epoxy group and / or oxetanyl group)
The structural unit having the epoxy group and / or oxetanyl group only needs to have at least one epoxy group or oxetanyl group in one structural unit, one or more epoxy groups and one or more oxetanyl groups, 2 It may have one or more epoxy groups, or two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups. It is more preferable to have one or two oxetanyl groups in total, and it is even more preferable to have one epoxy group or one oxetanyl group.

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

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

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

(Structural unit having an ethylenically unsaturated group)
Another example of the structural unit having a crosslinkable group is a structural unit having an ethylenically unsaturated group. The structural unit having an ethylenically unsaturated group is preferably a structural unit having an ethylenically unsaturated group in the side chain, having an ethylenically unsaturated group at the terminal, and having a side chain having 3 to 16 carbon atoms. Units are more preferred.

  In addition, for the structural unit having an ethylenically unsaturated group, the description of paragraphs 0072 to 0090 of JP2011-215580A and the description of paragraphs 0013 to 0031 of JP2008-256974A can be referred to. Is incorporated herein by reference.

(Structural unit having a group represented by —NH—CH ₂ —O—R)
As another example of the structural unit having the crosslinkable group, a structure having a group represented by —NH—CH ₂ —O—R (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). Units are also preferred. By having a structural unit, a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 9 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group. The structural unit is more preferably a structural unit having a group represented by the following formula a2-30.

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

R ³² is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
Specific examples of R ³² include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, an i-butyl group, an n-butyl group, and a methyl group are preferable.

  The molar ratio of the structural unit having a crosslinkable group with respect to all the structural units constituting the polymer p4 is not particularly limited, but is preferably 10 to 50 mol%.

<Constitutional unit having an acid group>
When the structural unit having a crosslinkable group is a structural unit having an epoxy group and / or an oxetanyl group, the polymer p4 preferably further includes a structural unit having an acid group. In this case, in the thermosetting step described above, the epoxy group and / or oxetanyl group reacts with the acid group to crosslink. In addition, the structural unit which has an acid group may be contained as a polymer different from the polymer p4.

The acid group in the present invention means a proton dissociable group having a pKa smaller than 11.
Examples of the acid group used in the present invention include a carboxylic acid group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, a sulfonamide group, a sulfonylimide group, and acid anhydride groups of these acid groups, And the group etc. which neutralized these acid groups and made it into salt structure are illustrated, and a carboxylic acid group and / or a phenolic hydroxyl group are preferable. Although there is no restriction | limiting in particular as said salt, An alkali metal salt, alkaline-earth metal salt, and organic ammonium salt can illustrate preferably.
The structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. . For example, the compounds described in JP2012-88459A, paragraphs 0021 to 0023 and paragraphs 0029 to 0044 can be used, the contents of which are incorporated herein. Among these, structural units derived from p-hydroxystyrene, (meth) acrylic acid, maleic acid, and maleic anhydride are 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 the structural unit a1-1-1, derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, an ethylenically unsaturated group, and an acid anhydride. Examples thereof include a structural unit a1-1-2 having a structure derived from a product and a structural unit a1-2-1 having a phenolic hydroxyl group, and preferred embodiments thereof are also the same.
Among these, as the structural unit a3 having an acid group, a structural unit derived from a compound selected from the group consisting of methacrylic acid, acrylic acid and p-hydroxystyrene (represented by any one of the following formulas a3-1 to a3-3): The structural unit derived from methacrylic acid (the structural unit represented by the following formula a3-1) or the structural unit derived from acrylic acid (the structural unit represented by the following formula a3-2). It is more preferable that it is a structural unit derived from methacrylic acid (a structural unit represented by the following formula a3-1).

  Although the molar ratio of the structural unit having an acid group to the total structural units constituting the polymer p4 is not particularly limited, it is preferably 10 to 50 mol%.

The content of the polymer p4 in the alignment film material is not particularly limited, but is preferably 0.1 to 99.9 parts by mass with respect to 100 parts by mass of the total solid components. For example, the lower limit is more preferably 10 parts by mass or more, and still more preferably 20 parts by mass or more. For example, the upper limit is more preferably 90 parts by mass or less, and still more preferably 80 parts by mass or less.
The polymer p4 may be used alone or in combination of two or more.

[Other structural units]
The above-described polymers p1 to p4 may contain other structural units.
The monomer for forming such a structural unit is not particularly limited, and examples thereof include styrenes, (meth) acrylic acid alkyl esters, (meth) acrylic acid cyclic alkyl esters, (meth) acrylic acid aryl esters, and unsaturated dicarboxylic acids. Examples include acid diesters, bicyclounsaturated compounds, maleimide compounds, and unsaturated aromatic compounds.
The monomer which forms another structural unit can be used individually by 1 type or in combination of 2 or more types.

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

  As other structural units, styrenes or structural units derived from monomers having an aliphatic cyclic skeleton are preferable from the viewpoint of electrical characteristics. Specific examples include styrene, methylstyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate.

Furthermore, as other structural units, structural units derived from alkyl (meth) acrylates are preferable from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable. In all the structural units constituting the polymer, the content of the structural unit is preferably 60 mol% or less, more preferably 50 mol% or less, and still more preferably 40 mol% or less. As a lower limit, although 0 mol% may be sufficient, it is preferable to set it as 1 mol% or more, for example, and it is more preferable to set it as 5 mol% or more. Various characteristics will become favorable in it being in the range of said numerical value.
[Molecular weight]
The molecular weight of the above-mentioned polymers p1 to 4 is a weight average molecular weight in terms of polystyrene, preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and still more preferably 10,000 to 20,000. It is a range. Various characteristics are favorable in the range of said numerical value. The ratio of the number average molecular weight Mn to the weight average molecular weight Mw (dispersity, Mw / Mn) is preferably 1.0 to 5.0, and more preferably 1.5 to 3.5.
In addition, it is preferable to measure the weight average molecular weight and the number average molecular weight in the present invention by a gel permeation chromatography (GPC) method. In the measurement by gel permeation chromatography in the present invention, HLC-8020GPC (manufactured by Tosoh Corporation) is used, and TSKgel Super HZ M-H, TSK gel Super HZ4000, TSKgel SuperHZ200 (Tosoh Corporation, 4.6 mm ID × 15 cm) are used as columns. ), And THF (tetrahydrofuran) is preferably used as an eluent.

(Synthesis method)
Various methods are known for synthesizing the above-described polymers p1-2, and 4. For example, radical polymerization including a radical-polymerizable monomer used to form each constituent unit described above is given. It can synthesize | combine by superposing | polymerizing a monomer mixture in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction. Moreover, about the polyimide precursor p3, it is compoundable by the method of Unexamined-Japanese-Patent No. 2014-66764, for example.

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

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

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

[Other ingredients]
For the specific alignment film material, one or more of an antioxidant, an ultraviolet absorber, a thickener, a surfactant, an organic or inorganic precipitation inhibitor, an adhesion improver, a quencher, etc. are added independently. Can do.

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

  Moreover, as surfactant, the compound of Unexamined-Japanese-Patent No. 2014-238438 Paragraph 0151-0155 can also be mentioned as a preferable example.

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

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

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In addition, when the amount of each component is simply described as “part”, “part by mass” is intended.

[Monomer synthesis]
Each monomer was synthesized as follows.

[Synthesis of monomer having photo-alignment group (monomer a-1)]
Methyl trans-4-hydroxycinnamate (manufactured by Tokyo Chemical Industry Co., Ltd., 12.5 g, 0.07 mol) and triethylamine (manufactured by Wako Pure Chemical Industries, Ltd., 7.79 g, 0.07 mol) were added to tetrahydrofuran (hereinafter referred to as “tetrahydrofuran”). , And abbreviated as “THF”) After dissolving in 100 mL and cooling to 0 ° C., methacrylic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd., 7.33 g, 0.07 mol) was gradually added dropwise.
Next, 500 g of water was added to the cloudy reaction system and stirred for 1 hour, followed by filtration to obtain 14 g of monomer a-1 having a cinnamate group as a photoalignable group. The structure was confirmed by NMR.

[Synthesis of monomer having photo-alignment group (monomer a-2)]
Ethyl 4-hydroxy-3-methoxycinnamate (manufactured by Tokyo Chemical Industry Co., Ltd., 22.2 g, 0.1 mol) was dissolved in 150 mL of dimethylacetamide, and potassium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) 30 g, 0.22 mol) was added and the temperature was raised to 90 ° C.
Next, 4-chlorobutanol (manufactured by Wako Pure Chemical Industries, Ltd., 21.6 g, 0.2 mol) was added dropwise and stirred for 3 hours.
Thereafter, the reaction solution was poured into 1 L of water, neutralized with 2N (normal) HCl, extracted with 700 mL of ethyl acetate, washed with saturated brine, and concentrated.
Subsequently, it fractionated by silica gel column chromatography, and 23g of intermediate compounds were obtained.
15 g (0.05 mol) of the intermediate compound and triethylamine (manufactured by Wako Pure Chemical Industries, Ltd., 5.6 g, 0.056 mol) were dissolved in 100 mL of THF and cooled to 0 ° C.
Next, methacrylic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd., 5.8 g, 0.056 mol) was added dropwise and stirred for 3 hours, and then the reaction solution was poured into 500 g of water, extracted with ethyl acetate, and concentrated.
Subsequently, it fractionated by silica gel column chromatography, and 20g of monomer a-2 which has spacer cinnamate as a photo-alignment group was obtained.

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

[Synthesis of monomer (monomer e-1) having a group in which an acid group is protected by an acid-decomposable group]
Methacrylic acid (Wako Pure Chemical Industries, Ltd., 86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (Tokyo Chemical Industry Co., Ltd., 4.6 g, 0.02 mol) was added.
Next, 2,3-dihydrofuran (manufactured by Kawaken Fine Chemical Co., Ltd., 71 g, 1 mol, 1.0 equivalent) was added dropwise to the reaction solution.
After stirring for 1 hour, saturated sodium hydrogen carbonate (500 mL) was added, and the mixture was extracted with ethyl acetate (500 mL).
Subsequently, after drying with magnesium sulfate, the insoluble matter was filtered and concentrated under reduced pressure at 40 ° C. or lower, and the yellow oily residue was distilled under reduced pressure to give a boiling point (bp.) Of 54 to 56 as monomer e-1. 125 g of tetrahydro-2H-furan-2-yl methacrylate as a colorless oily product was obtained (yield 80%).

[Synthesis of polymer]
Each polymer was synthesized as follows.

[Synthesis of Polymer (P1)]
22 g of diethylene glycol methyl ethyl ether (hereinafter abbreviated as “HS-EDM”) was heated and stirred at 70 ° C. in a nitrogen stream. Synthesized monomer a-1 (11.1 g, 45 mol%), hexafluoroisopropyl methacrylate (hereinafter abbreviated as “HFIP”) (manufactured by Tokyo Chemical Industry Co., Ltd., 3.5 g, 15 mol%), methacrylic acid (hereinafter referred to as “HFIP”) (Hereinafter abbreviated as “MAA”) (manufactured by Wako Pure Chemical Industries, Ltd., 1.7 g, 20 mol%), glycidyl methacrylate (hereinafter abbreviated as “GMA”) (manufactured by Wako Pure Chemical Industries, Ltd.), 2. 8 g, 20 mol%), a mixed solution of radical polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) 497 mg (2 mol%) and PGMEA (30 g) were added dropwise over 2 hours. After completion of the dropwise addition, the PGMEA solution (solid content concentration: 27%) of the polymer (P1) was obtained by further reacting at 70 ° C. for 4 hours.

[Synthesis of polymers (P2 to P7)]
Polymers (P2 to P7) were synthesized in the same manner as the polymer (P1) except that the types of the monomer, initiator and solvent, and the polymerization temperature were changed according to Table 1 below. In addition, the numerical value described in the column of each monomer of the following Table 1 is the usage-amount (mol%) of each monomer with respect to the total amount of a monomer. Moreover, the numerical value described in the column of a polymerization initiator is mol% when the total amount of monomers is 100 mol%. Table 1 shows the weight average molecular weight (Mw) of each polymer. Abbreviations shown in Table 1 below are as follows.

<Abbreviation>
A-1 to a-3: monomers a-1 to a-3 synthesized as described above
・ HFIP: Hexafluoroisopropyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ 6FM: trifluoroethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
・ MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.)
・ GMA: Glycidyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
OXE-30: (3-ethyloxetane-3-yl) methyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
E-1: monomer e-1 synthesized as described above
・ MMA: Methyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
V-65: radical polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd.)
V-601: radical polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd.)
HS-EDM: Diethylene glycol methyl ethyl ether (manufactured by Toho Chemical Industry Co., Ltd.)
・ PGMEA: Methoxypropylene glycol acetate (manufactured by Daicel Corporation)

[Synthesis of Polymer (P8)]
PGMEA (238 g) was heated and stirred at 90 ° C. under a nitrogen stream.
Subsequently, tetrahydro-2H-furan-2-yl methacrylate synthesized as monomer e-1 (240 g (corresponding to 61.1 mol% in all monomers)), MAA (50.4 g (17.6 mol% in all monomers)) ), MMA (27.9 g (corresponding to 21.3 mol% in all monomers)), radical polymerization initiator V-601 (14.7 g), and PGMEA (238 g) over 2 hours. Then, the mixture was further reacted at 90 ° C. for 2 hours. After cooling, PGMEA (42 g) was added to obtain a polymer (P8) solution (solid content concentration: 38%). The molecular weight was 15000.

[Synthesis of Polymer (P9)]
HS-EDM (145 g) was heated and stirred at 70 ° C. under a nitrogen stream.
Then, GMA (144.7 g (67.9 mol%)), MAA (16.7 g (12.9 mol%)), St (styrene) (28.1 g (18.0 mol%)), DCPM (dicyclopentanyl) Methacrylate) (3.87 g (1.2 mol%)), radical polymerization initiator V-65 (20.8 g (5.6 mol% monomer equivalent)), and HS-EDM (145 g) mixed solution for 2 hours It was dripped over. After completion of the dropwise addition, the polymer (P9) solution (solid content concentration: 35%) was obtained by reacting at 70 ° C. for 4 hours. The molecular weight was 10,000.

[Synthesis of Polymer (P10)]
HS-EDM (82 parts) was heated and stirred at 90 ° C. under a nitrogen stream.
Next, tetrahydro-2H-furan-2-yl methacrylate (43 parts (corresponding to 40.5 mol% in all monomers)) synthesized as monomer e-1, OXE-30 (48 parts (37. MAA (6 parts (corresponding to 9.5 mol% in all monomers)), hydroxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 11 parts (12.5 mol% in all monomers) Equivalent)), radical polymerization initiator V-601 (4.3 parts), and PGMEA (82 parts) mixed solution was added dropwise over 2 hours, and further reacted at 90 ° C. for 2 hours. P10) solution (solid content concentration: 40%) was obtained. The molecular weight was 15000.

[Synthesis of Polymer (P11)]
The following polymer (P11) was synthesized with reference to WO2013 / 018904.
Specifically, 1,6.3,4 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd., 1.00 mol) and 2394 g of NMP (N-methylpyrrolidone) (Wako Pure Chemical Industries, Ltd.) In the form of a slurry, 101.11 g of p-phenylenediamine (0.935 mol) manufactured by Tokyo Chemical Industry Co., Ltd. is added, NMP is further added so that the solid concentration is 8% by weight, and the mixture is stirred at room temperature for 24 hours. As a result, a solution (solid content concentration 8%) of a polymer (P11) of polyamic acid was obtained.

[Synthesis of Polymer (P12)]
To 100 g of the polymer (P10) solution obtained above, phthalic anhydride 1.0 was added as end-capping and stirred for 24 hours. To this solution, 0.1 g of camphor sulfonic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was added, 30 g of 2,3-dihydrofuran (manufactured by Kawaken Fine Chem Co., Ltd.) was added, and carbon was monitored while monitoring by NMR (nuclear magnetic resonance method) When the acid protection rate reaches 65%, 2.0 g of pyridine (manufactured by Wako Pure Chemical Industries, Ltd.) is added to stop the reaction, and the solid content concentration is adjusted to 5% with NMP. A solution of (P12) (solid content concentration 5%) was obtained.

[Preparation of photosensitive resin composition]
Each photosensitive resin composition (alignment film material) was prepared as follows. Since each of M1 to M12 has photopatterning properties and photoalignment properties and contains a thermosetting component, it corresponds to the specific alignment film material described above.

[Preparation of photosensitive resin composition (M1)]
55 parts of polymer (P6) in terms of solid content, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate as a polymerizable compound (ethylenically unsaturated compound) (KAYARAD (registered trademark) DPHA, Nippon Kayaku Co., Ltd.) 45 parts by mass, Etanone-1- {9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl} -1- (O-acetyloxime) (photo-initiator) After adding propylene glycol monomethyl ether acetate (PGMEA, Daicel Chemical) to 2.5 parts by mass of Irgacure OXE-02, BASF) and a solid concentration of 30% by mass, Millipore with a pore size of 0.5 μm The photosensitive resin composition M1 was obtained by filtering with a filter.

[Preparation of photosensitive resin composition (M2)]
55 parts of polymer (P11) in terms of solid content, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate as a polymerizable compound (ethylenically unsaturated compound) (KAYARAD (registered trademark) DPHA, Nippon Kayaku Co., Ltd.) 45 parts by mass, Etanone-1- {9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl} -1- (O-acetyloxime) (photo-initiator) After adding propylene glycol monomethyl ether acetate (PGMEA, Daicel Chemical) to 2.5 parts by mass of Irgacure OXE-02, BASF) and a solid concentration of 30% by mass, Millipore with a pore size of 0.5 μm The photosensitive resin composition M2 was obtained by filtering with a filter.

[Preparation of photosensitive resin composition (M3)]
75 parts of polymer (P6) in terms of solid content, 25 parts of quinonediazide compound (TAS-200, Toyo Gosei Co., Ltd.), 0 perfluoroalkyl group-containing surfactant (F-554, manufactured by DIC) .02 parts, a silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion improver was mixed with 2 parts, and diethylene glycol methyl ethyl ether (HS-EDM, so that the total solid content concentration was 11%. Toho Chemical Co., Ltd.) was added to obtain a photosensitive resin composition M3.

[Preparation of photosensitive resin composition (M4)]
75 parts of polymer (P7) in terms of solid content, 25 parts of quinonediazide compound (TAS-200, Toyo Gosei Co., Ltd.), 0 perfluoroalkyl group-containing surfactant (F-554, manufactured by DIC) .02 parts, a silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion improver was mixed with 2 parts, and HS-EDM was added so that the total solid content concentration was 11%, and photosensitivity Resin composition M4 was obtained.

[Preparation of photosensitive resin composition (M5)]
75 parts of polymer (P11) in terms of solid content, 25 parts of quinonediazide compound (TAS-200, Toyo Gosei Co., Ltd.), 0 perfluoroalkyl group-containing surfactant (F-554, manufactured by DIC) .02 parts, a silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion improver was mixed with 2 parts, and HS-EDM was added so that the total solid content concentration was 11%, and photosensitivity Resin composition M5 was obtained.

[Preparation of photosensitive resin composition (M6)]
5 parts of polymer (P1) in terms of solid content, 45 parts of polymer (P8) in terms of solid content, 50 parts of polymer (P9) in terms of solid content, PAG103 (manufactured by BASF) as a photoacid generator 3 parts, 0.02 part of triphenylimidazole as a quencher, 0.02 part of F-554 (manufactured by DIC) as a perfluoroalkyl group-containing surfactant, and a silane coupling agent (KBM-) as an adhesion improver 403, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with 2 parts, and HS-EDM was added so that the total solid content concentration was 11% to obtain a photosensitive resin composition M6.

[Preparation of photosensitive resin composition (M7)]
5 parts of polymer (P2) in terms of solids, 45 parts of polymer (P8) in terms of solids, 50 parts of polymer (P9) in terms of solids, PAG103 (manufactured by BASF) as a photoacid generator 3 parts, 0.02 part of triphenylimidazole as a quencher, 0.02 part of F-554 (manufactured by DIC) as a perfluoroalkyl group-containing surfactant, and a silane coupling agent (KBM-) as an adhesion improver 403, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with 2 parts, and HS-EDM was added so that the total solid content concentration was 11%, to obtain a photosensitive resin composition M7.

[Preparation of photosensitive resin composition (M8)]
5 parts of polymer (P3) in terms of solid content, 45 parts of polymer (P8) in terms of solid content, 50 parts of polymer (P9) in terms of solid content, PAG103 (manufactured by BASF) as a photoacid generator 3 parts, 0.02 part of triphenylimidazole as a quencher, 0.02 part of F-554 (manufactured by DIC) as a perfluoroalkyl group-containing surfactant, and a silane coupling agent (KBM-) as an adhesion improver 403, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with 2 parts, and HS-EDM was added so that the total solid content concentration was 11% to obtain a photosensitive resin composition M8.

[Preparation of photosensitive resin composition (M9)]
5 parts of polymer (P1) in terms of solid content, 95 parts of polymer (P10) in terms of solid content, 3 parts of PAG103 (manufactured by BASF) as a photoacid generator, and 0.03 of triphenylimidazole as a quencher. 02 parts, 0.02 part of F-554 (manufactured by DIC) as a perfluoroalkyl group-containing surfactant, and 2 parts of a silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion improver HS-EDM was added so that the total solid content concentration was 11% to obtain a photosensitive resin composition M9.

[Preparation of photosensitive resin composition (M10)]
100 parts of polymer (P4) in terms of solid content, 3 parts of PAG103 (manufactured by BASF) as a photoacid generator, 0.02 part of triphenylimidazole as a quencher, F as a perfluoroalkyl group-containing surfactant -554 (manufactured by DIC) is mixed with 0.02 parts, and a silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) is mixed with 2 parts as an adhesion improver so that the total solid content concentration becomes 11%. HS-EDM was added to obtain a photosensitive resin composition M10.

[Preparation of photosensitive resin composition (M11)]
100 parts of polymer (P5) in terms of solid content, 3 parts of PAG103 (manufactured by BASF) as a photoacid generator, 0.02 part of triphenylimidazole as a quencher, F as a perfluoroalkyl group-containing surfactant -554 (manufactured by DIC) is mixed with 0.02 parts, and a silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) is mixed with 2 parts as an adhesion improver so that the total solid content concentration becomes 11%. HS-EDM was added to obtain a photosensitive resin composition M11.

[Preparation of photosensitive resin composition (M12)]
100 parts of polymer (P12) in terms of solid content, 5 parts of PAG103 (manufactured by BASF) as a photoacid generator, 0.02 part of triphenylimidazole as a quencher, F as a perfluoroalkyl group-containing surfactant -554 (manufactured by DIC) is mixed with 0.02 parts, and a silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) is mixed with 6 parts as an adhesion improving agent so that the total solid content concentration becomes 9%. HS-EDM was added to obtain a photosensitive resin composition M12.

  Table 2 below shows the main components and parts by mass for each photosensitive resin composition (alignment film material). Moreover, about each photosensitive resin composition (alignment film material), the component or structural unit which contributes to photo patterning property, photo-alignment property, and thermosetting property is shown. Moreover, the structural unit which has a ubiquitous group is shown.

[Manufacture of LCD panels]
A liquid crystal display panel was manufactured by the steps shown in FIGS. 1 to 10 (Examples 1 to 12).
Hereinafter, each step will be described.

[Process (1): Substrate preparation process]
<Process (1-1): Coating film formation process>
The photosensitive resin composition (alignment film material) prepared as described above was applied onto a pair of substrates (array substrate, color filter substrate) to form a coating film (thickness: 0.5 μm). The array substrate and the color filter substrate are as follows.

(Array substrate)
An active element or the like (semiconductor layer, gate electrode, gate insulation) formed according to a known method by repeating normal etching of a semiconductor film, formation of a known insulating layer, etc. on a glass substrate and etching by photolithography. A substrate having a film, source-drain electrodes, video signal lines, scanning signal lines, and the like) was prepared.
Next, the interlayer insulating film was subjected to photopatterning, and a transparent conductive layer made of ITO (indium tin oxide) was formed on the insulating film by sputtering. Next, the transparent conductive layer was etched using a photolithography method to form a solid common electrode on the insulating film. Thereafter, an inorganic insulating film was formed by sputtering the SiN film, and a comb-like transparent electrode was further installed. In this way, an array substrate was obtained.

(Color filter substrate)
A color filter substrate was obtained by a known method. In this color filter substrate, a minute coloring pattern of three colors of red, green, and blue and a black matrix are arranged in a lattice pattern on a transparent substrate.

<Step (1-2): Removal step>
Then, exposure and development were performed with respect to the obtained coating film, and the coating film formed in the sealing material formation area was removed from the coating film. Specifically, it was exposed to ghi-line mixed light (wavelength 365 to 405 nm), and alkali development was performed.

<Process (1-3): Thermosetting process>
Furthermore, the coating film remaining after the removing step was thermally cured (230 ° C./30 minutes). In this manner, a thermosetting film (thickness: 0.5 μm) was formed in a region other than the sealing material formation region of the pair of substrates (array substrate, color filter substrate).

<Step (1-4): Photo-alignment treatment step>
Furthermore, the photo-alignment process was performed with respect to the obtained thermosetting film. Specifically, polarized exposure with polarized ultraviolet rays of 500 J / m ² including an emission line of 254 to 313 nm was performed using an Hg—Xe lamp and a Grand Taylor prism. In this manner, a photo-alignment film (thickness: 0.5 μm) was formed in a region other than the sealing material formation region of the pair of substrates (array substrate, color filter substrate).

[Step (2): Sealing material forming step]
A composition for forming a sealing material is applied to the sealing material forming region of the array substrate on which the photo-alignment film is formed by a dispenser, and the sealing material (ultraviolet curable acrylic) is applied to the sealing material forming region of the array substrate on which the photo-alignment film is formed. Resin and thermosetting epoxy resin).

[Step (3): Bonding step and Step (4): Liquid crystal layer forming step]
The sealing material for the array substrate obtained in the step (3) was matched with the sealing material forming region of the color filter substrate obtained in the step (1), and the pair of substrates were bonded together with the sealing material. At that time, a liquid crystal layer forming composition is sandwiched between a pair of substrates, and a liquid crystal layer (made of nematic liquid crystal and aligned in parallel with the substrate surface) in a space surrounded by the pair of substrates and the sealing material. Formed.
In this way, a liquid crystal display panel (color liquid crystal display element) was manufactured. The obtained liquid crystal display panel showed excellent operating characteristics and display characteristics.
In any of the examples, there is no etching step after forming a resist mask using a resist solution separately as in the method of Japanese Patent Application Laid-Open No. 2015-36721. .

[Evaluation]
[Softening temperature Tm of coating film]
The softening temperature Tm was measured using an indentation hardness apparatus (Micromaterials, Nano Indenter, Nano Test Vantage). Specifically, it measured as follows.
The photosensitive resin composition (alignment film material) used in each example was applied to a silicon wafer to prepare a 4.0 μm coating film. The obtained coating film was set in the indentation hardness apparatus, a load (100 mN) was applied, the temperature was increased from 90 ° C. to 350 ° C. by 5 ° C., and the displacement at each temperature was examined. The temperature at which the displacement became 0.4 μm or more was defined as the softening temperature Tm.

[Curing start temperature Tc of thermosetting component in coating film]
The curing start temperature Tc of the thermosetting component was measured using RT-IR (manufactured by Bruker, FT-IR (Fourier transform infrared spectroscopy) apparatus, VERTEX). Specifically, it measured as follows.
The photosensitive resin composition (alignment film material) used in each example was applied to a silicon wafer to prepare a 2.0 μm coating film. About the obtained coating film, IR (infrared branching method) was measured, raising 5 degreeC at 1 minute. The changes were followed while tracking 2500 to 3000 cm ⁻¹ . In addition, since the crosslinkable group of an epoxy or oxetane generate | occur | produces a hydroxyl group by reaction with an acid group, reaction can be traced (M1, 3, 4, 6-11). Moreover, since the hydroxyl group lose | disappears the change from the polyamic acid (polyimide precursor) which is a precursor to a polyimide, reaction can be traced (M2, 5, 12).

[Angle d1 of coating film]
The photosensitive resin composition (alignment film material) used in each example was applied on a glass substrate to form a coating film (thickness: 4.0 μm). Next, the formed coating film was exposed with a 5 μm line & space photomask using a PLA (registered trademark) -501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Then, development was performed at 25 ° C./60 seconds with a 0.4 mass% or 2.38 mass% tetramethylammonium hydroxide aqueous solution. Rinse was performed with ion-exchanged water to obtain a patterned coating film. SEM (scanning electron microscope) observation was performed about the edge part of the obtained pattern-like coating film, and the angle corresponding to the angle d1 mentioned above was measured. The results are shown in Table 2. Here, “> 100 °” indicates that the angle is greater than 100 degrees.

[An angle d2 of the thermosetting film]
After obtaining a patterned coating film by the same method as the measurement of the angle d1 of the coating film described above, by performing post-baking in an oven with a curing time of 230 ° C./60 minutes, a patterned thermosetting film ( A film thickness of about 3.0 μm) was obtained. SEM observation was performed about the edge part of the obtained pattern-shaped thermosetting film, and the angle corresponding to the angle d2 mentioned above was measured. The results are shown in Table 2.

From the comparison with Examples 1 to 12, in Examples 3 to 12 where the specific alignment film material is positive, the angle d2 of the thermosetting film is 30 to 90 degrees, and a liquid crystal display panel with a narrower frame can be obtained. I understood. Among them, in Examples 6 to 12 in which the specific alignment film material has an acid-decomposable group, the angle d2 of the thermosetting film is 50 to 90 degrees, and it was found that a liquid crystal display panel with a narrower frame can be obtained. Among them, in Examples 6 to 8 and 10 satisfying Tc ≦ Tm + 20, the angle d2 of the thermosetting film was 70 to 90 degrees, and it was found that a liquid crystal display panel having a particularly narrow frame can be obtained.
From the comparison of Examples 1 to 12, Examples 6 to 12 in which the coating film angle d1 is 70 to 90 degrees have a thermosetting film angle d2 of 60 to 90 degrees, and a liquid crystal display panel with a narrower frame is obtained. I found out that I could do it.
From the comparison of Examples 3 to 5 (a mode in which the alignment film material contains quinonediazide), Example 3 satisfying Tc ≦ Tm + 20 is a liquid crystal display panel having a narrower frame with an angle d2 of the thermosetting film of 50 to 90 degrees. It turns out that can be obtained.

a liquid crystal layer forming region b sealing material forming region c end region 10 pair of substrates 12 pair of substrates with a photo-alignment film 20 coating film 22 remaining after the removing step formed in liquid crystal layer forming region a of coating film 22 The coated film 22c The coated film 22p formed in the end region c of the coated film 22 The side end surface 22q in contact with the sealing material forming region b of the coated film 22a The surface d1 side end surface 22p of the coated film 22a in contact with the substrate 10 and the surface An angle with 22q 24 Thermosetting film 24a Thermosetting film 24c formed in liquid crystal layer forming region a of thermosetting film 24 Thermosetting film 24p formed in end region c of thermosetting film 24 Thermosetting film 24a Side end surface 24q in contact with the sealing material forming region b of the surface d2 of the thermosetting film 24a in contact with the substrate 10 Angle 26 between the side end surface 24p and the surface 24q of the thermosetting film 24a Formed in the liquid crystal layer forming region a of the photoalignment film 26 Photo-alignment film 26c photo alignment film end optical alignment film formed in a region c 30 sealant 40 liquid crystal layer 100 liquid crystal display panel of the 26

Claims (7)

Preparing a pair of substrates in which a photo-alignment film is formed in a region other than the sealing material forming region;
Forming a sealing material in the sealing material forming region of any one of the pair of substrates; and a sealing material forming step;
A bonding step of bonding the pair of substrates together with the sealing material;
A liquid crystal layer forming step for forming a liquid crystal layer in a space surrounded by the pair of substrates and the sealing material,
The substrate preparation step includes
A coating film forming step of forming a coating film made of an alignment film material having a photopatterning property and a photoalignment property and containing a thermosetting component on a pair of substrates having a sealing material forming region;
Removing the coating film formed in the sealing material formation region of the coating film by exposing and developing the coating film; and
Thermosetting the coating film remaining after the removing step, and forming a thermosetting film in a region other than the sealing material forming region of the pair of substrates;
A method of manufacturing a liquid crystal display panel, comprising: a photo-alignment treatment step, wherein the thermosetting film is subjected to a photo-alignment process, and a photo-alignment film is formed in a region other than the sealing material formation region of the pair of substrates.   Of the thermosetting film, an angle between a side end face of the thermosetting film formed in the liquid crystal layer forming region and a surface of the thermosetting film in contact with the substrate is 30 to 90 degrees. The manufacturing method of the liquid crystal display panel of Claim 1 which is.   The method for manufacturing a liquid crystal display panel according to claim 1, wherein the alignment film material is a positive type in which an exposed portion of a coating film to be formed is dissolved. When the softening temperature of the coating film is Tm [° C.] and the curing start temperature of the thermosetting component in the coating film is Tc [° C.]
The manufacturing method of the liquid crystal display panel of any one of Claims 1-3 with which said Tm and Tc satisfy | fill following formula (1) and (2).
Tm = 80 to 200 (1)
Tc ≦ Tm + 20 (2)   Of the coating film remaining after the removing step, the angle between the side end surface of the coating film formed in the liquid crystal layer forming region and the surface contacting the substrate of the coating film is 70 to 90 degrees. The manufacturing method of the liquid crystal display panel of any one of Claims 1-4.   The method for manufacturing a liquid crystal display panel according to claim 1, wherein a wavelength of light used in the exposure is longer than a wavelength of light used in the optical alignment treatment.   The manufacturing method of the liquid crystal display panel of any one of Claims 1-6 whose light used by the said photo-alignment process is linearly polarized light.