KR102016409B1 - Manufacturing method of liquid crystal display panel - Google Patents

Abstract

An object of this invention is to provide the manufacturing method of a simpler liquid crystal display panel. The manufacturing method of the liquid crystal display panel of this invention is a board | substrate preparation process which prepares a pair of board | substrate with which the photo-alignment film was formed in the area | regions other than a seal material formation area | region, and a sealing material in either seal material formation area | region of a pair of board | substrate. A method of manufacturing a liquid crystal display panel comprising a step of forming a substrate, a step of bonding substrates to each other by a sealing material, and a step of forming a liquid crystal layer in a space surrounded by the substrate and the sealing material, wherein the substrate preparation step is performed on the substrate. Forming a coating film made of an alignment film material having an optical patterning property and an optical alignment property and containing a thermosetting component; exposing and developing the coating film to remove the coating film formed in the sealing material forming region of the coating film; and a removing step Thermosetting the remaining coating film to form a thermosetting film in a region other than the sealing material forming region of the substrate; and photoaligning the thermosetting film. Carried out by a step of forming a photo alignment layer in a region other than the sealing material to form areas of the substrate.

Description

Manufacturing method of liquid crystal display panel

This invention relates to the manufacturing method of a liquid crystal display panel.

BACKGROUND ART Liquid crystal display panels are widely used in monitors and televisions such as personal computers, smartphones, and the like from various advantages such as low voltage, low power consumption, and miniaturization and thinness.

Generally, a liquid crystal display panel has a pair of board | substrates, the sealing material which bonds a pair of board | substrate, and the liquid crystal layer formed in the space surrounded by a pair of board | substrate and a sealing material. Moreover, the alignment film for controlling the initial orientation of a liquid crystal molecule is formed in the board | substrate. Conventionally, a rubbing treatment has been used as an alignment film. However, since static electricity and dust generated by the rubbing treatment may lead to defects, an alignment film manufactured without using a rubbing treatment such as an optical alignment treatment is also developed. have. In addition, in this specification, the orientation film manufactured by the photo-alignment process is also called "photo-alignment film."

By the way, when an oriented film is formed in the area | region which forms a sealing material (henceforth a "sealing material formation area | region"), there exists a problem that the adhesive strength of a sealing material will fall. In order to avoid such a problem, in the manufacturing method of the liquid crystal display panel disclosed by patent document 1, the sealing material is formed in a board | substrate after removing the optical orientation film formed in the sealing material formation area | region.

Patent Document 1: Japanese Unexamined Patent Publication No. 2015-36721

However, in the method of patent document 1, in the process of removing the photo-alignment film formed in the seal | sticker material formation area | region, since etching is performed after forming a resist mask using a resist liquid separately, there is a problem that the load on a process surface is large. There was.

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

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the said subject, it discovered that the said subject can be solved by providing not only optical orientation but also optical patterning property to an oriented film material.

(1) a substrate preparation step of preparing a pair of substrates on which an optical alignment film is formed in regions other than the seal material forming region;

A sealing material forming step of forming a sealing material in the sealing material forming region of any one of the pair of substrates;

A bonding step of bonding the pair of substrates together with the sealing material;

As a manufacturing method of the liquid crystal display panel containing the liquid crystal layer formation process of forming a liquid crystal layer in the space enclosed by the said pair of board | substrates and the said sealing material,

The substrate preparation process,

A coating film forming step of forming a coating film made of an alignment film material having a photopatterning property and a photo-alignment property and containing a thermosetting component on a pair of substrates having a seal material forming region;

A removal step of exposing and developing the coating film to remove the coating film formed in the seal material forming region of the coating film;

A thermosetting step of thermally curing the coating film remaining after the removing step to form a thermosetting film in a region other than the sealing material forming region of the pair of substrates;

And a photoalignment treatment step of subjecting the thermosetting film to a photoalignment process to form a photoalignment film in a region other than the sealant formation region of the pair of substrates.

(2) The angle between the side surface of the thermosetting film formed in the liquid crystal layer forming region of the thermosetting film in contact with the sealing material forming region and the surface in contact with the substrate of the thermosetting film is 30 to 90 degrees; The manufacturing method of the liquid crystal display panel as described in 1).

(3) The manufacturing method of the liquid crystal display panel as described in said (1) or (2) whose said oriented film material is a positive type in which the exposed part melt | dissolves in the coating film formed.

(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 said Tm and Tc satisfy the following formula (1) and (2), The manufacturing method of the liquid crystal display panel in any one of said (1)-(3).

Tm = 80-200 (1)

Tc≤Tm + 20 (2)

(5) Said (1) thru | or the angle of the side cross section which contact | connects the said seal material formation area of the coating film formed in the liquid crystal layer formation area | region after the said removal process, and the surface which contact | connects the board | substrate of the said coating film is 70-90 degree. The manufacturing method of the liquid crystal display panel in any one of (4).

(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 photoalignment 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 linearly polarized light.

As shown below, according to this invention, the manufacturing method of a simpler liquid crystal display panel can be provided.

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

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Although description of the element | module described below may be made | formed based on typical embodiment of this invention, this invention is not limited to such embodiment.

In addition, in this specification, the numerical range represented using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In the description of group (atom group) in this specification, the description which is not describing substitution and unsubstitution includes what has a substituent with the thing which does not have a substituent. For example, an "alkyl group" includes not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent.

In the present specification, "(meth) acrylate" is a notation indicating "acrylate" or "methacrylate", "(meth) acryl" is notation indicating "acryl" or "methacryl", "(Meth) acryloyl" is a notation indicating "acryloyl" or "methacryloyl", and "(meth) acryloyloxy" is "acryloyloxy" or "methacryloyl jade" The notation for "hour".

The manufacturing method of the liquid crystal display panel (liquid crystal display device) of this invention is equipped with the following process (1)-(4). In addition, hereafter, the manufacturing method of the liquid crystal display panel of this invention is also called "the manufacturing method of this invention."

Process (1): substrate preparation process

Process of preparing a pair of board | substrate with a photo-alignment film formed in the area | region other than a sealing material formation area | region

Process (2): Seal material forming process

Forming a sealing material in the sealing material forming region of any one of the pair of substrates

Process (3): bonding process

A step of bonding the pair of substrates together by the sealing material

Step (4): liquid crystal layer forming step

Forming a liquid crystal layer in a space surrounded by the pair of substrates and the sealing material

Here, the said board | substrate preparation process is equipped with the following process (1-1)-(1-4).

Step (1-1): coating film forming step

A step of forming a coating film made of an alignment film material having a photopatterning property and an optical orientation and containing a thermosetting component on a pair of substrates having a seal material forming region.

Step (1-2): Removal Step

Exposing and developing the coating film, and removing the coating film formed in the sealing material forming region of the coating film.

Process (1-3): thermosetting process

Process of thermosetting the coating film remaining after the said removal process, and forming a thermosetting film in the area | regions other than the said seal material formation area of the said pair of board | substrates.

Step (1-4): Photoalignment Treatment Step

Performing a photoalignment process on the thermosetting film to form a photoalignment film in a region other than the sealing material forming region of the pair of substrates;

First, the manufacturing method of this invention is demonstrated using drawing.

1-10 is a schematic diagram which shows one Embodiment of the manufacturing method of this invention in process order.

First, in a board | substrate preparation process, a pair of board | substrate with which the photo-alignment film 26 was formed in the area | regions other than the sealing material formation area | region b is prepared. Specifically, it is as follows.

1 is a cross-sectional view of a pair of substrates 10 used in one embodiment of the manufacturing method of the present invention. 2 is a plan view of the pair of substrates 10. Also, only one of the pair of substrates is shown. The liquid crystal layer forming region a exists near the center of the main surface of the pair of substrates 10, and the sealing material forming region b exists around the liquid crystal layer forming region, and the sealing member forming region is present. At the periphery of (b) there is an end region (c).

First, in the coating film forming step, the coating film 20 made of an alignment film material (hereinafter also referred to as a "specific alignment film material") on the pair of substrates 10 that contains photopatterning properties and photoalignment and contains a thermosetting component. ) (FIG. 3).

Next, in a removal process, exposure and image development are performed with respect to the coating film 20, and the coating film formed in the sealing material formation area b among the coating films 20 is removed (FIG. 4).

In the thermosetting step, the coating films 22 (22a and 22c) remaining after the removal step are thermosetted to form regions other than the sealing material forming region b of the pair of substrates 10 (liquid crystal layer forming region ( a), The thermosetting film 24 (24a, 24c) is formed in the edge region c (FIG. 5).

Thereafter, in the photo-alignment treatment step, the photo-alignment treatment is performed on the thermosetting film 24, and the photo-alignment film 26 (26a) is applied to a region other than the sealant forming region b of the pair of substrates 10. 26c)) (Figs. 6 and 7).

In this manner, a pair of substrates (substrate 12 with a pair of photo-alignment films) in which the photo-alignment film 26 is formed in a region other than the seal material forming region b is prepared.

Next, in the sealing material forming step, the sealing material 30 is formed in either of the sealing material forming regions b of the pair of substrates with the optical alignment film 12 (FIGS. 8 and 9).

Subsequently, in the bonding step, the sealing member 30 of the substrate 12 with the optical alignment film on the side where the sealing member is not formed is formed by the sealing member 30 of the substrate 12 with the optical alignment film on which the sealing member 30 is formed. According to (b), the pair of substrates with the optical alignment film 12 are bonded together by the sealing material 30.

Before or after the bonding step, the composition for forming a liquid crystal layer is sandwiched between the pair of substrates with a photoalignment film 12 in a space surrounded by the pair of substrates with a photoalignment film 12 and the sealing material 30. The liquid crystal layer 40 is formed. In this way, the liquid crystal display panel 100 is obtained (FIG. 10).

Hereinafter, the material and procedure used for each process are explained in full detail.

[Step (1): Substrate Preparation Step]

A board | substrate preparation process is a process of preparing a pair of board | substrate with which the photo-alignment film was formed in the area | regions other than a seal | sticker material formation area | region, and includes process (1-1)-(1-4) mentioned later.

[Step (1-1): Coating Film Formation Step]

A coating film formation process is a process of forming the coating film which consists of an orientation film material (specific orientation film material) which has photopatternability and photo-alignment property, and contains a thermosetting component on a pair of board | substrate which has a sealing material formation area. Hereinafter, the material used and the procedure are explained in full detail. In addition, a specific orientation film material is demonstrated in detail after description of all the processes.

<Substrate>

In the manufacturing method of the present invention, a pair of substrates is used. One of a pair of board | substrates is a board | substrate (henceforth "a 1st board | substrate") provided in the visual recognition side rather than the liquid crystal layer mentioned later, and the other side is opposite to the 1st board | substrate of the liquid crystal layer mentioned later (usually a backlight side). ) Is a substrate (hereinafter also referred to as "second substrate").

The substrate has a region (sealing material forming region) in which the sealing material is formed. In addition, although the board | substrate with which a sealing material is formed in a sealing material formation process is only one of a pair of board | substrates, in the subsequent bonding process, the sealing material formed in one board | substrate is bonded to the sealing material formation area of the other board | substrate. As a result, the sealing material is also formed in the sealing material forming region of the other substrate as a result. Therefore, normally, when a pair of board | substrates are opposed, both sealing material formation regions correspond in the main surface direction.

Although the shape of the sealing material forming region is not particularly limited, as shown in FIG. 2, it is preferable that the sealing member is formed in a band shape surrounding the circumference of the region where the liquid crystal layer is formed (liquid crystal layer forming region).

(First substrate)

It is preferable that a 1st board | substrate is equipped with a base material and a color filter (color filter substrate).

(1) mention

As said base material, the transparent substrate used for the liquid crystal cell of a conventionally well-known liquid crystal display panel can be used, For example, a glass substrate, a quartz substrate, a transparent resin substrate, etc. can be used. Especially, it is preferable to use a glass substrate.

(2) color filter

It does not specifically limit as said color filter, For example, a well-known thing can be used as a color filter of a liquid crystal display panel generally.

Such a color filter is usually comprised by the transparent coloring pattern of each color of red, green, and blue, and each of these transparent coloring patterns is comprised by the resin composition which the colorant melt | dissolved or disperse | distributed, Preferably pigment microparticles were disperse | distributed. .

In addition, although the formation of the said color filter may be performed by preparing the ink composition colored by the predetermined | prescribed color, and printing for every coloring pattern, photolithography using the photosensitive resin composition of the paint type containing the coloring agent of the predetermined | prescribed color. It is more preferable to carry out by a method.

(Second substrate)

It is preferable that a 2nd board | substrate is equipped with a base material, a thin film transistor, and a display electrode.

(1) mention

As said base material, the transparent substrate used for the liquid crystal cell of a conventionally well-known liquid crystal display panel can be used similarly to the above-mentioned 1st board | substrate, For example, a glass substrate, a quartz substrate, a transparent resin substrate, etc. can be used. . Especially, it is preferable to use a glass substrate.

(2) thin film transistor

As said thin film transistor (TFT), what is used by the well-known liquid crystal display panel can be used suitably, The structure is not specifically limited, A top gate type or a bottom gate type may be sufficient.

Specific examples of the thin film transistors include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like.

(3) display electrode

As said display electrode, what is used by the well-known liquid crystal display panel can be used suitably, As its constituent material, for example, indium tin oxide (ITO) and aluminum doped zinc oxide (AZO). And transparent conductive materials such as indium zinc oxide (IZO) can be used.

<Formation method of coating film>

Although the method of forming a coating film is not specifically limited, The method of apply | coating the specific orientation film material mentioned later on a pair of board | substrate, etc. are mentioned.

The method of coating is not specifically limited, Specifically, for example, the printing method (for example, the gravure printing method, the screen printing method, the flexographic printing method, the inkjet printing method, the imprint method etc.), the spin coating method, The slit coating method, the slit and spin coating method, the curtain coating method, etc. are mentioned.

When a specific orientation film material contains a solvent, you may include the solvent removal process which removes the solvent contained in a coating film before a removal process.

Although the solvent removal process differs in processing conditions according to the kind and quantity of a solvent, For example, when NMP (N-methylpyrrolidone) is used as a solvent, it is about 0.5 to 3 minutes at about 80-150 degreeC, It is preferable that it is a process to heat, and it is more preferable that it is a process to heat about 0.5 to 2 minutes at about 90-120 degreeC.

<Thickness of coating>

Although the thickness of a coating film is not specifically limited, It is preferable that it is 0.1-5 micrometers.

<Softening temperature Tm of coating film, Cure start temperature Tc of thermosetting component in coating film>

When the softening temperature of a coating film is set to Tm [degreeC] and the hardening start temperature of the thermosetting component in a coating film is set to Tc [degreeC], it is preferable that said Tm and Tc satisfy following formula (1) and (2). . When Tm and Tc satisfy following formula (1) and (2), the angle d2 of the thermosetting film formed by the thermosetting process mentioned later becomes large, and the liquid crystal display panel of a narrower frame can be obtained. In addition, a thermosetting component is as mentioned later.

Tm = 80-200 (1)

Tc≤Tm + 20 (2)

The softening temperature Tm [° C.] of the coating film was set by applying the load (100 mN) to the indentation hardness device, applying a load (100 mN), raising the temperature from 90 ° C. to 350 ° C. at 5 ° C., and calculating and calculating the displacement at each temperature. . Specifically, the temperature at which the displacement was changed by 10% or more was defined as the softening temperature Tm.

In addition, the hardening start temperature Tc [degreeC] of the thermosetting component in a coating film measured and calculated IR (infrared spectroscopy), heating a coating film for 5 minutes by 1 degreeC. Specifically, the temperature at which the amount of change in the IR spectrum of the reactive group in the curing reaction in each thermosetting component became a value of 10% or more relative to the amount of change in the final IR spectrum was defined as the curing start temperature Tc.

[Step (1-2): Removal Step]

A removal process is a process of exposing and developing the coating film formed in 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 ultra high pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generator, etc. can be used, i line (365 nm), h line (405 nm), g line (436 nm). Actinic rays having a wavelength of 300 nm or more and 450 nm or less, etc., can be preferably used. Moreover, irradiation light can also be adjusted through spectroscopic 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 apparatuses such as a mirror projection aligner, stepper, scanner, proximity, contact, micro lens array, lens scanner, laser exposure, and the like can be used. Moreover, exposure using what is called super resolution technique can also be performed. As a super-resolution technique, the multiple exposure which exposes several times, the method of using a phase shift mask, the circular band illumination method, etc. are mentioned. By using these super-resolution techniques, more precise pattern formation is attained, 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.

<Phenomena>

It is preferable that the aqueous solution of a basic compound is contained in the developing solution used for image development. As a basic compound, the compound of Paragraph 0171 of Unexamined-Japanese-Patent No. 2015/087829 is mentioned, Sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetra Butyl ammonium hydroxide and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferable. Moreover, the aqueous solution which added an appropriate amount of water-soluble organic solvents, such as methanol and ethanol, and surfactant to the aqueous solution of the said alkalis can also be used as a developing solution.

The pH of the developing solution is preferably 10.0 to 14.0.

The developing time is preferably 30 to 500 seconds, and the developing method may be any of a liquid fusing method (puddle method), a shower method and a dip method.

After image development, a rinse process can also be performed. In the rinsing step, the developer after the development is washed with pure water or the like to remove adhered developer and to remove the developer residue. The rinse method can use a well-known method. For example, shower rinse, deep rinse, etc. are mentioned.

<Angle of coating (d1)>

Although the angle d1 of the side surface of the coating film formed in the liquid crystal layer forming region and the surface in contact with the substrate of the coating film of the coating film formed after the removal process is not particularly limited, the liquid crystal display having a narrower frame. From the reason that a panel can be obtained, it is preferable that it is 50 degrees or more, It is more preferable that it is 70 degrees or more, It is more preferable that it is 70-90 degrees. Especially, it is preferable that an angle is large. That is, it is most preferable that it is 90 degrees. In addition, in this specification, the thing with large angle with respect to the angle to 90 degrees is also called simply "an angle."

As shown in FIG. 11 (partial sectional view after a removal process in one Embodiment of the manufacturing method of this invention), the angle d1 of a coating film is formed in the liquid crystal layer formation area | region a of the coating film remaining after a removal process. It is an angle between the side end surface 22p which contact | connects the sealing material formation area | region b of the coating film 22a, and the surface 22q which contact | connects the board | substrate 10 of the coating film 22a.

[Step (1-3): Thermosetting Step]

A thermosetting process is a process of thermosetting the coating film remaining after a removal process, and forming a thermosetting film in the area | regions other than the sealing material formation area of a pair of board | substrate.

<Thermal curing>

180-400 degreeC is preferable and, as for the heating temperature for thermosetting, 220 degreeC-350 degreeC is more preferable. As for heating time, 15 to 120 minutes are preferable. This heating can be performed using heating apparatuses, such as a hotplate and oven. Moreover, transparency can also be improved further by performing heat processing in nitrogen atmosphere.

Post-baking may be performed after baking at a relatively low temperature before thermosetting (postbaking) (addition of a middlebaking process). In the case of performing a middle bake, after heating at 90-150 degreeC for 1 to 60 minutes, it is preferable to post-bake at 200 degreeC or more high temperature. In addition, the middle bake and the post bake may be divided into three or more multi-steps and heated.

In addition, when a coating film contains a photo-acid generator, hardening reaction of a film | membrane can be accelerated by post-baking after whole surface re-exposure (post exposure) prior to post-baking. As a preferable exposure amount in the case of including a post exposure process, 100-3,000mJ / cm <^2> is preferable and 100-500mJ / cm <^2> is especially preferable.

<Thickness of thermosetting film>

Although the thickness in particular of a thermosetting film is not restrict | limited, It is preferable that it is 0.1-5 micrometers.

<Angle of thermal curing film (d2)>

Although the angle d2 between the side cross section of the thermosetting film formed in the liquid crystal layer forming region among the thermosetting films and the surface in contact with the substrate of the thermosetting film is not particularly limited, the angle d2 is not limited. For the reason that a liquid crystal display panel can be obtained, it is preferable that the angle is large. That is, it is most preferable that it is 90 degrees. It is preferable that it is 30-90 degree specifically, it is more preferable that it is 50-90 degree, and it is still more preferable that it is 70-90 degree.

The angle d2 of the thermosetting film is formed in the liquid crystal layer forming region a of the thermosetting film as shown in FIG. 12 (partial cross-sectional view after the thermosetting step in one embodiment of the manufacturing method of the present invention). It is an angle between the side end surface 24p which contact | connects the sealing material formation area | region b of the thermosetting film 24a, and the surface 24q which contact | connects the board | substrate 10 of the thermosetting film 24a.

[Step (1-4): Photoalignment Treatment Step]

A photo-alignment process is a process of performing a photo-alignment process on a thermosetting film, and forming a photo-alignment film in the area | regions other than the sealing material formation area of a pair of board | substrate.

It is preferable to use the light of wavelength 365nm or less for the photo-alignment process.

Photo-alignment treatment is preferable in order to obtain uniform orientation using polarized ultraviolet rays. In this case, the method of irradiating the polarized ultraviolet ray is not specifically limited. Moreover, there is no restriction | limiting in particular as polarized light, For example, linearly polarized light, circularly polarized light, elliptically polarized light, etc. are mentioned, Especially, linearly polarized light is preferable.

Moreover, what is necessary is just to acquire polarization substantially, and you may irradiate unpolarized light by inclining at an angle from the normal line of a thin film. In other words, you may irradiate non-polarization from the diagonal direction of the thin film surface. As long as it is a direction which inclined polar angle (theta) (0 <(theta) <90 degrees) with respect to the normal line direction of a thin film surface, there is no restriction | limiting and it can select suitably according to the objective, but "theta" is 20-80 degrees It is preferable.

As a light source of the light used, a xenon lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, etc. are mentioned, for example.

The wavelength range to irradiate can be restrict | limited by using an interference filter, a color filter, etc. with respect to the ultraviolet-ray obtained from such a light source. Moreover, linearly polarized light can be obtained by using a polarizing filter or a polarizing prism with respect to the light from these light sources.

[Step (2): Seal Material Formation Step]

A sealing material formation process is a process of forming a sealing material in either sealing material formation area | region of a pair of board | substrate obtained at the board | substrate preparation process.

Although the method of forming a sealing material is not specifically limited, The method of apply | coating the composition for sealing material formation to a sealing material formation area is preferable. Conventionally well-known things can be used as a composition for sealing material formation, For example, what contains both an acrylic resin type, an epoxy resin type, an acrylic resin, and an epoxy resin etc. is mentioned.

[Step (3): Bonding Step]

A bonding process is a process of bonding a pair of board | substrate together by a sealing material. That is, a sealing material of a pair of optical alignment film board | substrates is matched with the sealing material of the board | substrate with the optical orientation film in which the sealing material was formed by the sealing material formation process was matched with the sealing material formation area | region of the board | substrate with an optical orientation film in which the sealing material is not formed. It is a process of bonding by (30).

[Step (4): Liquid Crystal Layer Formation Step]

A liquid crystal layer formation process is a process of forming a liquid crystal layer in the space enclosed by a pair of board | substrate and the said sealing material. In the bonding process, the composition for liquid crystal layer formation is sandwiched between a pair of substrates with a photoalignment film (the sealing material is formed on one side) and spaced in a space surrounded by the pair of substrates with the photoalignment film and the sealing material 30. It is preferable to form a liquid crystal layer.

As a driving method for driving the liquid crystal layer, a twisted nematic (TN) method, a vertical alignment (VA) method, an in-plane-switching (IPS) method, a fringe field switching (FFS) method, an OCB (Optically Compensated Bend) method, etc. Can be mentioned. It is preferable that it is an IPS system among these drive systems.

In the liquid crystal cell of the IPS system, the rod-shaped liquid crystal molecules are oriented substantially parallel to the substrate, and the liquid crystal molecules respond planely by applying an electric field parallel to the substrate surface. That is, in the IPS system, the liquid crystal constituting the liquid crystal layer is a horizontally aligned liquid crystal. In the IPS system, black display is performed in the state where no electric field is applied, and the absorption axes of the upper and lower pairs of polarizing plates are perpendicular to each other.

[Alignment Film Material]

The alignment film material (specific alignment film material) used in the present invention has optical patterning property and optical alignment property. Moreover, it contains a thermosetting component. That is, the alignment film material used in the present invention has photopatterning properties, photoalignment properties and thermosetting properties.

The alignment film material may contain a single compound having all three characteristics (photopatterning, photoalignment, and thermosetting), and a plurality of compounds each having three characteristics (photopatterning, photoalignment, and thermosetting). It may contain. In addition, when an oriented film material contains a some compound, one of a some compound may have two or more of three characteristics (photopatterning property, photo-alignment property, and thermosetting).

Moreover, polymer p1 (photopatterning), p2 (photoalignment), p3 (photoalignment), and p4 (thermosetting component) which are mentioned later may be contained as a separate polymer, and may be contained as one polymer. That is, one polymer may be contained as a some polymer in the polymers p1-4.

For example, P4 and P5 used in the Example mentioned later have the polymer p1 (since the acidic radical has the structural unit which has the group protected by the acid-decomposable group, the structural unit which has a photo-alignment group, and the structural unit which has a crosslinkable group), Photopatterning), polymer p2 (photoalignment) and polymer p4 (thermosetting component).

[Optical patterning property]

As described above, the alignment film material used in the present invention has optical patterning property. That is, when exposing and developing the coating film formed of the alignment film material used in the present invention, the exposed part (exposed part) is dissolved (positive type) or the unexposed part (non-exposed part) is dissolved ( Negative) to form a pattern. It is preferable that the orientation film material used by this invention is the positive type which melt | dissolves the exposed part of the coating film formed because the angle d2 mentioned above becomes large.

As a preferable aspect for the alignment film material used by this invention to have optical patterning property, the following suitable aspects 1-3 are mentioned, for example.

(1) Suitable Embodiment 1: Positive Type (Chemical Amplification Type)

Acid groups contain polymers and photoacid generators comprising structural units having groups protected with acid-decomposable groups.

(2) Suitable Embodiment 2: Positive Type (quinonediazide compound)

It contains a quinonediazide compound.

(3) Suitable Embodiment 3: Negative

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.

<Side Mode 1: Positive Type (Chemical Amplification Type)>

Suitable embodiment 1 is an embodiment in which the alignment film material contains a polymer p1 comprising a structural unit in which the acid group has a group protected by an acid-decomposable group, and a photoacid generator (preferably, a photoacid generator for generating an acid of pKa3 or less). to be.

In the preferred embodiment 1, when the exposure film is exposed to the coating film formed of the alignment film material, the acid-decomposable group is decomposed in the exposed portion to generate an acid group, so that the exposed portion is dissolved by development, thereby forming a positive pattern. Suitable embodiment 1 is the so-called chemically amplified type.

In addition, the polyimide precursor p3 mentioned later also corresponds to the polymer p1, when X <^1> or X <^2> in Formula (p3) mentioned later is an acid-decomposable group.

(Polymer p1 in which the acidic group includes a structural unit having a group protected by an acid-decomposable group)

In the present specification, "group in which an acid group is protected with an acid-decomposable group" means a group that causes an acid-catalyzed deprotection reaction as a catalyst (or an initiator) to generate a structure decomposed with an acid group and a regenerated acid. The group in which an acidic group was protected by the acid-decomposable group can use a well-known thing as an acidic radical and an acid-decomposable group, It does not specifically limit.

As an acidic group, a carboxyl group, a phenolic hydroxyl group, etc. are mentioned preferably, for example.

Moreover, as an acid-decomposable group, it is comparatively decomposed | disassembled by the group (for example, an acetal-type functional group, such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group) which is comparatively easy to decompose | disassemble by an acid. Groups (for example, tertiary alkyl groups, such as tert- butyl ester group, tertiary alkyl carbonate groups, such as tert- butyl carbonate group) which are hard to mention, etc. are mentioned.

The structural unit in which the acid group has a group protected with an acid-decomposable group is a structural unit having a protective carboxyl group in which the carboxyl group is protected with an acid-decomposable group (hereinafter also referred to as a “structural unit having a protective carboxyl group protected with an acid-decomposable group”), or a phenolic hydroxyl group Is preferably a structural unit having a protective phenolic hydroxyl group protected with an acid-decomposable group (hereinafter also referred to as a "structural unit having a protective phenolic hydroxyl group protected with an acid-decomposable group").

Hereinafter, the structural unit which has the protective carboxyl group protected by the acid-decomposable group, and the structural unit which has the protective phenolic hydroxyl group protected by the acid-decomposable group are demonstrated in order, respectively.

(1) Structural units having a protective carboxyl group protected with an acid-decomposable group

The structural unit which has the protective carboxyl group protected by the said acid-decomposable group is a structural unit which has the protective carboxyl group protected by the acid-decomposable group demonstrated in detail below.

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 protective carboxyl group protected by the said acid-decomposable group, A well-known structural unit can be used. For example, the structural unit derived from the unsaturated carboxylic acid etc. which have at least 1 carboxyl group in a molecule | numerator, such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, and unsaturated tricarboxylic acid, and the structural unit which has both a structure derived from ethylenically unsaturated group and an acid anhydride. Can be mentioned.

Hereinafter, the structural unit derived from the unsaturated carboxylic acid etc. which have at least 1 carboxyl group in a molecule | numerator, and the structural unit which has both an ethylenically unsaturated group and the structure derived from an acid anhydride are demonstrated in order, respectively.

(1-1) Structural unit derived from unsaturated carboxylic acid etc. which have at least 1 carboxyl group in a molecule | numerator

As an unsaturated carboxylic acid used by this invention as a structural unit derived from the unsaturated carboxylic acid etc. which have at least one carboxyl group in the said molecule | numerator, the compound of Paragraph 0043 of Unexamined-Japanese-Patent No. 2014-238438 is mentioned, for example.

Especially, from a developable viewpoint, in order to form the said structural unit, acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, It is preferable to use 2- (meth) acryloyloxyethyl-phthalic acid or anhydride of unsaturated polyhydric carboxylic acid, etc., and it is more preferable to use acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid. Do.

The structural unit derived from the unsaturated carboxylic acid etc. which have at least 1 carboxyl group in the said molecule may be comprised individually by 1 type, and may be comprised by 2 or more types.

(1-2) Structural unit which has both an ethylenically unsaturated group and the structure derived from an acid anhydride

It is preferable that the structural unit which has both an ethylenically unsaturated group and the structure derived from an acid anhydride is a unit derived from the monomer obtained by making the hydroxyl group and acid anhydride which exist in the structural unit which has an ethylenically unsaturated group react.

As said acid anhydride, a well-known thing can be used, Specifically, Dibasic acid anhydrides, such as maleic anhydride, a succinic anhydride, itaconic anhydride, a phthalic anhydride, tetrahydro phthalic anhydride, a hexahydro phthalic anhydride, chloric anhydride, etc. ; Acid anhydrides, such as a trimellitic anhydride, a pyromellitic anhydride, a benzophenone tetracarboxylic anhydride, and a biphenyl tetracarboxylic anhydride, are mentioned. In these, phthalic anhydride, tetrahydro phthalic anhydride, or succinic anhydride is preferable from a developable viewpoint.

The reaction rate with respect to the hydroxyl group of the said acid anhydride is from a developable viewpoint, Preferably it is 10-100 mol%, More preferably, it is 30-100 mol%.

A well-known acid-decomposable group can be used as said acid-decomposable group which can be used for the structural unit which has the protective carboxyl group protected by the said acid-decomposable group.

In this invention, it is preferable that a carboxyl group is a protective carboxyl group protected by the form of acetal among acid-decomposable groups. Among the acid-decomposable groups, the carboxyl group is more preferably a protective carboxyl group protected in the form of acetal represented by the following formula a1-10 from the viewpoint of sensitivity. Further, when the carboxyl group to a protected carboxyl group protected in the form of an acetal represented by the formula a1-10, as the whole of the protected carboxyl groups, - a structure of a (C = O) -O-CR 101 R 102 (OR 103).

[Formula 1]

In said Formula a1-10, R <^101> and R <^102> represent a hydrogen atom or a hydrocarbon group each independently, except the case where R <^101> and R <^102> are all hydrogen atoms. R ¹⁰³ represents an alkyl group. R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be linked to each other to form a cyclic ether.

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

In the formula a1-10, when R ¹⁰¹ , R ¹⁰² and R ¹⁰³ represent an alkyl group, the alkyl group may be any of linear, branched or cyclic.

As said linear alkyl group, it is preferable that it is C1-C12, It is more preferable that it is C1-C6, It is more preferable that it is C1-C4. As a branched chain, it is more preferable that it is C3-C6, and it is still more preferable that it is C3-C4. 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-hex A real group, a texyl group (2, 3- dimethyl- 2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, etc. are mentioned.

As said cyclic alkyl group, it is preferable that it is C3-C12, It is more preferable that it is C4-C8, It is more preferable that it is C4-C6. As said cyclic alkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group etc. are mentioned, for example.

The said alkyl group may have a substituent and can illustrate a halogen atom, an aryl group, and an alkoxy group as a substituent. If having a halogen atom as a substituent, R ^101, R ^102, R ¹⁰³ is a haloalkyl group, if having an aryl group as a substituent, R ^101, R ^102, R ¹⁰³ is an aralkyl group.

As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are illustrated, 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, (alpha) -methylphenyl group, a naphthyl group, etc. can be illustrated, As a whole alkyl group substituted by the aryl group, ie, an aralkyl group, a benzyl group, (alpha)-methyl benzyl group, a phenethyl group, a naphthyl methyl group, etc. are mentioned. It can be illustrated.

As said alkoxy group, a C1-C6 alkoxy group is preferable, A C1-C4 alkoxy group is more preferable, A methoxy group or an ethoxy group is more preferable.

Moreover, when the said alkyl group is a cycloalkyl group, the said cycloalkyl group may have a C1-C10 linear or branched alkyl group as a substituent, and when a alkyl group is a linear or branched alkyl group, it is C3 as a substituent. You may have a cycloalkyl group of -12.

These substituents may further be substituted by the said substituent.

In said Formula a1-10, when R <^101> , R <^102> and R <^103> represent an aryl group, it is preferable that the said aryl group is C6-C12, and it is more preferable that it is C6-C10. The said aryl group may have a substituent and can preferably illustrate a C1-C6 alkyl group as said substituent. As an aryl group, a phenyl group, tolyl group, xylyl group, cumenyl group, 1-naphthyl group etc. can be illustrated, for example.

Moreover, R <^101> , R <^102> and R <^103> may combine with each other and become one with the carbon atom to which they couple | bond, and can form a ring. Examples of the ring structure in the case where R ¹⁰¹ and R ¹⁰² , R ¹⁰¹ and R ^103, or R ¹⁰² and R ¹⁰³ combine with each other include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group and an ac And a dantilyl group and a tetrahydropyranyl group.

In formula a1-10, one of R ¹⁰¹ and R ¹⁰² is preferably a hydrogen atom or a methyl group.

A commercially available radical may be used for the radically polymerizable monomer used in order to form the structural unit which has a protective carboxyl group represented by said formula a1-10, and what synthesize | combined by a well-known method can also be used. For example, Paragraph 0037 of Unexamined-Japanese-Patent No. 2011-221494-the synthesis method as described in 0040, etc. can be synthesize | combined.

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

[Formula 2]

In formula, R <^1> and R <^2> represents a hydrogen atom, an alkyl group, or an aryl group each independently, At least either of R <^1> and R <^2> is an alkyl group or an aryl group, R <^3> represents an alkyl group or an aryl group, R <^1> Alternatively, 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> is an alkyl group, a C1-C10 alkyl group is preferable. When R <^1> and R <^2> is an aryl group, a phenyl group is preferable. R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R <^3> represents an alkyl group or an aryl group, a C1-C10 alkyl group is preferable, and a 1-6 alkyl group is more preferable.

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 a protective carboxyl group protected by the said acid-decomposable group is a structural unit represented by a following formula.

[Formula 3]

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

The following structural unit can be illustrated as a preferable specific example of the structural unit which has the protective carboxyl group protected by the said acid-decomposable group. In addition, R represents a hydrogen atom or a methyl group.

[Formula 4]

(2) Structural units having a protective phenolic hydroxyl group protected with an acid-decomposable group

As a structural unit which has the protective phenolic hydroxyl group protected by the said acid-decomposable group, the structural unit in hydroxy styrene-type structural unit and novolak-type resin is mentioned.

Among these, the structural unit derived from hydroxy styrene or (alpha) -methylhydroxy styrene is preferable from a viewpoint of a sensitivity.

Moreover, as a structural unit which has a phenolic hydroxyl group, the structural unit of Paragraph 0065 of Unexamined-Japanese-Patent No. 2014-238438-0073 is also preferable from a viewpoint of a sensitivity.

Although the molar ratio of the structural unit in which an acidic radical has the group protected by the acid-decomposable group with respect to the whole structural unit which comprises polymer p1 is not restrict | limited, It is preferable that it is 10-100 mol%, and it is more preferable that it is 20-90 mol%. .

Although content in particular of the polymer p1 in an oriented film material is not restrict | limited, 0.1-99.9 mass parts is preferable with respect to 100 mass parts of total solid components. For example, 10 mass parts or more are more preferable, and, as for a minimum, 20 mass parts or more are more preferable. For example, 90 mass parts or less are more preferable, and, as for an upper limit, 80 mass parts or less are more preferable.

Polymer p1 may be used independently and may be used in combination of 2 or more type.

(Mine generator)

The photoacid generator is not particularly limited.

The photoacid generator is preferably a compound which generates an acid in response to an active light having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm, but the chemical structure is not limited. Moreover, also about the photo-acid generator which does not directly respond to actinic light of wavelength 300nm or more, if it is a compound which responds to actinic light of wavelength 300nm or more by using together with a sensitizer and produces | generates an acid, it can be used preferably in combination with a sensitizer.

As the photoacid generator used in the present invention, a photoacid generator for generating an acid having a pKa of 3 or less is preferable, and a photoacid generator for generating an acid having a pKa of 2 or less is more preferable.

Here, pKa basically refers to pKa in 25 degreeC water. What cannot be measured in water points out the thing measured by changing into the solvent suitable for a measurement. Specifically, pKa described in a chemical handbook or the like can be referred to.

Moreover, as acid whose pKa is 3 or less, it is preferable that it is sulfonic acid or phosphonic acid, and it is more preferable that it is sulfonic acid.

In addition, the photoacid generator preferably 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, imidosulfonate compounds, and oxime sulfonates Compounds and the like. Among these, an onium salt compound, an imidosulfonate compound, and an oxime sulfonate compound are preferable, and an onium salt compound and an oxime sulfonate compound are especially preferable. A photoacid generator can be used individually by 1 type or in combination of 2 or more types.

As a specific example of trichloromethyl-s-triazines, diaryl iodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane compounds, Paragraph No. 0083 of Unexamined-Japanese-Patent No. 2011-221494 is mentioned. The compound described in -0088 and the compound of Paragraph No. 0013 of Unexamined-Japanese-Patent No. 2011-105645-0049 can be illustrated, These content is integrated in this specification.

As a specific example of an imido sulfonate compound, Paragraph No. 0065 of WO2011 / 087011-the compound of 0075 can be illustrated, These content is integrated in this specification.

Moreover, it is also preferable to use the triarylsulfonium salt of the following structure.

[Formula 5]

As an oxime sulfonate compound, ie, a compound which has an oxime sulfonate structure, the compound containing the oxime sulfonate structure represented by the following general formula (B1-1) can be illustrated preferably.

General formula (B1-1)

[Formula 6]

In General Formula (B1-1), R ²¹ represents an alkyl group or an aryl group. The dashed line represents the bond with other groups.

In general formula (B1-1), either may be substituted and the alkyl group in R <^21> may be linear, branched, or cyclic may be sufficient as it. Acceptable substituents are described below.

As an alkyl group of R <^21> , a C1-C10 linear or branched alkyl group is preferable. The alkyl group of R ²¹ includes a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloaliphatic alicyclic group such as a cycloalkyl group (7,7-dimethyl-2-oxo nobornyl group). And preferably a bicycloalkyl group).

As an aryl group of R <^21> , a C6-C11 aryl group 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.

It is preferable that the said compound containing the oxime sulfonate structure represented by said general formula (B1-1) is also an oxime sulfonate compound of Paragraph No. 0108 of Unexamined-Japanese-Patent No. 2014-238438-0133.

As an imidosulfonate type compound, a naphthalene imide type compound is preferable, and description of international publication WO11 / 087011 can be referred, and these content is integrated in this specification.

In this invention, 0.1-20 mass parts is preferable with respect to 100 mass parts of total solids of an orientation film material as content of a photo-acid generator. For example, 0.2 mass part or more is more preferable, and, as for a minimum, 0.5 mass part or more is more preferable. For example, 10 mass parts or less are more preferable, and, as for an upper limit, 5 mass parts or less are more preferable.

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 two or more types of photoacid generators, it is preferable that the total amount becomes said range.

<Side Mode 2: Positive Type (quinonediazide compound)>

Suitable embodiment 2 is an embodiment in which the alignment film material contains a quinonediazide compound.

In the suitable aspect 2, when exposure is performed to the coating film formed from the oriented film material, since a carboxy group is normally produced from the quinone diazide compound of an exposure part, an exposure part melt | dissolves by image development and a positive pattern is formed. In suitable Embodiment 2, it is preferable to include the polymer containing the structural unit which has a crosslinkable group mentioned later in an orientation film material.

(Quinonediazide compound)

As said quinonediazide compound, the 1, 2- quinonediazide compound which generate | occur | produces a carboxylic acid by irradiation of actinic light can be used. As a 1, 2- quinonediazide compound, the condensate of a phenolic compound or an alcoholic compound (henceforth "mother nucleus"), and a 1, 2- naphthoquinone diazido sulfonic-acid halide can be used. As a specific example of these compounds, Paragraph 0075 of Unexamined-Japanese-Patent No. 2012-088459-description of 0078 can be referred, for example, This content is integrated in this specification.

In the condensation reaction of a phenolic compound or an alcoholic compound (parent nucleus) with 1,2-naphthoquinonediazidosulfonic acid halide, preferably 30 to 85 mol%, based on the number of OH groups in the phenolic compound or the alcoholic compound, More preferably, 1,2-naphthoquinone diazido sulfonic-acid halide corresponding to 50-70 mol% can be used. Condensation reaction can be implemented by a well-known method.

Moreover, as a 1, 2- quinone diazide compound, the 1, 2- naphthoquinone diazido sulfonic acid amides which changed the ester bond of the above-mentioned mother core to the amide bond, for example, 2,3, 4- triamino Benzophenone-1,2-naphthoquinone diazido-4-sulfonic acid amide etc. are also used suitably. Moreover, 4,4 '-{1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene} bisphenol (1.0 mol) and 1,2-naphthoquinone diazido- Condensate of 5-sulfonic acid chloride (3.0 moles), 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mole) and 1,2-naphthoquinonediazido-5-sulfonic acid chloride (2.0 Mole), a condensate of 2,3,4,4'-tetrahydroxybenzophenone (1.0 mole) and 1,2-naphthoquinone diazido-5-sulfonic acid ester (2.44 mole) You may also

These quinonediazide compounds can be used individually by 1 type or in combination of 2 or more types.

As for content of the quinonediazide compound in an oriented film material, 1-50 mass parts is preferable with respect to 100 mass parts of total solids, 2-40 mass parts is more preferable, 10-30 mass parts is more preferable. By making the compounding quantity of a quinone diazide compound into the said range, the difference of the solubility of the irradiated part and the unirradiated part of the actinic ray with respect to the alkaline aqueous solution used as a developing solution is large, and patterning performance becomes favorable and the solvent resistance of the cured film obtained becomes favorable. .

Suitable Mode 3: Negative Type

Suitable aspect 3 is an aspect in which the alignment film material contains a compound (polymerizable compound) having two or more groups having an ethylenically unsaturated bond and a photopolymerization initiator.

In the case of the suitable aspect 3, when exposure is performed to the coating film formed from an oriented film material, since an exposure part will bridge | crosslink normally, a non-exposure part will melt | dissolve by image development, and a negative pattern will be formed. In suitable Embodiment 3, it is preferable to include the polymer containing the structural unit which has a crosslinkable group mentioned later in an orientation film material.

(Polymerizable compound)

As a group which has an ethylenically unsaturated bond which a polymeric compound has, a vinyl group, a (meth) allyl group, a (meth) acryloyl group, etc. are mentioned, A (meth) acryloyl group is preferable.

The polymerizable compound may be any of chemical forms such as a monomer, a prepolymer, an oligomer, and a polymer. Monomers and / or polymers are preferred. It is preferable that the molecular weight of a monomer type polymeric compound is 100-3000. It is preferable that the weight average molecular weights of a polymeric type polymerizable compound are 3,000-2,000,000. 1,000,000 or less are preferable and, as for an upper limit, 500,000 or less are more preferable. 4,000 or more are preferable and, as for a minimum, 5,000 or more are more preferable.

The polymerizable compound is preferably a (meth) acrylate compound. The compound which has two or more (meth) acryloyl groups in 1 molecule is preferable, and the (meth) acrylate compound has a more preferable compound which has three or more (meth) acryloyl groups. 15 or less are preferable, as for the upper limit of the number of a (meth) acryloyl group, 10 or less are more preferable, 8 or less are more preferable, and 6 or less are especially preferable. As these specific compounds, Paragraph 0095-0108 of Unexamined-Japanese-Patent No. 2009-288705, Paragraph 0227 of Unexamined-Japanese-Patent No. 2013-29760, Paragraph No. 0254 of Unexamined-Japanese-Patent No. 2008-292970 can be referred to. The contents of which are incorporated herein by reference.

Polymeric compounds include dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320; Nippon Kayaku Co., Ltd.). Made), dipentaerythritol penta (meth) acrylate (as a commercial item, KAYARAD D-310; made by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate, dipentaerythritol pentaacrylate, and die Mixtures of pentaerythritol hexaacrylate (as commercially available products such as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and their (meth) acryloyl groups are ethylene glycol; Preference is given to structures having lycol and propylene glycol residues (eg, SR454, SR499, available from Sartomer). These oligomer types can also be used. Moreover, KAYARAD RP-1040, DPCA-20 (made by Nippon Kayaku Co., Ltd.), and M-321 (made by Toagosei Co., Ltd.) can also be used.

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

The polymerizable compound is also a preferred embodiment of a compound having a caprolactone structure. The polymeric compound which has a caprolactone structure is marketed as a KAYARAD DPCA series from Nippon Kayaku Co., Ltd., For example, DPCA-20, DPCA-30, DPCA-60, DPCA-120 etc. are mentioned.

The polymeric compound which has an alkyleneoxy group can also be used for a polymeric compound. The polymeric compound which has an ethyleneoxy group and / or a propyleneoxy group is preferable, as for the polymeric compound which has an alkyleneoxy group, the polymeric compound which has an ethyleneoxy group is more preferable, (meth) which has 4-20 ethyleneoxy groups More preferred are acrylate compounds. As a commercial item of the polymeric compound which has an alkyleneoxy group, 6 which has six pentyleneoxy groups made by SR-494 and Nippon Kayaku Co., Ltd. which are tetrafunctional acrylates which have four ethyleneoxy groups made by Satomer, for example. DPCA-60 which is a functional acrylate, TPA-330 which is trifunctional acrylate which has three isobutylene oxy groups, etc. are mentioned.

The polymerizable compound is described in Urete No. 48-41708, Japanese Patent Application Laid-open No. 51-37193, Japanese Patent Application Laid-Open No. 2-32293 and Japanese Patent Application Laid-open No. 2-16765. Ethylene oxide-based skeletons described in inacrylates, Japanese Patent Application Laid-Open No. 58-49860, Japanese Patent Application Laid-open No. 56-17654, Japanese Patent Application Laid-open No. 62-39417 and Japanese Patent Application Laid-open No. 62-39418 Suitable urethane compounds are also suitable. As a commercial item, urethane oligomer UAS-10, UAB-140 (made by Sanyo Kokusaku pulp Co., Ltd.), U-15HA, U-6LPA, UA-7200 (made by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha), etc. are mentioned.

It is also preferable that a polymeric compound is a polymer (henceforth a polymeric polymer) which has a group which has an ethylenically unsaturated bond in a side chain. It is preferable that content of the structural unit which has group which has an ethylenically unsaturated bond in a side chain is 5-100 mass% of all the structural units of a polymerizable polymer. 10 mass% or more is more preferable, and, as for a minimum, 15 mass% or more is more preferable. 95 mass% or less is more preferable, and, as for an upper limit, 90 mass% or less is more preferable.

The polymerizable polymer may include other structural units in addition to the structural unit having a group having an ethylenically unsaturated bond in the side chain. Another structural unit may contain functional groups, such as an acidic radical, and does not need to contain a functional group. As an acidic radical, a carboxyl group, a sulfonic acid group, and a phosphoric acid group are illustrated. One type of acidic radical may be included and may be included two or more types. Examples of other functional groups include development accelerators such as lactones, acid anhydrides, amides, and cyano groups, long chain and cyclic alkyl groups, aralkyl groups, aryl groups, polyalkylene oxide groups, hydroxyl groups, maleimide groups, and amino groups. It can introduce | transduce suitably.

It is preferable that a polymeric polymer contains the structural unit which has an acidic radical. It is preferable that the ratio of the structural unit which has an acidic radical is 1-50 mass% of all the structural units which comprise a polymeric polymer. 2 mass% or more is more preferable, and, as for a minimum, 3 mass% or more is more preferable. 35 mass% or less is more preferable, and, as for an upper limit, 30 mass% or less is more preferable. When a polymerizable polymer contains the structural unit which has an acidic radical, it is preferable that the acid value of a polymerizable polymer is 10-150 mgKOH / g. 20 mgKOH / g or more is preferable and, as for a minimum, 30 mgKOH / g or more is more preferable. 140 mgKOH / g or less is preferable and, as for an upper limit, 130 mgKOH / g or less is more preferable.

As a commercial item of a polymerizable polymer, Diamond NR series (made by Mitsubishi Rayon Corporation), Photomer 6173 (COOH containing polyurethane acrylic oligomer.Diamond Shamrock Co., Ltd.), biscot R-264, KS resist 106 (all Osaka Yuki Kagaku Kogyo Co., Ltd., cyclomer P series (e.g., ACA230AA), Plaxel CF200 series (all made by Daicel Kagaku Kogyo Co., Ltd.), Ebecryl3800 (Diessel Yusubi Kagushiki Co., Ltd.) ) And Acrycure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.).

10 mass parts or more are preferable with respect to 100 mass parts of total solid components, as for content of the polymeric compound in an orientation film material, 20 mass parts or more are more preferable, 30 mass parts or more are more preferable. As for an upper limit, 99 mass parts or less are more preferable, for example. The alignment film material may include only one type of the polymerizable compound or may include two or more types. When it contains two or more types, it is preferable that the total amount becomes said range.

(Photoinitiator)

As described above, in a suitable embodiment 3, the alignment film material contains a photopolymerization initiator.

As a photoinitiator, there is no restriction | limiting in particular as long as it has the ability to start superposition | polymerization of a polymeric compound, It can select suitably from well-known photoinitiators. For example, it is preferable to have photosensitivity to visible light from an ultraviolet range. It is preferable that a photoinitiator contains at least 1 sort (s) of compound which has at least about 50 molar extinction coefficient in the range of about 300 nm-800 nm (330 nm-500 nm are more preferable).

As a photoinitiator, For example, an acyl phosphine compound, an alkyl phenone type compound, the (alpha)-amino ketone compound, a benzophenone type compound, a benzoin ether type compound, a ketal derivative compound, a thioxanthone compound, an oxime compound, hexaaryl bi Imidazole compound, trihalomethyl compound, azo compound, organic peroxide, diazonium compound, iodonium compound, sulfonium compound, azinium compound, metallocene compound, organic boron salt compound, disulfone compound, thiol compound Etc. can be mentioned. From a viewpoint of a sensitivity, an oxime compound and an alkyl phenone type compound are preferable. As a photoinitiator, Paragraph No. 0061 of Unexamined-Japanese-Patent No. 2011-186398-description of 0073 can be referred, for example, This content is integrated in this specification.

As the oxime compound, commercially available IRGACURE OXE-01 (manufactured by BASF Corporation), IRGACURE OXE-02 (manufactured by BASF Corporation), TR-PBG-304 (Changzhou Tronly New Electronic Materials Co., Ltd.) Company), Adeka Ackles NCI-831 (made by ADEKA Corporation), Adeka Ackles NCI-930 (made by ADEKA Corporation), etc. can be used.

This invention can also use the oxime compound which has a fluorine atom as a photoinitiator. As a specific example of the oxime compound which has a fluorine atom, the compound of Unexamined-Japanese-Patent No. 2010-262028, the compound of Unexamined-Japanese-Patent No. 2014-500852, the compound 24, 36-40, and the compound of Unexamined-Japanese-Patent No. 2013-164471 (C-3) etc. are mentioned. This content is taken in into this specification.

As an alkyl phenone type compound, a hydroxyalkyl phenone compound, an aminoalkyl phenone type compound, etc. are mentioned. As the hydroxyalkyl phenone compound, commercially available IRGACURE 184, DAROCUR 1173, IRGACURE 500, IRGACURE 2959, and IRGACURE 127 (trade names: all manufactured by BASF Corporation) can be used. As the aminoalkyl phenone-based compound, commercially available IRGACURE 907, IRGACURE 369, and IRGACURE 379EG (trade names: all manufactured by BASF Corporation) can be used.

As the acyl phosphine compound, commercially available IRGACURE 819 or DAROCUR-TPO (trade name: all 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. If it is this range, more favorable sensitivity and pattern formability will be obtained. The alignment film material may include only one type of photopolymerization initiator or may include two or more types. When it contains two or more types, it is preferable that the total amount becomes said range.

[Optical orientation]

As described above, the alignment film material used in the present invention has photoalignment.

As a preferable aspect for the alignment film material to have photo-alignment property, the following suitable aspects 1-2 are mentioned, for example.

(1) Suitable embodiment 1: Embodiment containing a polymer p2 comprising a structural unit having a photoalignable group

(2) Suitable aspect 2: Embodiment containing the polyimide precursor p3 represented by Formula (p3) mentioned later

Hereinafter, each aspect is explained in full detail.

<Fit Embodiment 1: Embodiment containing the polymer p2 containing the structural unit which has a photo-alignment group>

As a suitable aspect 1, the aspect in which an oriented film material contains the polymer p2 containing the structural unit which has a photo-alignment group is mentioned.

Here, a photo-orientation group means the photoreactive group which provides orientation by any one of a photodimerization reaction, a photoisomerization reaction, and a photolysis reaction. Especially, the photoreactive group which provides orientation by photodimerization reaction is preferable.

Moreover, as a group which gives orientation by a photodimerization reaction, the group introduce | transduced from at least 1 sort (s) of derivative chosen from the group which consists of a maleimide derivative, a cinnamic acid derivative, and a coumarin derivative etc. are mentioned, for example, Specifically, cinnamate group and a chalcone group are mentioned suitably. Especially, cinnamate group is preferable.

As the cinnamate group and the chalcone group, for example, the following structures (in the following formula, * represents a linking site to the polymer chain and R represents a hydrogen atom or a monovalent organic group) can be introduced. In addition, the connection site | part to the polymer chain shown by * may be directly connected to the main chain of a polymer, and may be couple | bonded through the bivalent coupling group. As a monovalent organic group which R represents, an alkyl group or an aryl group is preferable. Moreover, 1-10 are preferable and, as for carbon number of the monovalent organic group which R represents, 1-7 are more preferable.

[Formula 7]

On the other hand, as a reactive group which isomerizes by the action of light, specifically, the group etc. which consist of a skeleton of at least 1 sort (s) of compound chosen from the group which consists of an azobenzene compound, a stilbene compound, and a spiropyran compound are suitable, for example. It can be heard.

Moreover, as a reactive group decomposed by the action of light, specifically, the group which consists of a skeleton of a cyclobutane compound, etc. are mentioned suitably, for example.

Among these, it is preferable that it is group which provides orientation by the photodimerization reaction which reacts with short wave light from the reason of the irreversibility of reaction, and it is more preferable that it is at least 1 sort (s) chosen from the group which consists of a cinnamate group and a chalcone group.

The polymer p2 having a structural unit having a photo-alignment group is not particularly limited in its main chain skeleton, but the molecular design of the side chains is varied, and the main chain formation by the radical polymerization reaction of the ethylenically unsaturated compound is easy, and the following general formula (III) It is preferable that it is a polymer (polymer) which has a repeating unit (structural unit) represented by ().

[Formula 8]

(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 carbon number.) L represents a single bond or a divalent linking group, and P represents a photoalignable group.)

Here, in general formula (III), R <^1> represents a hydrogen atom or an alkyl group, As an alkyl group, a C1-C4 alkyl group (for example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-view) And the like. It is preferable that R <^1> is a hydrogen atom or a methyl group.

In General Formula (III), L represents a single bond or a divalent linking group, and as the divalent linking group, a group formed by combining -O-, -S-, an alkylene group, an arylene group, or a plurality thereof is preferable. Although the linear, branched, or cyclic structure may be sufficient as the alkylene group which L represents, it is preferable that it is 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, As a specific example, a chalcone group, a cinnamate group, a stilbenyl group, a maleimide group, and an azobenzyl group are mentioned suitably. Especially, a chalcone group and a cinnamate group are more preferable. In addition, the photo-alignment group which P represents may have a substituent unless the photo-alignment property is lost. As a specific substituent, a halogeno group, an alkyl group, an aryl group, etc. are mentioned, for example, It is preferable that it is an alkyl group or an aryl group. 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.

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

Although the molar ratio of the structural unit which has a photo-alignment group with respect to the total structural unit which comprises polymer p2 is not specifically limited, It is preferable that it is 10-100 mol%, and it is more preferable that it is 20-90 mol%.

Although content of the polymer p2 in an oriented film material is not specifically limited, 0.1-99.9 mass parts is preferable with respect to 100 mass parts of total solid components. For example, 10 mass parts or more are more preferable, and, as for a minimum, 20 mass parts or more are more preferable. For example, 90 mass parts or less are more preferable, and, as for an upper limit, 80 mass parts or less are more preferable.

Polymer p2 may be used independently and may be used in combination of 2 or more type.

(Structural Embodiment 1a: Embodiment in which the polymer p2 further includes a structural unit having a localized group)

As a suitable embodiment of the polymer p2, for example, a structure having at least one partial structure selected from the group consisting of a fluorine-substituted hydrocarbon group, a siloxane skeleton and an alkyl group having 10 to 30 carbon atoms (hereinafter also referred to as a "local group"). The polymer p2a which further contains a unit is mentioned. Since the oriented group is unevenly distributed on the surface of a film by including the structural unit which has a locality group, content of the polymer p2 can be suppressed.

Hereinafter, each local knitting machine is demonstrated in detail.

(1) Structural unit having partial structure of fluorine-substituted hydrocarbon group

The fluorine-substituted hydrocarbon group may be a hydrocarbon group substituted with at least one fluorine atom, and at least one hydrogen atom in an alkyl group or an alkylene group (hereinafter abbreviated as "alkyl group" in the present paragraph) is fluorine. Alkyl group substituted by the atom, etc. are mentioned, The alkyl group etc. which substituted all hydrogen atoms, such as an alkyl group, with a fluorine atom are more preferable.

It is preferable that such a fluorine-substituted hydrocarbon group is group represented by the following general formula (I) from a ubiquitous viewpoint.

[Formula 17]

In general formula (I), R <^2> represents a hydrogen atom or a C1-C4 alkyl group, and * shows the connection site | part 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. In addition, when m is 1, some R <^2> may be same or different, respectively.

M in General formula I represents the integer of 1-3, and it is preferable that it is 1 or 2.

N in General formula I represents the integer of 1 or more, It is preferable that it is an integer of 1-10, It is more preferable that it is an integer of 1-4, It is especially preferable that it is 1 or 2.

R in General formula I represents the integer of 0 or 1-2, It is preferable that it is 1 or 2, It is more preferable that it is 2.

Moreover, the connection site | part to the polymer chain shown by * may be directly connected to the main chain of a polymer, and may be a polyoxyalkylene group, an alkylene group, an ester group, a urethane group, a cyclic alkylene group which may contain a hetero atom, and poly (capro) You may couple | bond via bivalent coupling groups, such as a lactone) and an amino group. It is preferable to couple through a polyoxyalkylene group.

As a C1-C4 alkyl group represented by R <^2> in General formula I, a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, an isobutyl group, a tert-butyl group, etc. are mentioned, Preferably, , A hydrogen atom or a methyl group, more preferably a hydrogen atom.

In General Formula I, when X is a single bond, it means that the polymer main chain and the carbon atom which R <^2> couple | bonds are connected directly.

Also, when X is a divalent connecting group, examples of the connecting group, -O-, -S-, -N (R 4) - it may be mentioned, -CO- and the like. Among these, -O- is more preferable. Here, R <^4> represents a hydrogen atom or a C1-C4 alkyl group. As an alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, isobutyl group, tert- butyl group, etc. are mentioned, Preferably, they are a hydrogen atom and a methyl group.

As a method of introducing a fluorine-substituted hydrocarbon group into a polymer, The method of introducing a fluorine-substituted hydrocarbon group into a polymer by polymer reaction; A method of copolymerizing a monomer having a fluorine-substituted hydrocarbon group (hereinafter referred to as a "fluorine-substituted hydrocarbon group-containing monomer") to introduce a structural unit having a fluorine-substituted hydrocarbon group into the polymer; Etc. can be mentioned.

As a fluorine-substituted hydrocarbon group containing monomer in the method of copolymerizing a fluorine-substituted hydrocarbon group containing monomer and introducing the structural unit which has a fluorine-substituted hydrocarbon group into a polymer, the monomer represented by following General formula II is mentioned as a preferable thing. have.

[Formula 18]

In General Formula II, R <^1> represents a hydrogen atom, a halogen atom, the methyl group which may have a substituent, or the ethyl group which may have a substituent. Moreover, all of R <^2> , X, m, n, and r are synonymous with R <^2> , X, m, n, and r in General formula I, and a preferable example is also the same.

Moreover, 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 manufacturing method of such a fluorine-substituted hydrocarbon group containing monomer, pages 117-118 of "Synthesis and function of a fluorine compound" (Survey: Nobuo, Ishikawa, Published by CMC, 1987) , 747-752, "Chemistry of Organic Fluorine Compounds II" (Monograph 187, Ed by Milos Hudlicky and Attila E. Pavlath, American Chemical Society 1995).

Moreover, as a specific example of the monomer represented by General formula II, the tetrafluoroisopropyl methacrylate represented by following formula (IIa), the hexafluoroisopropyl methacrylate represented by following formula (IIb), etc. are mentioned.

Moreover, as another specific example, the compound of Unexamined-Japanese-Patent No. 2010-18728 Paragraph No.-0058-[0061] is mentioned. Among these, the structure which the fluorine-substituted hydrocarbon group couple | bonded with the polyoxyalkylene group is preferable.

[Formula 19]

(2) Structural unit having partial structure of siloxane skeleton

If the siloxane skeleton has "-Si-O-Si-", there is no restriction | limiting in particular and it is preferable to contain a polyoxyalkylene group.

In this invention, it is preferable that a siloxane skeleton copolymerizes the compound which has a (meth) acryloyloxy group and an alkoxy silyl group from a viewpoint of ubiquitous, and introduces the structural unit which has a partial structure of a siloxane skeleton into a polymer. .

Here, as an alkoxy silyl group, group represented by following formula (X) is preferable, for example.

[Formula 20]

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 one is an alkoxy group. * Represents a bonding position.

In said Formula (X), at least one of R <^3> -R <^5> is an alkoxy group, As an alkoxy group, it is preferable that it is a C1-C15 alkoxy group, It is more preferable that it is a C1-C8 alkoxy group, It is C1-C8 It is more preferable that it is an alkoxy group of 4, and it is especially preferable that it is an ethoxy group or a methoxy group.

In this invention, when R <^2> -R <^5> is two when an alkoxy group and one is an alkyl group, or when three are an alkoxy group, it is preferable. Especially, it is more preferable that 3 is an alkoxy group, ie, a trialkoxy silyl group.

As a compound which has such an alkoxy silyl group and a (meth) acryloyloxy group, specifically, 3- (meth) acryloxypropyl methyl dimethoxy silane and 3- (meth) acryloxypropyl trimes Oxy silane, 3- (meth) acryloxypropyl methyl diethoxy silane, 3- (meth) acryloxypropyl triethoxy silane, etc. are mentioned.

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

[Formula 21]

In said structural formula (A), R <^7> is a C2-C6 linear or branched alkylene group which may have substituents, such as a hydroxyl group, an amine group, and a halogen atom, or the bivalent coupling group represented by following structural formula (B). Indicates.

[Formula 22]

In said structural formula (B), R <^4> represents a hydrogen atom, a methyl group, and an ethyl group. n1, n2, and n3 are the integers of 0-100 each independently. Here, although two or more R <^4> exists in structural formula (B), they may differ, respectively and may be the same.

In said structural formula (A), x1, x2, and x3 are integers whose sum satisfy | fills 1-100.

In addition, y1 is an integer of 1-30.

In said structural formula (A), X <^2> is a bivalent group represented by a single bond or the following structural formula (C).

[Formula 23]

In said structural formula (C), R <^8> represents the C1-C6 linear or branched alkylene group which may have substituents, such as a hydroxyl group, an amine group, and a halogen atom, Q <^1> and Q <^2> are oxygen An atom, a sulfur atom, or -NRB- is represented, and Q <^1> , Q <^2> may respectively differ and may be the same. RB represents a hydrogen atom or a C1-C4 alkyl group.

In said structural formula (C), Q <^2> couple | bonds with R <^7> in the said structural formula (A).

In said structural formula (A), Y <^2> represents the monovalent group represented by following structural formula (D)-the following structural formula (F).

[Formula 24]

In said structural formula (D)-(F), R <^5> represents a hydrogen atom or a C1-C6 linear or branched alkyl group.

In said structural formula (A), Z <^1> , Z <^2> , Z <^3> respectively independently represents the monovalent group represented by the following structural formula (G).

[Formula 25]

Of the structural formula (G), R ⁶ is a 1-4C alkyl group non-substituted, y ² is an integer of from 1 to 100, preferably from 1 to 50 integer, and more preferably from 1 to 20 of the Is an integer.

Moreover, as a siloxane skeleton, although the structure described in Paragraph No. 0092-0094 of Unexamined-Japanese-Patent No. 2010-18728 is mentioned as a specific example of said Formula (A), it is not limited to these.

Among these, the structure in which the siloxane structure couple | bonded with the polymer through polyoxyalkylene group is preferable.

(3) A structural unit having a partial structure of an alkyl group having 10 to 30 carbon atoms

Although the C10-C30 alkyl group may contain the branched structure or the cyclic structure, it is preferable that carbon number of the part of a linear structure exists in the range of 10-30, and it is more preferable that all are linear structure.

Moreover, it is preferable that carbon number of an alkyl group is 10-20.

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

[Formula 26]

In general formula (a3-1), n _a3 represents the integer of 10-30, * shows the position which connects with the main chain or side chain of a polymer. It is preferable that n <_a3> is an integer of 10-20.

The method of introducing the structure of the general formula (a3-1) into the main chain or the side chain of the polymer is not particularly limited. For example, when a monomer having the structure of (a3-1) is appropriately selected and applied at the time of synthesis, The structure of (a3-1) can be introduce | transduced in the repeating unit of the polymer obtained.

Moreover, although the commercially available compound can be used for the monomer which has the structure of the said general formula (a3-1), the desired structure contained in (a3-1) with respect to the commercially available monomer which does not have the structure of (a3-1). You may introduce | transduce and use suitably. There is no limitation in the method of introducing the structure of (a3-1) to a commercially available monomer, What is necessary is just to apply a well-known method suitably.

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

[Formula 27]

In said general formula (a3-2), R <^32> represents a hydrogen atom, a methyl group, an ethyl group, or a halogen atom, X <^31> represents a bivalent coupling group, R <^33> represents a single bond or an alkyleneoxy group. In addition, n _a3 is synonymous including the said general formula (a3-1) and a preferable range.

In general formula (a3-2), R <^32> is a hydrogen atom, a methyl group, an ethyl group, or a halogen atom, More preferably, it is a hydrogen atom or a methyl group, More preferably, it is a methyl group.

In the formula (a3-2), as the divalent linking group as ^{X 31, -O-, -S-, -N} (R 4) - may be mentioned, and the like. Among these, -O- is more preferable.

Here, R <^4> represents a hydrogen atom or a C1-C4 alkyl group. The alkyl group may be a straight chain structure or a branched structure, and may include a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group, isobutyl group, tert-butyl group, etc., preferably a hydrogen atom, Methyl group.

Moreover, as an alkyleneoxy group of R <^33> , it is preferable that it is C1-C4. The alkyleneoxy group may have a branched structure. Moreover, you may have a substituent and may be unsubstituted. As a substituent which you may have, a halogen atom etc. are mentioned. As a specific example of an alkyleneoxy group, a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, etc. can be illustrated.

Among these, it is preferable that R <^33> is a C1-C4 unsubstituted linear alkyleneoxy group or a single bond, and it is more preferable that it is a single bond.

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

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

[Formula 28]

In the general formula (U-a3-1), n _a3 is synonymous with the general formula (a3-1), including a preferable range, and R ³² , X ³¹ , and R ³³ are the general formula (a3-). 2) and preferred ranges are also included.

Hereinafter, the specific example of the monomer represented by general formula (a3-2) is shown. However, this invention is not limited to these.

[Formula 29]

Although the molar ratio of the structural unit which has a ubiquitous group with respect to the whole structural unit which comprises polymer p2a is not specifically limited, It is preferable that it is 1-50 mol%, and it is more preferable that it is 10-30 mol%.

Although content in particular of the polymer p2a in an oriented film material is not restrict | limited, 0.1-99.9 mass parts is preferable with respect to 100 mass parts of total solid components. As for a minimum, 1 mass part or more is more preferable, for example. For example, 20 mass parts or less are more preferable, and, as for an upper limit, 10 mass parts or less are more preferable.

Polymer p2a may be used independently and may be used in combination of 2 or more type.

<Fit embodiment 2: embodiment containing the polyimide precursor p3 represented by Formula (p3)>

As a suitable aspect 2, the aspect in which an oriented film material contains the polyimide precursor p3 (polymer p3) represented by Formula (p3) is mentioned.

It is estimated that the said polyimide precursor p3 is ring-closed (cyclized) by the above-mentioned thermosetting process, becomes a polyimide, and is decomposed | disassembled and orientated in the part of A in Formula (p3) by the photo-alignment process mentioned above. .

As mentioned above, since polyimide precursor p3 cyclizes by the thermosetting process, it shows thermosetting property. That is, the polyimide precursor p3 has photoalignment and also corresponds to a thermosetting component described later.

Hereinafter, polyimide precursor p3 is demonstrated.

Equation (p3)

[Formula 30]

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

In said formula (p3), it is preferable that A is at least 1 sort (s) of structure chosen from following formula (A-1)-following formula (A-5). Especially, it is preferable that it is a structure of Formula (A-1) from a viewpoint of showing the more excellent optical orientation.

[Formula 31]

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

A in said formula (p3) can contain a tetravalent aromatic hydrocarbon group and / or a tetravalent chain hydrocarbon group. As a tetravalent aromatic hydrocarbon group, the tetravalent group by which four hydrogen of the mother skeleton of an aromatic hydrocarbon was substituted is mentioned specifically ,.

Examples of the chain hydrocarbons 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. Can be mentioned. In addition, these tetravalent chain hydrocarbon groups may contain an aromatic ring in at least one part of the structure.

In said formula (p3), it is preferable that B is a bivalent aromatic hydrocarbon group or a bivalent alicyclic group, and following formula (B-1)-following formula (B-10) and following formula (4)-(5) It is more preferable that it is at least 1 sort (s) of structure chosen from.

[Formula 32]

R <^5> represents a hydrogen atom, a C1-C6 alkyl group, or a hydroxyl group each independently in said Formula (B-1)-said Formula (B-8).

[Formula 33]

In said formula (5), Z <_1> is a single bond, an ester bond, an amide bond, a thioester bond, or a C2-C10 divalent organic group.

The specific example and suitable aspect of the acid-decomposable group represented by X <^1> and X <^2> in said Formula (p3) are the same as the acid-decomposable group which polymer p1 mentioned above has.

In addition, when the formula (p3) of the X ¹ or X ² is an acid-decomposable group, because the polyimide precursor is p3, p1 in the above-described polymer, the alignment film material is set to indicate Chengdu optical patterning.

Although content in particular of the polyimide precursor p3 in an orientation film material is not restrict | limited, 0.1-99.9 mass parts is preferable with respect to 100 mass parts of total solid components. For example, 10 mass parts or more are more preferable, and, as for a minimum, 20 mass parts or more are more preferable. For example, 90 mass parts or less are more preferable, and, as for an upper limit, 80 mass parts or less are more preferable.

Polyimide precursor p3 may be used independently and may be used in combination of 2 or more type.

[Thermosetting component]

As described above, the alignment film material used in the present invention contains a thermosetting component. A thermosetting component hardens | cures (crosslinking, cyclization, etc.) by the above-mentioned thermosetting process.

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 demonstrated in detail.

<Structural unit having a crosslinking group>

The crosslinkable group is not particularly limited as long as it is a group that generates a curing reaction by heat treatment.

As the embodiment of the constituent unit having a preferred crosslinking group, an epoxy group (for example, an oxirane group, a 3,4-epoxy cyclohexyl group and the like), an oxetane group, a -NH-CH ₂ -OR (R is a hydrogen atom or a carbon atoms And a structural unit containing at least one selected from the group consisting of a group represented by an alkyl group of 1 to 20), an ethylenically unsaturated group, and a block isocyanate group, and an epoxy group, an oxetanyl group, and -NH-CH. _It is a structural unit containing at least 1 sort (s) chosen from the group which consists of group represented by _2- OR (R represents a hydrogen atom or a C1-C20 alkyl group), a (meth) acryloyl group, and a block isocyanate group. A constituent group comprising at least one member selected from the group consisting of an epoxy group, an oxetanyl group, and a group represented by -NH-CH ₂ -OR (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) It is more preferable that it is the above.

(Structural unit having an epoxy group and / or oxetanyl group)

The structural unit which has the said epoxy group and / or oxetanyl group should just have at least one epoxy group or oxetanyl group in one structural unit, and it is 1 or more epoxy groups, 1 or more oxetanyl groups, 2 or more epoxy groups, or Although it may have two or more oxetanyl groups, it is not specifically limited, It is preferable to have one or three epoxy groups and / or oxetanyl groups in total, and it has one or two epoxy groups and / or oxetanyl groups in total. It is more preferable, and it is more preferable to have one epoxy group or oxetanyl group.

As a specific example of the radically polymerizable monomer used in order to form the structural unit which has an epoxy group, For example, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycine (alpha)-n-propyl acrylate Cydyl, α-n-butyl acrylate glycidyl, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-3,4-epoxycyclohexylmethyl, methacrylic acid-3, 4-epoxycyclohexylmethyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, p-vinylbenzylglycidylether And the compound containing the alicyclic epoxy skeleton of Paragraph 0031 of Unexamined-Japanese-Patent No. 4168443-0035, etc. These content is integrated in this specification.

As a specific example of the radically polymerizable monomer used in order to form the structural unit which has an oxetanyl group, the (meth) acrylic acid ester etc. which have the oxetanyl group as described in Paragraph 0011-0016 of Unexamined-Japanese-Patent No. 2001-330953, etc. These contents are integrated in this specification.

As a specific example of the radically polymerizable monomer used in order to form the structural unit which has the said epoxy group and / or oxetanyl group, it is preferable that it is a monomer containing a methacrylic acid ester structure, and a monomer containing an acrylic acid ester structure.

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

The following structural unit can be illustrated as a preferable specific example of the structural unit which has an epoxy group and / or oxetanyl group. In addition, R represents a hydrogen atom or a methyl group.

[Formula 34]

(Structural unit having an ethylenically unsaturated group)

As another example of the structural unit which has the said crosslinkable group, the structural unit which has an ethylenically unsaturated group is mentioned. As a structural unit which has the said ethylenically unsaturated group, the structural unit which has an ethylenically unsaturated group in a side chain is preferable, and the structural unit which has an ethylenically unsaturated group at the terminal and has a C3-C16 side chain is more preferable.

In addition, about the structural unit which has an ethylenically unsaturated group, Paragraph 0072 of Unexamined-Japanese-Patent No. 2011-215580-description of 0090, and Paragraph 0013-0031 of Unexamined-Japanese-Patent No. 2008-256974 can be referred, The contents are incorporated herein by reference.

(Structural unit having a group represented by -NH-CH ₂ -OR)

Other examples of structural units having a crosslinking group, -NH-CH ₂ -OR is also preferable structural unit having a group represented by (R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). By having a structural unit, hardening reaction can be raise | generated by gentle heat processing, and the cured film excellent in all the 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, still more preferably an alkyl group having 1 to 4 carbon atoms. Moreover, although an alkyl group may be any of a linear, branched or cyclic alkyl group, it is preferable that it is a linear or branched alkyl group. As for a structural unit, it is more preferable that it is a structural unit which has group represented by following formula a2-30.

[Formula 35]

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. Moreover, although an alkyl group may be any of a linear, branched or cyclic alkyl group, Preferably it is a linear or branched alkyl group.

As a specific example of R <^32> , a methyl group, an ethyl group, n-butyl group, i-butyl group, a cyclohexyl group, and n-hexyl group are mentioned. Especially, i-butyl group, n-butyl group, and a methyl group are preferable.

Although the molar ratio of the structural unit which has a crosslinkable group with respect to the whole structural unit which comprises polymer p4 is not restrict | limited, It is preferable that it is 10-50 mol%.

<Structural unit having an acid group>

When the structural unit which has the said crosslinkable group is a structural unit which has an epoxy group and / or an oxetanyl group, it is preferable that the polymer p4 also includes the structural unit which has an acidic group. In this case, in the above-mentioned thermosetting process, an epoxy group and / or oxetanyl group and an acidic group react and bridge | crosslink. In addition, the structural unit which has an acidic radical may be contained as a polymer different from the polymer p4.

The acidic radical in this invention means the proton dissociable group whose pKa is smaller than 11.

As an acid group used by this invention, a carboxylic acid group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, a sulfonamide group, a sulfonyl imide group, the acid anhydride group of these acid groups, and these acid groups are neutralized, and is salted. The group etc. which made into a structure are illustrated, 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, an alkaline earth metal salt, and an organic ammonium salt can be illustrated preferably.

It is more preferable that the structural unit containing the acid group used by this invention is a structural unit derived from styrene, the structural unit derived from a vinyl compound, (meth) acrylic acid, and / or its ester. For example, Paragraph 0021-0023 of Unexamined-Japanese-Patent No. 2012-88459, and the compound of Paragraph 0029-0044 can be used, This content is integrated in this specification. Especially, the structural unit derived from p-hydroxy styrene, (meth) acrylic acid, maleic acid, and maleic anhydride is preferable.

As structural unit a3 which has an acidic radical, the structural unit which has a carboxyl group or the structural unit which has a phenolic hydroxyl group is preferable from a viewpoint of a sensitivity, and the structural unit which has a carboxyl group is more preferable.

Specifically as structural unit a3 which has an acidic radical, Structural unit a1-1-1 which derives from the structural unit a1-1-1 derived from unsaturated carboxylic acid etc. which have at least 1 carboxyl group in the molecule mentioned above, an ethylenically unsaturated group, and an acid anhydride is mentioned. The structural unit a1-2-1 which has 1-2 and phenolic hydroxyl group is mentioned, A preferable aspect is also the same.

Especially, as structural unit a3 which has an acidic radical, the structural unit derived from the compound selected from the group which consists of methacrylic acid, acrylic acid, and p-hydroxy styrene (structural unit represented by either of following formula a3-1-formula a3-3) ), More preferably a structural unit derived from methacrylic acid (structural unit represented by the following formula a3-1) or a structural unit derived from acrylic acid (structural unit represented by the following formula a3-2), and methacrylic acid It is more preferable that it is a derived structural unit (structural unit represented by following formula a3-1).

[Formula 36]

Although the molar ratio in particular of the structural unit which has an acidic radical with respect to the total structural unit which comprises polymer p4 is not restrict | limited, It is preferable that it is 10-50 mol%.

Although content in particular of the polymer p4 in an oriented film material is not restrict | limited, 0.1-99.9 mass parts is preferable with respect to 100 mass parts of total solid components. For example, 10 mass parts or more are more preferable, and, as for a minimum, 20 mass parts or more are more preferable. For example, 90 mass parts or less are more preferable, and, as for an upper limit, 80 mass parts or less are more preferable.

Polymer p4 may be used independently and may be used in combination of 2 or more type.

[Other structural units]

The polymer p1-4 mentioned above may contain other structural units.

There is no restriction | limiting in particular as a monomer which forms such a structural unit, For example, styrene, (meth) acrylic-acid alkylester, (meth) acrylic-acid cyclic alkylester, (meth) acrylic-acid arylester, unsaturated dicarboxylic acid diester And bicyclo unsaturated 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.

Other structural units may specifically include styrene, methyl styrene, α-methyl styrene, acetoxy styrene, methoxy styrene, ethoxy styrene, chloro styrene, methyl vinyl benzoate, ethyl vinyl benzoate, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid 2- Structural units of hydroxyethyl, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate and the like Can be mentioned. In addition, Paragraph 0021 of Unexamined-Japanese-Patent No. 2004-264623-the compound of 0024 can be mentioned.

Moreover, as another structural unit, the structural unit derived from the styrene or the monomer which has an aliphatic cyclic skeleton is preferable from a viewpoint of an electrical property. Specifically, styrene, methyl styrene, α-methyl styrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, etc. Can be mentioned.

Moreover, as another structural unit, the structural unit derived from the (meth) acrylic-acid alkylester is preferable from a viewpoint of adhesiveness. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, etc. are mentioned, Methyl (meth) acrylate is more preferable. 60 mol% or less is preferable, as for the content rate of the said structural unit among all the structural units which comprise a polymer, 50 mol% or less is more preferable, 40 mol% or less is more preferable. 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. If it exists in the range of said numerical value, all the characteristics will become favorable.

〔Molecular Weight〕

The molecular weight of the above-mentioned polymers p1-4 is polystyrene conversion weight average molecular weight, Preferably it is 1,000-200,000, More preferably, it is 2,000-50,000, More preferably, it is the range of 10,000-20,000. If it is in the range of said numerical value, all the characteristics are favorable. 1.0-5.0 are preferable and, as for ratio (dispersion degree, Mw / Mn) of number average molecular weight Mn and weight average molecular weight Mw, 1.5-3.5 are more preferable.

In addition, it is preferable to measure the weight average molecular weight and number average molecular weight in this invention by the gel permeation chromatography (GPC) method. The measurement by the gel permeation chromatography method in this invention uses TLCgel Super HZM-H, TSKgel Super HZ4000, TSKgel Super HZ200 (made by Tosoh Corporation) as a column using HLC-8020GPC (made by Tosoh Corporation). , 4.6 mm ID x 15 cm), and THF (tetrahydrofuran) is preferably used as the eluent.

[Synthesis method]

Although various methods are known for the synthesis | combining method of the above-mentioned polymers p1-2 and 4, For example, the radically polymerizable monomer mixture containing the radically polymerizable monomer used in order to form each structural unit mentioned above is radical in an organic solvent. It can synthesize | combine by superposing | polymerizing using a polymerization initiator. Moreover, it can also synthesize | combine by what is called a polymer reaction. Moreover, about polyimide precursor p3, it can synthesize | combine by the method of Unexamined-Japanese-Patent No. 2014-66764, for example.

[Organic solvent]

It is preferable that a specific orientation film material contains the organic solvent other than the component mentioned above.

As the organic solvent, a known organic solvent can be used, and ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, and propylene glycol monoalkyl ethers , Propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl Examples of ethers, butylene glycol diacetates, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, alcohols, esters, ketones, amides, lactones, and the like Can be. As a specific example of these organic solvents, Paragraph 0062 of Unexamined-Japanese-Patent No. 2009-098616 can be referred.

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

From the viewpoint of applicability, the boiling point of the organic solvent is preferably 100 ° C to 300 ° C, more preferably 120 ° C to 250 ° C.

The organic solvent which can be used for this invention can use together single 1 type or 2 types or more. It is also preferable to use solvents with different boiling points in combination.

It is preferable that it is 100-3,000 mass parts per 100 mass parts of total solids of a composition from a viewpoint of adjusting content to the viscosity suitable for application | coating in the case of containing an organic solvent, It is more preferable that it is 200-2,000 mass parts, 250-1,000 It is more preferable that it is a mass part.

As solid content concentration of a composition, 3-50 mass% is preferable, and it is more preferable that it is 20-40 mass%.

[Other components]

As the specific alignment film material, an antioxidant, an ultraviolet absorber, a thickener, a surfactant, an organic or inorganic precipitation inhibitor, an adhesion improving agent, a tea, and the like can be added, individually or individually.

<Surfactant>

As the surfactant, any of anionic, cationic, nonionic, and amphoteric compounds can be used, but preferred surfactants are nonionic surfactants. As surfactant, a nonionic surfactant is preferable and a fluorine-type surfactant is more preferable.

As surfactant which can be used for a 1st aspect, For example, Megapak F142D, copper F172, copper F173, copper F176, copper F177, copper F183, copper F479, copper F482, copper F554, copper F780, copper which is a commercial item F781, copper F781-F, copper R30, copper R08, copper F-472SF, copper BL20, copper R-61, copper R-90 (manufactured by DIC Corporation), fluoride FC-135, copper FC-170C, copper FC-430, copper FC-431, Novec FC-4430 (product made by Sumitomo 3M Co., Ltd.), Asahi Guard AG7105, 7000, 950, 7600, Supron S-112, copper S-113, copper S-131, copper S -141, East S-145, East S-382, East SC-101, East SC-102, East SC-103, East SC-104, East SC-105, East SC-106 (made by Asahi Glass Co., Ltd.) F-top EF351, 352, 801, 802, 802 (made by Mitsubishi Material Denshi Kasei Co., Ltd.), and Pgentgent 250 (made by Neos Co., Ltd.) are mentioned. Moreover, in addition to the above, KP (made by Shin-Etsu Kagaku Kogyo Co., Ltd.), polyflo (made by Kyoeisha Kagaku Co., Ltd.), F-top (made by Mitsubishi Material Denshi Kasei Co., Ltd.), mega pack (DIC ( Co., Ltd.), a fluoride (made by Sumitomo 3M Co., Ltd.), Asahi Guard, a suffron (made by Asahi Glass Co., Ltd.), PolyFox (made by OMNOVA), etc. are mentioned.

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

As for content in the case of containing surfactant, 0.001-5.0 mass parts is preferable with respect to 100 mass parts in the total solid of a composition, and its 0.01-2.0 mass part is more preferable.

One type of surfactant may be included and may be included two or more types. When it contains two or more types, it is preferable that the total amount becomes said range.

<Adhesive improver>

An alkoxysilane compound etc. are mentioned as an adhesion improving agent.

The alkoxysilane compound is a compound which improves the adhesion between the inorganic material serving as the base material, for example, silicon compounds such as silicon, silicon oxide, silicon nitride, and metals such as gold, copper, molybdenum, titanium, aluminum and the insulating film. It is preferable.

As a specific example of an adhesion | attachment improving agent, (gamma) -aminopropyl trimethoxysilane, (gamma) -aminopropyl triethoxysilane, (gamma)-glycidoxy propyl trimethoxysilane, (gamma)-glycidoxy propyl trie Oxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-chloropropyltrimethoxysilane Phosphorus, γ-mercaptopropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane and the like. Among these, γ-glycidoxy propyl trimethoxy silane and γ-methacryloxypropyl trimethoxy silane are preferable, and γ-glycidoxy propyl trimethoxy silane is more preferable. These can be used individually by 1 type or in combination of 2 or more types.

It is preferable that it is 0.001-15 mass parts with respect to 100 mass parts of total solid components of a composition, and, as for content of an adhesive improving agent, it is more preferable that it is 0.005-10 mass parts. One type of adhesion improving agent may be used and may be used two or more types. When using two or more types, it is preferable that the total amount becomes said range.

Example

Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In addition, when it describes simply as "part" about the quantity of each component, the "mass part" is intended.

Synthesis of Monomer

Each monomer was synthesize | combined as follows.

[Synthesis of Monomer (monomer a-1) Having a Photoalignment Group]

Methyl trans-4-hydroxycinnamate (manufactured by Tokyo Kasei Kogyo Co., Ltd., 12.5 g, 0.07 mol) and triethylamine (manufactured by Wako Junyaku Kogyo Co., Ltd., 7.79 g, 0.07 mol) are tetrahydrofuran (hereinafter referred to as Dissolved in 100 mL, and cooled to 0 ° C., methacrylic acid chloride (produced by Tokyo Kasei Kogyo Co., Ltd., 7.33 g, 0.07 mol) was slowly added dropwise.

Subsequently, 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 the photoalignable group. The structure was confirmed by NMR.

[Synthesis of monomer (monomer a-2) having photoalignment group]

Ethyl 4-hydroxy-3-methoxycinnamate (made by Tokyo Kasei Kogyo Co., Ltd., 22.2 g, 0.1 mol) was dissolved in 150 mL of dimethylacetamide, and 30 g of potassium carbonate (made by Wako Junyaku Kogyo Co., Ltd.) , 0.22 mol) was added to raise the temperature to 90 ° C.

Then, 4-chlorobutanol (made by Wako Junyaku Kogyo Co., Ltd., 21.6g, 0.2mol) was dripped, and it stirred for 3 hours.

Thereafter, the reaction solution was poured into 1 L of water, neutralized with 2N (normative) HCl, extracted with 700 mL of ethyl acetate, washed with saturated brine, and concentrated.

Subsequently, silica gel column chromatography fractionated and 23g of intermediate compounds were obtained.

15 g (0.05 mol) of this intermediate compound and triethylamine (5.6 g, 0.056 mol by Wako Junyaku Kogyo Co., Ltd.) were dissolved in 100 mL of THF, and cooled to 0 degreeC.

Then, methacrylic acid chloride (5.8 g, 0.056 mol of Tokyo Kasei Kogyo Co., Ltd. product) was dripped, and after stirring for 3 hours, the reaction solution was poured into 500 g of water, and extracted with ethyl acetate, and it concentrated.

Subsequently, silica gel column chromatography fractionated and obtained 20g of monomer a-2 which has a spacer cinnamate as a photo-alignment group.

[Synthesis of Monomer (monomer a-3) Having a Photoalignment Group]

Hydroquinone (63.8 g, 0.58 mol) manufactured by Wako Junyaku Kogyo Co., Ltd. was dissolved in 500 mL of dimethylacetamide, and potassium carbonate (40 g, 0.29 mol) was added to Waco Junyaku Kogyo Co., Ltd. The temperature was raised to 90 ° C.

Subsequently, 4-chlorobutyl methacrylic acid (made by Wako Junyaku Kogyo Co., Ltd., 25.6 g, 0.145 mol) was dripped, and it stirred for 3 hours.

Thereafter, the reaction solution was poured into 1 L of water, neutralized with 2NHCl, extracted with 700 mL of ethyl acetate, washed with saturated brine, and concentrated. The crude crystals were taken out and separated by silica gel column chromatography to obtain 18 g of intermediate compound.

18 g of this intermediate compound and triethylamine (7.79 g, 0.07 mol of Wako Junyaku Kogyo Co., Ltd.) were dissolved in 100 mL of THF and cooled to 0 ° C.

Then, cinnamoyl chloride (13.1 g, 0.07 mol of Tokyo Kasei Kogyo Co., Ltd. product) was dripped, and after stirring for 3 hours, the reaction solution was poured into 500 g of water, and extracted with ethyl acetate, and it concentrated.

Subsequently, silica gel column chromatography fractionated and obtained 22g of monomer a-3 which has a chalcone group as a photo-alignment group.

[Synthesis of monomer (monomer e-1) having an acid group protected by an acid-decomposable group]

Methacrylic acid (Wako Junyaku Kogyo Co., Ltd. make, 86 g, 1 mol) was cooled to 15 degreeC, and camphor sulfonic acid (Tokyo Kasei Kogyo Co., Ltd. make, 4.6 g, 0.02 mol) was added.

Next, 2,3-dihydrofuran (71 g, 1 mol, 1.0 equivalent) of Kawaken Fine Chemical Co., Ltd. was dripped at the reaction solution.

After stirring for 1 hour, saturated sodium hydrogen carbonate (500 mL) was added, followed by extraction with ethyl acetate (500 mL).

Subsequently, after drying with magnesium sulfate, the insolubles were concentrated under reduced pressure at 40 ° C. or lower after filtration, and the yellow oily substance was distilled under reduced pressure to give a boiling point (bp.) 54 as monomer e-1. 125g of methacrylic acid tetrahydro-2H-furan-2-yl of -56 degreeC / 3.5mmHg oil fraction was obtained as a colorless oily thing (yield 80%).

[Synthesis of Polymer]

Each polymer was synthesize | combined 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 degreeC under nitrogen stream. Synthesized monomer a-1 (11.1 g, 45 mol%), hexafluoroisopropyl methacrylate (hereinafter abbreviated as "HFIP") (manufactured by Tokyo Kasei Kogyo Co., Ltd., 3.5 g, 15 mol%), methacryl Acid (hereinafter abbreviated as "MAA") (made by Wako Junyaku Kogyo Co., Ltd., 1.7 g, 20 mol%), glycidyl methacrylate (hereinafter abbreviated as "GMA") (Wakko Junyaku High School ( A mixed solution of Co., Ltd., 2.8 g, 20 mol%), 497 mg (2 mol%) of a radical polymerization initiator (V-65, manufactured by Wako Junyaku Kogyo Co., Ltd.), and PGMEA (30 g) were added dropwise for 2 hours. After completion of the dropwise addition, the mixture was further reacted at 70 ° C for 4 hours to obtain a PGMEA solution (solid content concentration: 27%) of the polymer (P1).

[Synthesis of Polymers (P2 to P7)]

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

<Abbreviation>

A-1 to a-3: monomers a-1 to a-3 synthesized as described above

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

6FM: trifluoroethyl methacrylate (manufactured by Osaka Yuki Chemical Co., Ltd.)

MAA: Methacrylic acid (made by Wako Junyaku Kogyo Co., Ltd.)

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

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

E-1: monomer e-1 synthesized as described above

MMA: Methyl methacrylate (made by Wako Junyaku Kogyo Co., Ltd.)

V-65: radical polymerization initiator (made by Wako Junyaku Kogyo Co., Ltd.)

V-601: radical polymerization initiator (made by Wako Junyaku Kogyo Co., Ltd.)

HS-EDM: diethylene glycol methyl ethyl ether (manufactured by Toho Kagaku Kogyo Co., Ltd.)

PGMEA: methoxy propylene glycol acetate (manufactured by Daicel Co., Ltd.)

TABLE 1

[Synthesis of Polymer (P8)]

PGMEA (238g) was heated and stirred at 90 degreeC under nitrogen stream.

Next, methacrylic acid tetrahydro-2H-furan-2-yl synthesized as monomer e-1 (240 g (corresponding to 61.1 mol% of the total monomers)) and MAA (50.4 g (corresponding to 17.6 mol% of the total monomers)) ), MMA (27.9 g (corresponding to 21.3 mol% of the total monomers)), a mixed solution of radical polymerization initiator V-601 (14.7 g), and PGMEA (238 g) were added dropwise over 2 hours, and further at 90 ° C. for 2 hours. It was made to react and PGMEA (42g) was added after cooling, and the solution (solid content concentration: 38%) of the polymer (P8) was obtained. The molecular weight was 15000.

Synthesis of Polymer (P9)

HS-EDM (145g) was heated and stirred at 70 degreeC under 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) ( A mixed solution of 3.87 g (1.2 mol%), radical polymerization initiator V-65 (20.8 g (5.6 mol% monomer amount)), and HS-EDM (145 g) were added dropwise for 2 hours. After completion of the dropwise addition, the solution (solid content concentration: 35%) of the polymer (P9) was obtained by reacting at 70 ° C for 4 hours. The molecular weight was 10000.

Synthesis of Polymer (P10)

HS-EDM (82 parts) was heated and stirred at 90 degreeC under nitrogen stream.

Subsequently, methacrylic acid tetrahydro-2H-furan-2-yl synthesized as monomer e-1 (43 parts (corresponding to 40.5 mol% of the total monomers)) and OXE-30 (48 parts (37.5 mol% of the total monomers) Equivalent)), MAA (6 parts (corresponding to 9.5 mol% in total monomers)), hydroxyethyl methacrylate (manufactured by Wako Junyaku Kogyo Co., Ltd., 11 parts (corresponding to 12.5 mol% in total monomers)) , The mixed solution of the radical polymerization initiator V-601 (4.3 parts) and PGMEA (82 parts) was added dropwise for 2 hours and further reacted at 90 ° C. for 2 hours to give a solution of the polymer (P10) (solid content concentration: 40%) Got. The molecular weight was 15000.

Synthesis of Polymer (P11)

With reference to WO2013 / 018904, the following polymer (P11) was synthesized.

Specifically, 1,96,34 g of 1,2,3,4-cyclobutane tetracarboxylic dianhydride (1.00 mol manufactured by Tokyo Kasei Co., Ltd.) is 2394 g of NMP (N-methylpyrrolidone) manufactured by Wako Junyaku Kogyo Co., Ltd. ) Dissolved in the form of a slurry, 101.11 g of p-phenylenediamine (0.935 mol, manufactured by Tokyo Kasei Co., Ltd.) was added, and further NMP was added so that the solid content concentration was 8% by weight, and stirred at room temperature for 24 hours, The solution (solid content concentration 8%) of the polymer (P11) of polyamic acid was obtained.

Synthesis of Polymer (P12)

With respect to 100 g of the solution of the polymer (P10) obtained above, phthalic anhydride 1.0 was added as a terminal sealing and stirred for 24 hours. 0.1 g of camphorsulfonic acid (manufactured by Wako Junyaku Co., Ltd.) was added to the solution, 30 g of 2,3-dihydrofuran (manufactured by Kawaken Fine Chemicals Co., Ltd.) was added, and the carboxylic acid was monitored by NMR (nuclear magnetic resonance method). When the protection rate is 65%, 2.0 g of pyridine (manufactured by Wako Junyaku Co., Ltd.) is added to stop the reaction, and further adjusted to a solid content concentration of 5% by NMP to give a solution of the polymer of acetal protection of polyamic acid (P12). (Solid content concentration 5%) was obtained.

[Preparation of Photosensitive Resin Composition]

Each photosensitive resin composition (alignment film material) was prepared as follows. Since M1-M12 all have photopatterning property, photoalignment property, and contain a thermosetting component, it corresponds to the specific orientation film material mentioned above.

[Preparation of Photosensitive Resin Composition (M1)]

55 parts of polymers (P6) in terms of solid content, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate as a polymerizable compound (ethylenically unsaturated compound) (KAYARAD® DPHA, Nippon Kayakusa ( Note) agent) 45 mass parts, ethanone-1- {9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl} -1- (O-acetyl oxime) (yield) as a photoinitiator After adding propylene glycol monomethyl ether acetate (PGMEA, Daicel Kagaku) so that 2.5 mass parts and 30 mass% of solid content concentrations may respectively be made into cure Cure OXE-02, BASF company, and 0.5 micrometer of pore diameters The photosensitive resin composition M1 was obtained by filtering by the Millipore filter.

[Preparation of Photosensitive Resin Composition (M2)]

55 parts of polymers (P11) in terms of solid content, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate as a polymerizable compound (ethylenically unsaturated compound) (KAYARAD® DPHA, Nippon Kayakusa ( Note) agent) 45 mass parts, ethanone-1- {9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl} -1- (O-acetyl oxime) (yield) as a photoinitiator After adding propylene glycol monomethyl ether acetate (PGMEA, Daicel Kagaku) so that 2.5 mass parts and 30 mass% of solid content concentrations may respectively be made into cure Cure OXE-02, BASF company, and 0.5 micrometer of pore diameters Photosensitive resin composition M2 was obtained by filtering by a Millipore filter.

[Preparation of Photosensitive Resin Composition (M3)]

75 parts of polymers (P6) in terms of solid content, 25 parts of quinonediazide compound (TAS-200, Toyo Kosei Kogyo Co., Ltd.) (NQD), and a perfluoroalkyl group-containing surfactant (F-554, manufactured by DIC Corporation) 0.02 part and a silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) are made into 2 parts as a close_contact | adherence improving agent, and it mixes diethylene glycol methyl ethyl ether (HS- so that the total solid concentration may be 11%). EDM and the Toho Chemical Co., Ltd. product) were further added, and photosensitive resin composition M3 was obtained.

[Preparation of Photosensitive Resin Composition (M4)]

75 parts of polymers (P7) in terms of solid content, 25 parts of quinonediazide compounds (TAS-200, Toyo Kosei Kogyo Co., Ltd.) (NQD), and a perfluoroalkyl group-containing surfactant (F-554, manufactured by DIC Corporation) 0.02 parts and a silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) are made into 2 parts as an adhesion improving agent, HS-EDM is further added so that the total solid content may be 11%, and the photosensitive resin composition M4 was obtained.

[Preparation of Photosensitive Resin Composition (M5)]

75 parts of polymers (P11) in terms of solid content, 25 parts of quinonediazide compound (TAS-200, Toyo Kosei Kogyo Co., Ltd.) (NQD), and a perfluoroalkyl group-containing surfactant (F-554, manufactured by DIC Corporation) 0.02 parts and a silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) are made into 2 parts as an adhesion improving agent, HS-EDM is further added so that the total solid content may be 11%, and the photosensitive resin composition M5 was obtained.

[Preparation of Photosensitive Resin Composition (M6)]

5 parts of polymer (P1) in terms of solids, 45 parts of polymer (P8) in terms of solids, 50 parts of polymer (P9) in terms of solids, 3 parts of PAG103 (manufactured by BASF) as a photoacid generator, 0.02 parts of phenylimidazole, 0.02 parts of F-554 (manufactured by DIC Corporation) as a perfluoroalkyl group-containing surfactant, and 2 parts of silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) as an adhesion improving agent. It mixed, HS-EDM was further added so that the total solid content concentration might be 11%, and the photosensitive resin composition M6 was obtained.

[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, 3 parts of PAG103 (manufactured by BASF) as a photoacid generator, 0.02 parts of phenylimidazole, 0.02 parts of F-554 (manufactured by DIC Corporation) as a perfluoroalkyl group-containing surfactant, and 2 parts of silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) as an adhesion improving agent. It mixed, HS-EDM was further added so that the total solid content concentration might be 11%, and the photosensitive resin composition M7 was obtained.

[Preparation of Photosensitive Resin Composition (M8)]

5 parts of polymer (P3) in terms of solids, 45 parts of polymer (P8) in terms of solids, 50 parts of polymer (P9) in terms of solids, 3 parts of PAG103 (manufactured by BASF) as a photoacid generator, 0.02 parts of phenylimidazole, 0.02 parts of F-554 (manufactured by DIC Corporation) as a perfluoroalkyl group-containing surfactant, and 2 parts of silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) as an adhesion improving agent. It mixed, HS-EDM was further added so that the total solid content concentration might be 11%, and the photosensitive resin composition M8 was obtained.

[Preparation of Photosensitive Resin Composition (M9)]

5 parts of polymer (P1) in terms of solids, 95 parts of polymer (P10) in terms of solids, 3 parts of PAG103 (manufactured by BASF) as a photoacid generator, 0.02 parts of triphenylimidazole as a difference, perfluoro 0.02 parts of F-554 (manufactured by DIC Corporation) as the alkyl group-containing surfactant and 2 parts of the silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) as the adhesion improving agent were mixed, and the total solid concentration was 11%. HS-EDM was further added so that the photosensitive resin composition M9 might be obtained.

[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 parts of triphenylimidazole as a difference, and F-554 (manufactured by DIC Corporation) as a surfactant containing a perfluoroalkyl group. ) Is mixed with 0.02 parts of silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) as two parts, and additionally HS-EDM is added so that the total solid concentration becomes 11%. Resin composition M10 was obtained.

[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 parts of triphenylimidazole as a difference, and F-554 (manufactured by DIC Corporation) as a perfluoroalkyl group-containing surfactant. ) Is mixed with 0.02 parts of silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) as two parts, and additionally HS-EDM is added so that the total solid concentration becomes 11%. Resin composition M11 was obtained.

[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 parts of triphenylimidazole as a difference, and F-554 (manufactured by DIC Corporation) as a perfluoroalkyl group-containing surfactant. ) Was mixed with 0.02 parts of silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) as 6 parts, and additionally HS-EDM was added so that the total solid concentration was 9%. Resin composition M12 was obtained.

In following Table 2, a main component and a mass part are collectively shown about each photosensitive resin composition (alignment film material). Moreover, about each photosensitive resin composition (alignment film material), the component or structural unit which contributes to photopatterning property, photoalignment property, and thermosetting property is shown. Moreover, the structural unit which has a locality group is shown.

[Manufacture of Liquid Crystal Display Panel]

By the process shown in FIGS. 1-10, the liquid crystal display panel was produced (Examples 1-12).

Hereinafter, each process is demonstrated.

[Step (1): Substrate Preparation Step]

<Step (1-1): Coating Film Formation Step>

The photosensitive resin composition (alignment film material) prepared as mentioned above was apply | coated on a pair of board | substrate (array substrate, a color filter substrate), and the coating film (thickness: 0.5 micrometer) was formed. The array substrate and the color filter substrate are as follows.

(Array substrate)

On a glass substrate, an active element formed by a known method (such as a semiconductor layer, a gate electrode, a gate insulating film, a source-, etc.) by repeating etching according to a photolithography method, or the like, by repeating ordinary semiconductor film film formation, known insulating layer formation, or the like. A substrate having a drain electrode, a video signal line, a scan signal line, and the like) was prepared.

Next, the interlayer insulation film was optically patterned, and the transparent conductive layer which consists of ITO (indium tin oxide) was formed on the insulation film using the sputtering method. Next, the transparent conductive layer was etched using the photolithography method to form a solid common electrode on the insulating film. After that, an inorganic insulating film was formed by sputtering the SiN film, and a comb-shaped transparent electrode was further provided. In this way, an array substrate was obtained.

(Color filter board)

The color filter substrate was obtained by a well-known method. In this color filter substrate, a fine color pattern of three colors of red, green and blue and a black matrix are arranged in a lattice shape on a transparent substrate.

<Step (1-2): Removal Step>

Then, the obtained coating film was exposed and developed, and the coating film formed in the sealing material formation area among the coating films was removed. Specifically, exposure was performed by ghi-ray mixed light (wavelength 365-405 nm), and alkali image development was performed.

<Step (1-3): Thermosetting Step>

Moreover, the coating film remaining after the removal process was thermosetted (230 degreeC / 30 minutes). Thus, the thermosetting film (thickness: 0.5 micrometer) was formed in the area | regions other than the sealing material formation area of a pair of board | substrate (array substrate, a color filter substrate).

<Step (1-4): Photoalignment Treatment Step>

Moreover, the photo-alignment process was performed about the obtained thermosetting film. Specifically, polarized light exposure of polarized ultraviolet light 500 J / m < ² > containing 254-313 nm bright line was performed using the Hg-Xe lamp and the Glen Taylor prism. In this way, an optical alignment film (thickness: 0.5 μm) was formed in a region other than the sealant formation region of the pair of substrates (array substrate, color filter substrate).

[Step (2): Seal Material Formation Step]

The 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 curing acrylic resin and thermosetting epoxy resin is applied to the sealing material forming region of the array substrate on which the photo-alignment film is formed. Including).

[Step (3): Bonding Step, and Step (4): Liquid Crystal Layer Forming Step]

The sealing material of the array substrate obtained at the process (3) was bonded together with a pair of board | substrate with the sealing material according to the sealing material formation area of the color filter substrate obtained at the process (1). At that time, the composition for liquid crystal layer formation was sandwiched between a pair of board | substrates, and the liquid crystal layer (made of nematic liquid crystal and orientating parallel to a board | substrate surface) was formed in the space enclosed by a pair of board | substrate and sealing material.

Thus, the liquid crystal display panel (color liquid crystal display element) was manufactured. The obtained liquid crystal display panel showed the outstanding operating characteristic and display characteristic.

In any of the examples, since there is no step of etching after forming a resist mask using a separate resist liquid as in the method of JP-A-2015-36721, the load on the process surface is small and convenient.

[evaluation]

[Softening Temperature Tm of Coating Film]

Softening temperature Tm was measured using the indentation hardness apparatus (Micro Materials, Nano Indenter apparatus, Nano test bandage). Specifically, it measured as follows.

The photosensitive resin composition (alignment film material) used in each Example was apply | coated to a silicon wafer, and the coating film of 4.0 micrometers was produced. The obtained coating film was set to the said indentation hardness apparatus, the load (100 mN) was applied, the temperature was raised from 90 degreeC to 350 degreeC by 5 degreeC, and the displacement in each temperature was investigated. And the temperature which the displacement became 0.4 micrometer or more was made into softening temperature Tm.

[Cure Start Temperature Tc of Thermosetting Component in Coating Film]

The hardening start temperature Tc of the thermosetting component was measured using RT-IR (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 apply | coated to a silicon wafer, and the coating film of 2.0 micrometers was produced. About the obtained coating film, IR (infrared spectroscopy) was measured, increasing by 5 degreeC for 1 minute. Changes were observed by tracing between 2500 and 3000 cm ^-1 . In addition, since the hydroxyl group generate | occur | produces by reaction with an acidic radical, the crosslinkable group of epoxy or oxetane can track reaction (M1, 3, 4, 6-11). The change from polyamic acid (polyimide precursor), which is a precursor, to polyimide can track the reaction because hydroxyl groups are lost (M2, 5, 12).

[Angle (d1) of Coating Film]

The photosensitive resin composition (alignment film material) used in each Example was apply | coated on the glass substrate, and the coating film (thickness: 4.0 micrometers) was formed. Subsequently, exposure was performed with the photomask of a line & space of 5 micrometers using the PLA (trademark) -501F exposure machine (ultra high pressure mercury lamp) by a Canon Corporation. And image development was performed at 25 degreeC / 60 second by the 0.4 mass% or 2.38 mass% tetramethylammonium hydroxide aqueous solution. Rinse was performed with ion-exchange water, and the patterned coating film was obtained. SEM (scanning electron microscope) observation was performed about the edge part of the obtained pattern shape coating film, and the angle corresponded to the angle d1 mentioned above. The results are shown in Table 2. Here, "> 100 degrees" means larger than 100 degrees.

[Angle of thermal curing film d2]

After obtaining a pattern-like coating film by the same method as the measurement of the angle d1 of the coating film mentioned above, a post-baking is performed in 230 degreeC / 60-minute hardening time, and a pattern-shaped thermosetting film (film thickness about 3.0 μm). SEM observation was performed with respect to the edge part of the obtained thermosetting film | membrane, and the angle corresponded to the angle d2 mentioned above. The results are shown in Table 2.

TABLE 2

From the contrast of Examples 1-12, in Examples 3-12 whose specific orientation film material is positive type, it turns out that the angle d2 of a thermosetting film becomes 30-90 degree, and can obtain a narrower frame liquid crystal display panel. there was. Especially, in Examples 6-12 which a specific alignment film material has an acid-decomposable group, it turned out that the angle d2 of a thermosetting film became 50-90 degree, and the narrower frame liquid crystal display panel was obtained. Especially, in Examples 6-8 and 10 which satisfy | fills Tc <= Tm + 20, it turned out that the angle d2 of a thermosetting film became 70-90 degree, and the liquid crystal display panel of especially narrow frame was obtained.

From the contrast of Examples 1-12, in Examples 6-12 whose angle d1 of a coating film is 70-90 degree, the angle d2 of a thermosetting film becomes 60-90 degree, and can obtain a liquid crystal display panel of a narrower frame. I could see.

From the contrast of Examples 3 to 5 (the embodiment in which the alignment film material contains quinonediazide), in Example 3, in which Tc ≦ Tm + 20 is satisfied, the angle d2 of the thermosetting film becomes 50 to 90 degrees, which is narrower. It turned out that the liquid crystal display panel of a frame can be obtained.

a liquid crystal layer forming area
b sealing material forming area
c end area
10 pairs of substrates
12 A pair of photo-alignment films
20 coat
22 Coating Film Left After Removal Process
The coating film formed in the liquid-crystal layer formation area | region a of the 22a coating film 22
Coating film formed in the end area | region c of the 22c coating film 22
Side cross section which is in contact with the sealing material forming region b of the 22p coating film 22a
Surface in contact with the substrate 10 of the 22q coating film 22a
d1 angle of side face 22p and face 22q
24 thermosets
The thermosetting film formed in the liquid crystal layer forming region a of the 24a thermosetting film 24.
The thermosetting film formed in the end region c of the 24c thermosetting film 24.
Side cross section which contacts the sealing material formation area | region b of the 24p thermosetting film 24a
Surface in contact with the substrate 10 of the 24q thermosetting film 24a
d2 side cross section (24p) and face (24q) angle
26 Photoalignment Film
The photoalignment film formed in the liquid crystal layer formation region a of the 26a photoalignment film 26
The photoalignment film formed in the end region c of the 26c photoalignment film 26.
30 days
40 liquid crystal layer
100 liquid crystal display panel

Claims (7)

A substrate preparation step of preparing a pair of substrates on which a photo-alignment film is formed in regions other than the seal material formation region,
A sealing material forming step of forming a sealing material in the sealing material forming region of any one of the pair of substrates;
A bonding step of bonding the pair of substrates together with the sealing material;
As a manufacturing method of the liquid crystal display panel containing the liquid crystal layer formation process of forming a liquid crystal layer in the space enclosed by the said pair of board | substrates and the said sealing material,
The substrate preparation process,
A coating film forming step of forming a coating film made of an alignment film material having a photopatterning property and a photo-alignment property and containing a thermosetting component on a pair of substrates having a seal material forming region;
A removal step of exposing and developing the coating film to remove the coating film formed in the seal material forming region of the coating film;
A thermosetting step of thermally curing the coating film remaining after the removing step to form a thermosetting film in a region other than the sealing material forming region of the pair of substrates;
And a photoalignment treatment step of subjecting the thermosetting film to a photoalignment process to form a photoalignment film in a region other than the sealant formation region of the pair of substrates. The method according to claim 1,
Manufacturing of the liquid crystal display panel whose angle between the side surface of the thermosetting film formed in the liquid-crystal layer formation area | region of the said thermosetting film in contact with the said sealing material formation area | region, and the surface which contact | connects the board | substrate of the said thermosetting film is 30-90 degree. Way. The method according to claim 1 or 2,
The said orientation film material is a manufacturing method of the liquid crystal display panel of the positive type in which the exposed part of the coating film formed is melt | dissolved. The method according to claim 1 or 2,
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 which said Tm and Tc satisfy following formula (1) and (2).
Tm = 80-200 (1)
Tc≤Tm + 20 (2) The method according to claim 1 or 2,
The method of manufacturing a liquid crystal display panel, wherein an angle between a 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 among the coating films remaining after the removing step. The method according to claim 1 or 2,
The manufacturing method of the liquid crystal display panel in which the wavelength of the light used by the said exposure is longer than the wavelength of the light used by the said photoalignment process. The method according to claim 1 or 2,
The manufacturing method of the liquid crystal display panel whose light used by the said photo-alignment process is linearly polarized light.

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