JP2017198740A - Liquid crystal display device and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal display device suppressing local reduction in a voltage retention rate and having excellent reliability while achieving a narrow frame.SOLUTION: A liquid crystal display device 100 includes a first glass substrate 101 and a second glass substrate 103 in which peripheral edges are bonded by a sealing material 105, and a liquid crystal layer 106 between the substrates. The liquid crystal display device 100 includes: a liquid crystal alignment film 109, 111 on at least one substrate, formed in a region inside the sealing material 105; and a blocking material 110 disposed on the substrate where the liquid crystal alignment film 109, 111 is formed, between an end edge of the substrate and an end edge of the liquid crystal alignment film 109, 111 in such a manner that the sealing material 105 and the liquid crystal alignment film 109, 111 are in a non-contact state from each other. The blocking material 110 is formed by using a silicon-based resin or a fluorine-based resin having a fluorine-containing group having 1 to 40 carbon atoms in a side chain.SELECTED DRAWING: Figure 2

Description

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

  In general, a liquid crystal display device has a peripheral portion of a pair of substrates bonded with a sealing material, a liquid crystal layer sandwiched in a space surrounded by the pair of substrates and the sealing material, and a liquid crystal layer on the liquid crystal layer side substrate. The structure has an alignment film. In addition, the liquid crystal layer is generally sensitive to moisture, and there is a concern that display quality such as display unevenness may be deteriorated when moisture enters the liquid crystal display device. Therefore, the sealing material portion needs to have a structure with high sealing performance.

  In recent years, in a touch panel type display panel typified by a smartphone or a tablet PC, attempts have been made to narrow the frame in order to make the movable area of the touch panel wider and to make the panel compact. For example, in Patent Document 1, a liquid repellent film is formed between an end portion of a liquid crystal alignment film formed on a substrate and a region where the seal material is formed, thereby bringing the alignment film and the seal material closer to each other. It is disclosed that they can be arranged.

JP 2011-186026 A

  When the sealing performance of the sealing material portion is inferior in the liquid crystal display device, there is a concern that external moisture may enter the liquid crystal display device and cause a local decrease in voltage holding ratio. Further, when narrowing the frame of the liquid crystal display device, it is important not to lower the reliability (for example, reliability against heat) of the liquid crystal display device. Particularly, in recent years, with the diversification of liquid crystal display devices, the liquid crystal display devices are expected to be used in harsh environments such as high temperatures as compared with conventional ones. In addition, high-definition liquid crystal televisions are mainly used, and the spread of small display terminals is progressing, and the demand for reliability of liquid crystal display devices is further increased.

  The present invention has been made in view of the above problems, and provides a liquid crystal display device that is excellent in reliability while suppressing a decrease in local voltage holding ratio while achieving a narrow frame. Objective.

  The present invention employs the following means in order to solve the above problems.

  The first configuration is a liquid crystal display in which the peripheral portions of the first substrate and the second substrate arranged to face each other are bonded together with a sealing material, and a liquid crystal layer is provided between the first substrate and the second substrate. An apparatus comprising: a liquid crystal alignment film formed in a region inside the sealing material on at least one of the first substrate and the second substrate; and a substrate on which the liquid crystal alignment film is formed. A blocking material disposed between the edge of the substrate and the edge of the liquid crystal alignment film so that the sealing material and the liquid crystal alignment film are not in contact with each other, and the blocking material Is formed using a silicon-based resin or a fluorine-based resin having a fluorine-containing group having 1 to 40 carbon atoms in the side chain.

  In the first configuration, the blocking material for suppressing contact between the liquid crystal alignment film and the sealing material is formed using a silicon-based resin or a fluorine-based resin having a fluorine-containing group having 1 to 40 carbon atoms in the side chain. It was set as the structure to do. By adopting such a configuration, it is possible to obtain a liquid crystal display device that is less likely to reduce the local voltage holding ratio of the liquid crystal display device and is excellent in reliability (particularly thermal reliability) while narrowing the frame. .

  The second configuration is characterized in that the silicon-based resin is at least one of polysiloxane and polysilazane. A third configuration is characterized in that the fluororesin is a resin having a fluoroalkyl group having 1 to 12 carbon atoms in the side chain. According to such a configuration, it is possible to form a blocking material having high liquid repellency with respect to the liquid crystal aligning agent and excellent adhesion to the substrate. Therefore, when applying the polymer composition for forming the liquid crystal alignment film, the wetting and spreading of the polymer composition can be effectively controlled. Further, even when a positional shift occurs during application, it is possible to further suppress the liquid crystal alignment film from being formed in the region of the sealing material due to the liquid repellency of the blocking material.

  In a fourth configuration, the blocking material includes a first blocking material formed on the first substrate, and a second blocking material formed on the second substrate, and the first blocking material and the Between the 2nd blocking material, the said sealing material is interposed in the state which contacted the said 1st blocking material and the said 2nd blocking material, It is characterized by the above-mentioned. According to such a configuration, the first substrate and the second substrate can be bonded to each other by the laminated structure including the first blocking material, the sealing material, and the second blocking material, and the region for forming the sealing material on the substrate is narrowed. It is possible to further narrow the frame.

  The fifth configuration is the above-described fourth configuration, wherein the contact surface between the first blocking material and the sealing material and the contact surface between the second blocking material and the sealing material have uneven patterns having different film thicknesses. It is characterized by that. According to this configuration, the contact area between the blocking material and the sealing material is increased, so that the adhesion between them can be improved. Thereby, the penetration | invasion of the water | moisture content from the interface of a blocking material and a sealing material can be suppressed more suitably.

  A sixth configuration relates to a method of manufacturing a liquid crystal display device, and a step of forming a blocking material on at least one of the first substrate and the second substrate so as to surround a display region in a central portion of the substrate; A step of forming a liquid crystal alignment film in the display region after the formation of the blocking material; and a step of forming the sealing material on the outer side of the display region after the formation of the liquid crystal alignment film. And the step of bonding the two substrates together, wherein the blocking material is formed using a silicon-based resin or a fluorine-based resin having a fluorine-containing group having 1 to 40 carbon atoms in the side chain. .

  In the sixth configuration, the blocking material for suppressing contact between the liquid crystal alignment film and the sealing material is formed using a silicon-based resin or a fluorine-based resin having a fluorine-containing group having 1 to 40 carbon atoms in the side chain. As a result, it is possible to obtain a liquid crystal display device that is less likely to cause a local voltage holding ratio of the liquid crystal display device and is excellent in thermal reliability while narrowing the frame.

  A seventh configuration is characterized in that, in the sixth configuration, the liquid crystal alignment film is formed by subjecting a coating film formed using a liquid crystal aligning agent to a photo-alignment treatment. According to this configuration, it is possible to obtain a liquid crystal display device with less alignment unevenness in the periphery of the sealing material.

  The eighth configuration is characterized in that, in the sixth configuration, the blocking material is formed by a photolithography process. According to the photolithography process, an alignment accuracy of 1 μm or less can be ensured. Therefore, the width of the blocking material can be designed narrower than when the blocking material is formed by, for example, a dispenser method or a screen printing method, which is advantageous for narrowing the frame.

  In a ninth configuration, in the sixth configuration, the step of forming the blocking material is a step of forming the blocking material on each of the first substrate and the second substrate. In the step of bonding the substrate and the second substrate, the sealing material is between the first blocking material formed on the first substrate and the second blocking material formed on the second substrate. It is a step of bonding the first substrate and the second substrate through the sealing material so as to be in a state of being in contact with the first blocking material and the second blocking material. To do. According to this configuration, since the first substrate and the second substrate are bonded together by the laminated structure including the first blocking material, the sealing material, and the second blocking material, the region where the sealing material is formed can be further narrowed. . Moreover, since the blocking material is formed of the above material, the adhesiveness with the sealing material is also good. Therefore, it is possible to further achieve both the narrowing of the frame and the product yield.

  In a tenth configuration, in the ninth configuration, the blocking material is formed using a radiation-sensitive resin composition containing a polymer having an acid dissociable group and an acid generator, and the blocking material The step of heating the blocking material or irradiating the blocking material with radiation after the formation of the film is characterized.

  According to the tenth configuration, the acid dissociable group of the polymer component in the blocking material is eliminated by heating or radiation irradiation, and a polar functional group (such as a hydroxyl group or a carboxyl group) is generated, whereby the component of the sealing material Interaction with the functional group possessed by. Thereby, the adhesiveness of a blocking material and a sealing material can further be improved.

The top view of the liquid crystal display device of 1st Embodiment. 1 is a cross-sectional view of a liquid crystal display device according to a first embodiment. 1 is a cross-sectional view of a liquid crystal display device according to a first embodiment. Sectional drawing of the liquid crystal display device of 2nd Embodiment Sectional drawing of the liquid crystal display device of another example. Sectional drawing of the liquid crystal display device of another example. Sectional drawing of the liquid crystal display device of a comparative example.

(First embodiment)
Hereinafter, a liquid crystal display device and a first embodiment of a manufacturing method thereof will be described with reference to the drawings as appropriate. In the following embodiments, parts that are the same or equivalent to each other are denoted by the same reference numerals in the drawings, and the description of the same reference numerals is used.

  The liquid crystal display device 100 of this embodiment is an IPS (In-Plane Switching) mode type, and includes a pair of glass substrates including a first glass substrate 101 and a second glass substrate 103 as shown in FIGS. I have. On the first glass substrate 101, there are various wirings such as scanning lines and signal lines, pixel electrodes made of a transparent conductor such as a thin film transistor (TFT), ITO (Indium Tin Oxide) as a switching element, and a flat surface. The TFT substrate 102 is constructed by these. On the first glass substrate 101, a plurality of pixels are arranged, for example, in a matrix, and the central portion of the substrate on which the plurality of pixels are arranged becomes a display region R1 constituting the display screen of the liquid crystal display device 100. ing. On the pixel electrode of the TFT substrate 102, a first alignment film 109 as a liquid crystal alignment film for regulating the alignment of the liquid crystal is provided over the entire display region R1. The pair of substrates is not limited to a glass substrate, and for example, a transparent plastic substrate or the like may be used.

  On the second glass substrate 103, a common electrode made of a color conductor, a transparent conductor such as ITO, a light shielding layer, an overcoat layer, and the like are provided, and the counter substrate 104 is constructed by these. On the common electrode of the counter substrate 104, a second alignment film 111 as a liquid crystal alignment film that regulates the alignment of the liquid crystal is provided over the entire display region R1. The TFT substrate 102 and the counter substrate 104 are disposed to face each other, and the peripheral portions of the both substrates disposed to face each other are bonded to each other with a sealant 105 interposed therebetween. On the counter substrate 104, a plurality of spacers 113 (for example, columnar photo spacers) for maintaining a cell gap between the two substrates are provided. A liquid crystal layer 106 is provided between the TFT substrate 102 and the counter substrate 104 so as to be in contact with the first alignment film 109 and the second alignment film 111.

  The sealing material 105 is disposed on the TFT substrate 102 and the counter substrate 104 along the periphery of each substrate so as to surround the display region R1 in a state of being bonded to each substrate. As a material of the sealing material 105, a known material (for example, a thermosetting resin or a photocurable resin) is used as a sealing material for a liquid crystal display device. A space surrounded by the TFT substrate 102, the counter substrate 104, and the sealing material 105 is filled with liquid crystal, and a liquid crystal layer 106 is formed. A terminal region 107 is provided at one end of the TFT substrate 102, and a driver IC 108 for driving liquid crystal is connected to the terminal region 107.

  On the respective surfaces of the TFT substrate 102 and the counter substrate 104 on the liquid crystal layer 106 side, a blocking material 110 made of a hydrophobic resin is disposed as a member for suppressing contact between the liquid crystal alignment films 109 and 111 and the sealing material 105. Yes. 2 and 3, the blocking material 110 is formed between the edge 102a of the TFT substrate 102 and the edge 109a of the first alignment film 109, and between the edge 104a of the counter substrate 104 and the second alignment film 111. The sealing material 105 and the liquid crystal alignment films 109 and 111 are arranged in a non-contact state between the end edge 111a of each of them. In the present embodiment, the first blocking material 110a provided on the TFT substrate 102 is disposed between the sealing material 105 and the edge 109a of the first alignment film 109 so as to surround the display region R1. Further, the second blocking material 110b provided on the counter substrate 104 is disposed so as to surround the display region R1 between the sealing material 105 and the edge 111b of the second alignment film 111 (FIGS. 1 and FIG. 1). 2). In particular, in this embodiment, the blocking material 110 is formed using a silicon resin or a fluorine resin having a fluorine-containing group having 1 to 40 carbon atoms in the side chain.

  In the present embodiment, as shown in FIGS. 2 and 3, the first blocking material 110a and the second blocking material 110b are in a non-contact state in the height direction. Further, the upper end surface of the first blocking material 110a and the upper end surface of the second blocking material 110b may be in contact with each other by expanding the second blocking material 110b in the height direction. In the liquid crystal display device 100, a polarizing plate 114 is disposed outside each of the TFT substrate 102 and the counter substrate 104.

Next, a method for manufacturing the liquid crystal display device 100 of the present embodiment will be described. This manufacturing method includes the following steps A to C.
Step A: A step of disposing a blocking material 110 on each of the TFT substrate 102 and the counter substrate 104 so as to surround the display region R1 in the central portion of the substrate.
Step B: Step of forming the liquid crystal alignment films 109 and 111 in the display region R1 on each of the TFT substrate 102 and the counter substrate 104 after the arrangement of the blocking material 110.
Step C: A step of bonding the TFT substrate 102 and the counter substrate 104 through the sealing material 105 disposed outside the display region R1 after the liquid crystal alignment films 109 and 111 are formed.

  Since the blocking material 110 and the liquid crystal alignment films 109 and 111 are the same for the TFT substrate 102 and the counter substrate 104, the TFT substrate 102 will be described in steps A and B below. Description is omitted.

  In step A, the first blocking material 110a is formed on the electrode formation surface of the TFT substrate 102 so as to surround the display region R1 in the central portion of the substrate. In the present embodiment, the first blocking material 110a is formed in a region R2 between the region where the first alignment film 109 is formed, that is, the display region R1 and the region R3 where the sealing material 105 is disposed. Examples of a method for forming the blocking material 110 include a photolithography method, a dispenser method, a screen printing method, and the like. Among them, by using the photolithography method, it is possible to ensure alignment accuracy of 1 μm or less, which is more preferable from the viewpoint of narrowing the frame. The height and width of the first blocking material 110a are appropriately set according to the size of the substrate.

  Since a known method can be used for the step of forming the first blocking material 110a by the photolithography method, a detailed description is omitted here, but usually a method including a film formation step, a radiation irradiation step, and a development step. To do. First, in a film formation process, the radiation sensitive resin composition containing the polymer [A] which has an acid dissociable group, and an acid generator is apply | coated on a board | substrate, and a coating film is formed. When the radiation sensitive resin composition contains a solvent, it is preferable to remove the solvent by prebaking the coated surface. In the subsequent radiation irradiation step, at least a part of the coating film is irradiated with radiation and exposed. The exposure is performed through a photomask having a predetermined pattern corresponding to the shape of the blocking material 110. Next, the coating film irradiated with radiation is developed (development process). As a result, unnecessary portions (irradiated portions if positive type) are removed, and the blocking material 110 having a predetermined pattern is formed. The developer is preferably an alkaline aqueous solution. After the development, a heating step for heating the coating film may be included. The developer can be sufficiently removed by heating, and the curing reaction of the polymer [A] is accelerated as necessary.

  In the subsequent process B, a liquid crystal aligning agent is applied to the display region R1 on the TFT substrate 102 by, for example, an offset printing method, an ink jet printing method, or the like to form a coating film. In addition, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied liquid crystal aligning agent, and baking (post-baking) is preferably performed for the purpose of completely removing the solvent in the coating film. The pre-baking temperature at this time is preferably 30 to 200 ° C., and the pre-baking time is preferably 0.25 to 10 minutes. The post-bake temperature is preferably 80 to 300 ° C., and the post-bake time is preferably 5 to 200 minutes.

As the liquid crystal aligning agent, for example, a liquid crystal formed by dispersing or dissolving one or more polymer components such as polyamic acid, polyimide, polyamic acid ester, polyamide, polyorganosiloxane, and poly (meth) acrylate in an organic solvent. An alignment agent is used. In this embodiment, as a liquid crystal aligning agent, a photo-alignment treatment using a photo-alignment agent containing a polymer having a photo-alignment group and irradiating a coating film formed using the photo-alignment agent with polarized or non-polarized radiation. Is performed to form the first alignment film 109. A photo-alignment group is a functional group that imparts anisotropy to a film by photo-isomerization reaction, photo-dimerization reaction or photo-decomposition reaction by light irradiation. Examples thereof include a benzoate structure. In the photo-alignment treatment, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used as the radiation applied to the coating film, for example. Preferably, it is an ultraviolet ray containing light having a wavelength of 200 to 400 nm. The radiation dose is preferably 400 to 50,000 J / m ² , more preferably 1,000 to 20,000 J / m ² .

  The method for forming the first alignment film 109 is not limited to the photo-alignment method, and a rubbing process in which the coating film is rubbed in a certain direction with a roll wound with a cloth made of fibers such as nylon, rayon, and cotton may be used. .

  In the subsequent process C, a sealing material 105 for bonding the TFT substrate 102 and the counter substrate 104 is applied along the periphery of at least one of the TFT substrate 102 and the counter substrate 104. At this time, since the blocking material 110 is provided on the substrate, the liquid crystal alignment films 109 and 111 are not formed in the region R3 in which the sealing material 105 is disposed. Thereby, it is suppressed that the sealing material 105 is formed on the liquid crystal alignment films 109 and 111. Thereafter, a liquid crystal is dropped or applied on one substrate coated with the sealing material 105 by, for example, an ODF (One Drop Filling) method or an inkjet method, and the other substrate is attached so that the liquid crystal alignment films 109 and 111 face each other. Match. However, the method for constructing the liquid crystal display device 100 is not limited to the above. For example, the peripheral portions of a pair of substrates opposed to each other with a cell gap interposed therebetween are bonded together via the sealing material 105, and the substrate surface and the sealing material 105 are bonded. A method of sealing the injection hole after injecting and filling the liquid crystal in the cell gap surrounded by may be adopted. Thereafter, a polarizing plate 114 is bonded to the outside of the TFT substrate 102 and the counter substrate 104, whereby the liquid crystal display device 100 is obtained.

  In step A of the present embodiment, the blocking material 110 is disposed on each of the TFT substrate 102 and the counter substrate 104. However, a liquid crystal alignment film is provided only on one of the TFT substrate 102 and the counter substrate 104. Alternatively, the blocking material 110 may be formed only on the substrate on which the liquid crystal alignment film is formed.

  Next, the material constituting the blocking material 110 will be described in detail. The blocking material 110 is formed using a silicon resin or a fluorine resin having a fluorine-containing group having 1 to 40 carbon atoms in the side chain.

The silicon-based resin is not particularly limited as long as it is a resin having a silicon atom in the basic skeleton, but is preferably at least one of polysiloxane and polysilazane. Polysiloxane refers to a polymer containing a Si—O bond in a repeating unit. For example, “— (Si (R) ₂ —O) _n —” (R is a hydroxyl group, a halogen atom, or a monovalent organic group. And n is an integer of 2 or more). Polysilazane refers to a polymer containing a Si—N bond in a repeating unit. From the viewpoint of ease of synthesis, polysiloxane can be preferably used as the silicon resin.

  The silicon-based resin preferably has at least one of an oxetanyl group and an oxiranyl group in the side chain from the viewpoint of improving adhesion to the substrate. A silicon resin having at least one of an oxetanyl group and an oxiranyl group in the side chain can be obtained, for example, by polymerization using a monomer having an oxetanyl group or an oxiranyl group. The content ratio of the structural unit derived from the monomer having an oxetanyl group or oxiranyl group in the silicon-based resin should be 10 mol% or more based on the total constitutional unit in terms of sufficiently obtaining the adhesion improving effect. Is preferable, and it is more preferable to set it as 30 mol% or more.

  The main skeleton of the fluorine-based resin having a fluorine-containing group having 1 to 40 carbon atoms in the side chain (hereinafter also referred to as “side-chain fluorine-based resin”) is not particularly limited, but a monomer having an ethylenically unsaturated bond A polymer containing a structural unit derived from is preferably used. Examples of the monomer having an ethylenically unsaturated bond include (meth) acrylic compounds, vinyl compounds, maleimide compounds and the like. The side chain type fluorine resin is preferably a (meth) acrylic polymer. In this specification, the (meth) acrylic polymer is a polymer using only a (meth) acrylic compound as a monomer, and a copolymer using a (meth) acrylic compound and another monomer. It means to include. In the latter, the content ratio of the structural unit derived from the (meth) acrylic compound is preferably 30 mol% or more, more preferably 40 mol% or more, and more preferably 60 mol% with respect to all the structural units of the side chain fluorine-based resin. The above is more preferable.

  Examples of the fluorine-containing group having 1 to 40 carbon atoms that the side chain fluorine-containing resin has include groups in which one or more hydrogen atoms in a hydrocarbon group having 1 to 40 carbon atoms are substituted with fluorine atoms. In the present specification, the “hydrocarbon group” is a concept including a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Among these, the fluorine-containing group of the side chain fluororesin is preferably a group obtained by substituting one or more hydrogen atoms in a chain hydrocarbon group having 1 to 40 carbon atoms with a fluorine atom. More preferably, it is a 1-12 fluoroalkyl group. The number of fluorine atoms in the fluorine-containing group is appropriately set according to the number of carbon atoms in the fluorine-containing group, but is preferably 1-20, more preferably 3-15.

（式（１）中、Ｒ^１は炭素数１〜４のアルキル基又は炭素数４〜２０の１価の脂環式炭化水素基であり、Ｒ^２及びＲ^３は、それぞれ独立に炭素数１〜４のアルキル基若しくは炭素数４〜２０の１価の脂環式炭化水素基であるか、又はＲ^２とＲ^３とが結合してそれぞれが結合している炭素原子とともに炭素数４〜２０の２価の脂環式炭化水素基を形成している。式（２）及び式（３）中、Ｒ^４及びＲ^５は、それぞれ独立に水素原子又はメチル基であり、Ｒｆは、１価の炭化水素基が有する水素原子の少なくとも１個がフッ素原子で置換された基である。） The blocking material 110 is formed, for example, by applying a polymer composition obtained by dispersing or dissolving a silicon-based resin or a side chain fluorine-based resin in a suitable organic solvent on a substrate. For the purpose of removing the organic solvent, the polymer composition applied on the substrate may be subjected to a treatment such as heating as necessary. When the blocking material 110 is formed by photolithography, the polymer [A] having an acid dissociable group may be a silicon-based resin, a side chain fluorine-based resin, or silicon. It may be other polymers other than the base resin and the side chain type fluororesin. A silicon resin or a side chain type fluorine resin is preferable.
As the acid-dissociable group, a group that substitutes a hydrogen atom in a polar functional group such as a hydroxyl group or a carboxyl group and dissociates in the presence of an acid is used. By using such a group, development with an alkaline developer becomes possible. Specific examples thereof include groups represented by the following formulas (1) to (3), a tetrahydropyranyl group, a tetrahydrofuranyl group, an alkoxy-substituted methyl group, and an alkylsulfanylmethyl group.

(In the formula (1), R ¹ is an alkyl group having 1 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, and R ² and R ³ each independently have 1 carbon atom. An alkyl group having 4 to 4 carbon atoms or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms, or a carbon atom having 4 to 20 carbon atoms together with carbon atoms to which R ² and R ³ are bonded to each other. In formulas (2) and (3), R ⁴ and R ⁵ are each independently a hydrogen atom or a methyl group, and Rf is a monovalent group. This is a group in which at least one hydrogen atom of the hydrocarbon group is substituted with a fluorine atom.)

  Here, in the formation process of the liquid crystal alignment films 109 and 111, the liquid crystal alignment films 109 and 111 are formed up to the region R3 where the sealing material 105 is formed by spreading the liquid crystal alignment agent applied on the substrate in the outer peripheral direction. Sometimes. In addition, when the liquid crystal aligning agent is applied on each substrate by using an ink jet printing method or an offset printing method, high throughput can be realized. It is also possible to enter the region R3.

  Further, when the liquid crystal alignment films 109 and 111 are formed up to the region R3 of the sealing material 105, the sealing material 105 is disposed on the liquid crystal alignment film so that the adhesion of the sealing material 105 to the substrate is insufficient. There is concern about becoming. In addition, as a result of insufficient adhesion of the sealing material 105, moisture permeation from the interface between the sealing material 105 and the liquid crystal alignment films 109 and 111 is allowed, and display unevenness and local voltage holding ratio (VHR) : Voltage Holding Ratio) may be reduced. In order to suppress the formation of the liquid crystal alignment films 109 and 111 up to the region R3 of the sealing material 105, a sufficient space is provided between the formation region of the liquid crystal alignment films 109 and 111 and the region R3 of the sealing material 105. Although applying a liquid crystal aligning agent is also considered, the display area | region R1 of the liquid crystal display device 100 will become narrow in this case, and the problem that a narrow frame cannot be achieved will arise.

  In this respect, in the liquid crystal display device 100 having the above-described configuration, the sealing material 105 and the liquid crystal alignment films 109 and 111 are disposed between the edges 102a and 104a of the respective substrates and the edges 109a and 111a of the liquid crystal alignment films 109 and 111. Since the blocking material 110 is formed so as to be in a non-contact state, when the liquid crystal aligning agent is applied, the liquid crystal aligning agent may be wet spread in the outer peripheral direction or may be misaligned in printing. The liquid crystal alignment films 109 and 111 can be prevented from being formed up to the region R3 where the sealing material 105 is disposed. In particular, in the present embodiment, the blocking material 110 is formed using a silicon-based resin or a side-chain-type fluorine-based resin, so that a local decrease in voltage holding ratio can be suppressed and a thermal reliability is high. 100 can be obtained. Therefore, the liquid crystal display device 100 with a good manufacturing yield can be obtained while narrowing the frame.

(Second Embodiment)
Next, the liquid crystal display device 100 of the second embodiment will be described focusing on the differences from the first embodiment. In the first embodiment, the sealing material 105 is bonded to the surfaces of the TFT substrate 102 and the counter substrate 104. On the other hand, in the liquid crystal display device 100 of the second embodiment, the sealing material 105 is not bonded to the TFT substrate 102 and the counter substrate 104, and as shown in FIG. The sealing material 105 is arranged between the first blocking material 110a and the second blocking material 110b.

  The blocking material 110 is formed of a silicon-based resin or a fluorine-based resin having a fluorine-containing group having 1 to 40 carbon atoms in the side chain, as in the first embodiment. For this reason, the adhesiveness between the blocking material 110 and the sealing material 105 and the adhesiveness between the blocking material 110 and the substrate (TFT substrate 102, counter substrate 104) are high, and entry of moisture into the apparatus is suitably suppressed. Further, since the sealing material 105 is disposed in a region overlapping the blocking material 110 in plan view, a wider display region R1 can be secured. Thereby, it is possible to further reduce the frame while improving the product yield.

  In particular, in the present embodiment, as shown in FIG. 4, the first blocking material 110 a has a thickness different from the facing surface 110 c of the first blocking material 110 a facing the facing substrate 104 and the facing surface 110 d of the second blocking material 110 b facing the TFT substrate 102. It has an uneven pattern. This uneven shape increases the contact area between the sealing material 105 and the blocking material 110 and makes it possible to further improve the adhesion between them. Therefore, in the case where the sealing material 105 is formed so as to overlap the blocking material 110 in plan view, it is possible to more effectively suppress the intrusion of moisture.

  Note that the shape of the concavo-convex pattern on the facing surface and the number of concave portions and convex portions are not particularly limited as long as the contact area between the sealing material 105 and the blocking material 110 can be increased. As the concavo-convex pattern, for example, periodic structures having various shapes such as a columnar shape, a conical shape, a hemispherical shape, and a pyramid shape can be employed.

  The blocking material 110 having a concavo-convex pattern is formed using a photolithography method using a multi-tone mask such as a halftone mask. Specifically, a radiation-sensitive resin composition containing a polymer [A] having an acid-dissociable group and an acid generator is applied onto a substrate to form a coating film, and applied through a multi-tone mask. It is formed by irradiating the film with radiation. The description of the first embodiment is applied to the description of the polymer [A]. Among them, the polymer [A] is preferably a side chain fluorine-based resin having an acid dissociable group, and more preferably the acid dissociable group has a fluorine atom. Examples of such a polymer include a polymer having a structural unit containing a group represented by the above formula (2) or formula (3).

  In addition, when the coating film formed using the said radiation sensitive resin composition is irradiated with a radiation, the acid dissociable group of a radiation irradiation part will detach | desorb, and a recessed part will be formed in a radiation irradiation part by subsequent image development processing. At this time, a hydroxyl group or a carboxyl group is generated in the irradiated portion due to elimination of the acid dissociable group by irradiation. When the sealing material 105 is formed on such a blocking material 110, the contact area between the blocking material 110 and the sealing material 105 is increased by the uneven pattern, and in addition, the hydroxyl group generated in the radiation irradiated portion of the blocking material 110 or Interaction occurs between the carboxyl group and the functional group (for example, epoxy group, carboxyl group, etc.) of the component of the sealing material 105, thereby improving the adhesion between the blocking material 110 and the sealing material 105. It becomes possible.

The manufacturing method of the liquid crystal display device of this embodiment may include a step of heating the blocking material 110 or irradiating the blocking material 110 with radiation after the formation of the blocking material 110. At this time, the acid-dissociable group of the polymer [A] in the blocking material 110 is eliminated by heating or radiation treatment, and the hydroxyl group or carboxyl group generated by the elimination and the functional group of the component of the sealing material 105 are removed. It is possible to improve the adhesion between the blocking material 110 and the sealing material 105 due to the interaction between them. In this step, the heating temperature is preferably in the range of 70 to 300 ° C, more preferably in the range of 80 to 250 ° C. The radiation irradiation is preferably by radiation having a wavelength in the range of 190 to 450 nm, and more preferably by radiation including ultraviolet rays of 365 nm. Exposure is preferably in the range of 500~6,000J / ^{m 2,} and more preferably in the range of 1,000~2,000J / ^{m 2.}

  In addition, when the acid dissociable group has a fluorine atom, it exhibits sufficiently high liquid repellency when the liquid crystal aligning agent is applied, and the acid dissociable group is eliminated by subsequent heating or radiation irradiation. , A hydroxyl group or a carboxyl group is formed and a fluorine atom is eliminated. Thereby, the liquid repellency of the blocking material 110 is lowered, and the adhesion between the blocking material 110 and the sealing material 105 can be further improved. The treatment for heating or irradiating the blocking material 110 may be performed after the blocking material 110 is formed on the substrate, and may be performed either before the sealing material 105 is disposed or after the sealing material 105 is disposed. The former is preferred. In addition, the process of heating the blocking material 110 may be performed simultaneously with the heating (post-baking) for forming the liquid crystal alignment films 109 and 111, and the process of irradiating the blocking material 110 with radiation is performed. It may be performed simultaneously with the photo-alignment treatment for obtaining 111. This is preferable because the number of steps can be reduced.

  The configuration in which the sealing material 105 is interposed between the first blocking material 110a and the second blocking material 110b in the contacted state is not limited to the above. For example, as shown in FIG. 5, a part of the sealing material 105 is bonded to the TFT substrate 102 and the counter substrate 104, and at least a part of the remaining part is composed of the first blocking material 110 a and the second blocking material 110 b. It is good also as a structure which is contacting the opposing surfaces 110c and 110d. In addition, as shown in FIG. 6, the first blocking material 110 a and the second blocking material 110 b may be configured such that the concavity and convexity patterns are not provided on the facing surfaces 110 c and 110 d of the substrate and the sealing material 105 is in contact with a flat surface. Good. In these cases, the polymer [A] is preferably a side chain fluorine-based resin having an acid dissociable group, and more preferably the acid dissociable group has a fluorine atom. Further, it is preferable to perform a step of heating or irradiating the blocking material 110 after the blocking material 110 is formed, so that the adhesion between the blocking material 110 and the sealing material 105 can be further improved.

  In the first embodiment and the second embodiment, the IPS mode liquid crystal display device of the horizontal electric field type has been described. However, the present invention is not limited to this. For example, a liquid crystal display device of FFS (Fringe Field Switching) mode, The present invention can be applied to liquid crystal display devices of various modes such as an electric field type TN (Twisted Nematic) mode, VA (Vertical Alignment) mode, MVA (Multi-domain Vertical Alignment) mode, and PSA (Polymer Sustained Alignment) mode. The liquid crystal display device 100 can be effectively applied to various applications, such as a clock, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, a digital camera, a mobile phone, a smartphone, and various types. It can be used as various display devices such as a monitor, a liquid crystal television, and an information display.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to a following example. In the examples, “parts” and “%” are based on mass unless otherwise specified. Various measurements in the examples were performed as follows.
[Weight Average Molecular Weight (Mw) and Number Average Molecular Weight (Mn) of Polymer]] The polymer was determined by polystyrene conversion by gel permeation chromatography (GPC) method. Measurement by the GPC method was carried out using tetrahydrofuran as a solvent under the following conditions, and dissolving 1 g of organopolysiloxane in 100 cc of tetrahydrofuran to prepare a sample. As the standard polystyrene, standard polystyrene manufactured by US Pressure Chemical Company was used.
Apparatus: US Waters, constant temperature high speed gel permeation chromatogram (model 150-CALC / GPC)
Column; manufactured by Showa Denko KK, SHODEX A-80M, length 50 cm
Measurement temperature: 40 ° C
Flow rate: 1 cc / min [Solution viscosity of polymer solution (mPa · s)] A solution prepared to a polymer concentration of 10% by mass using a predetermined solvent was measured at 25 ° C. using an E-type rotational viscometer.

<Synthesis of polymer>
[Synthesis Example 1]
A reactor equipped with a reflux condenser and a stirrer was charged with 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine, and mixed at room temperature. 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the reaction was carried out at 80 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer is taken out, washed with 0.2% by weight ammonium nitrate aqueous solution until the water after washing becomes neutral, and then the solvent and water are distilled off under reduced pressure to have an oxiranyl group. Polyorganosiloxane was obtained as a viscous transparent liquid.
Next, this transparent liquid is poured into methanol to recover the generated precipitate, which is dissolved in ethyl acetate to form a solution. The solution is washed with water three times, and then the solvent is distilled off to remove the oxiranyl group. 6.3 g of polyorganosiloxane (PSi-1) having white powder was obtained. The weight average molecular weight in terms of polystyrene measured by GPC for this polyorganosiloxane (PSi-1) was 3,500.

[Synthesis Example 2]
In a reactor equipped with a reflux condenser and a stirrer, 25 parts of 2-methacryloyloxyethyl succinic acid, 3,3,4,4,5,5,6,6,7,7,8,8,8-tri 53 parts of decafluoro-1-vinyloxy-octane, 1.1 parts of pyridinium paratoluenesulfonate, and 200 parts of tetrahydrofuran were charged, heated to 60 ° C., and reacted for 9 hours. After cooling, the reaction solution was quenched by adding 0.5 part of pyridine. The obtained reaction solution was washed with water and separated, the solvent was removed with a rotary evaporator, and unreacted components were removed by distillation under reduced pressure to obtain an acetalization product (M-1).
Subsequently, in a reactor equipped with a reflux condenser and a stirrer, 8 parts of dimethyl 2,2′-azobis (2-methylpropionate), 2 parts of 2,4-diphenyl-4-methyl-1-pentene and diethylene glycol 200 parts of dimethyl ether was charged. Next, after adding 75 parts of the acetalization product (M-1) obtained above and 25 parts of benzyl methacrylate and replacing with nitrogen, the temperature of the solution was raised to 80 ° C. while gently stirring. Was polymerized by holding for 4 hours to obtain a solution containing a polymer (P-1) as a copolymer. The solid content concentration of this solution was 34.5%. The weight average molecular weight in terms of polystyrene of the polymer (P-1) was 24,100.

[Synthesis Example 3]
Into a 100 mL four-necked flask containing a stirrer, 2.73 g of a compound represented by the following formula (da-1) was added, and then 59.2 g of N-methyl-2-pyrrolidone (NMP) was added and stirred. And dissolved. Next, 2.23 g of triethylamine and 1.1 g of p-phenylenediamine were added and dissolved by stirring. While stirring this solution, 8.43 g of a compound represented by the following formula (ad-1) was added, and 10.59 g of NMP was further added, followed by stirring at 40 ° C. for 3 hours to obtain a solution viscosity of 18.2 mPa · A solution of s was obtained. The obtained solution was put into 512 g of methanol, and the resulting precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyamic acid ester (PE-1) powder. The molecular weight in terms of polystyrene of this polyamic acid ester (PE-1) was Mn = 11,200 and Mw = 28,500. 1.6 g of the resulting polyamic acid ester powder was placed in a 100 mL Erlenmeyer flask containing a stirrer, 11.8 g of NMP was added, and the mixture was stirred and dissolved at room temperature for 18 hours, whereby polyamic acid ester (PE-1) was dissolved. A solution containing was obtained.

[Synthesis Example 4]
19.61 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 19.92 g of 4,4′-diaminodiphenylamine as diamine were dissolved in 420 g of NMP and reacted at 40 ° C. for 4 hours. By doing so, a solution containing polyamic acid (PA-1) having a solution viscosity of 180 mPa · s was obtained.
[Synthesis Example 5]
NMP 200g with 18.22 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 31.28 g of bis [2- (4-aminophenyl) ethyl] hexanedioic acid as diamine By dissolving and reacting at 40 ° C. for 6 hours, a solution containing polyamic acid (PA-2) having a solution viscosity of 125 mPa · s was obtained.
[Synthesis Example 6]
19.61 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride as tetracarboxylic dianhydride and 5.95 g of 4,4′-diaminodiphenylmethane as diamine and N4, N4′-bis- (4- Aminophenyl) -N4, N4′-dimethylbiphenyl-4,4′-diamine (27.62 g) was dissolved in 370 g of NMP and reacted at 40 ° C. for 3 hours to give a polyamic acid (PA-3) having a solution viscosity of 165 mPa · s. ) Was obtained.

<Liquid crystal display device>
[Example 1]
In Example 1, for the liquid crystal display device 100 shown in FIGS. 1 to 3 (the liquid crystal display device corresponding to the first embodiment), a blocking material 110 was manufactured using a silicon-based resin, and performance evaluation was performed. .
(Preparation of blocking material)
The polyorganosiloxane (PSi-1) obtained in Synthesis Example 1 was mixed with propylene glycol monomethyl ether acetate (PGMEA), N-methyl-2-pyrrolidone (NMP) and butyl acetate (BTLAC) (PGMEA: NMP: BTLAC = 30: 30: 40 (mass ratio) was dissolved to obtain a solution having a solid content concentration of 28.5% by mass. The blocking material (B-1) was prepared by filtering this solution with a filter having a pore size of 0.2 μm.

(Preparation of liquid crystal aligning agent)
A solution containing the polyamic acid ester (PE-1) obtained in Synthesis Example 3 and a solution containing the polyamic acid (PA-1) obtained in Synthesis Example 4 were combined into a polyamic acid ester (PE-1): polyamic acid. (PA-1) was dissolved in an NMP / BCS mixed solution (mass ratio = 50: 50) so as to be 50:50 (mass ratio) to prepare a solution having a solid content concentration of 3.5 mass%. After sufficiently stirring each solution, a liquid crystal aligning agent (AL-1) was prepared by filtering using a filter having a pore size of 1 μm.

(Manufacture and evaluation of liquid crystal display devices)
The liquid crystal display device 100 shown in FIGS. 1 to 3 was manufactured using the blocking material and the liquid crystal aligning agent (AL-1) prepared above, and subjected to the following evaluations (1) and (2). In this embodiment, the first blocking material 110a is formed by a screen printing method between the region where the first alignment film 109 is formed and the region where the sealing material 105 is disposed, and the second alignment film 111 is formed. The second blocking material 110b was formed by a screen printing method between the region to be formed and the region where the sealing material 105 is disposed. The liquid crystal alignment films 109 and 111 are formed by forming a blocking material 110 on a substrate, applying a liquid crystal aligning agent (AL-1) to the inner region of the blocking material 110 by an offset printing method, and then applying a hot plate at 80 ° C. The film was pre-baked for 1 minute and heated (post-baked) at 230 ° C. for 30 minutes in an oven in which the inside of the chamber was replaced with nitrogen, and then liquid crystal alignment ability was imparted by photo-alignment treatment. The photo-alignment treatment was performed by irradiating the coating film with ultraviolet rays of 254 nm at a dose of 100 mJ / cm ² through a polarizing plate.

(1) VHR evaluation of surrounding pixels of sealing material Using the liquid crystal display device 100 manufactured above, VHR evaluation of the surrounding region of the sealing material was performed. First, a pulse signal is applied to the gate scanning line at a frequency of 60 Hz, a rectangular wave signal having an amplitude that is halftone is applied to the signal line at a frequency of 30 Hz, and the liquid crystal display device 100 is driven on the backlight. . Then, using the response speed detector RD-80SA manufactured by TOPCON Corporation, the Flicker (light flicker) intensity at the frequency of 60 Hz in the center portion of the liquid crystal display device 100 and the sealing material peripheral region within 2 cm from the frame portion The Flicker intensity at a frequency of 60 Hz was measured by Fast Fourier Transform (FFT). The Flicker intensity at a frequency of 60 Hz corresponds to the VHR of the liquid crystal display device 100. The better the VHR, the lower the Flicker intensity is detected. In this measurement, when the Flicker strength in the peripheral portion of the seal material exceeds 20% or more of the Flicker strength in the central portion of the liquid crystal display device 100, the VHR characteristic is “impossible (×)”. “△” ”is 5% or more and less than 10%,“ Good (◯) ”, and 5% or less is“ Excellent (◎) ”. As a result, the VHR characteristic of the liquid crystal display device 100 was “excellent”.

(2) Evaluation of thermal reliability Thermal reliability evaluation after the high temperature and high humidity test was performed using the liquid crystal display device 100 manufactured as described above. The liquid crystal display device 100 was stored in a high-temperature and high-humidity container having a temperature of 80 ° C. and a humidity of 80% for 72 hours, and then the lighting of the liquid crystal display device 100 was checked at room temperature. In this test, when the display unevenness was confirmed in the peripheral portion of the seal material, the thermal reliability was “defective (×)”, and when the display unevenness was not confirmed, it was determined as “good (◯)”. As a result, the thermal reliability of the liquid crystal display device 100 was “good”.

[Example 2]
In Example 2, the blocking material 110 of the liquid crystal display device 100 (the liquid crystal display device corresponding to the first embodiment) shown in FIGS. 1 to 3 was manufactured using a fluororesin, and performance evaluation was performed.
(Preparation of blocking material)
100 parts of the polymer (P-1) obtained in Synthesis Example 2, 2 parts of N-hydroxynaphthalimide-trifluoromethanesulfonic acid ester as an acid generator, 1 part of 2-isopropylthioxanthone as a sensitizer, and as a quencher 0.05 parts of 2-phenylbenzimidazole, dipentaerythritol hexaacrylate as a polymerizable compound, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one as a radiation-sensitive polymerization initiator ( 2 parts of Irgacure (registered trademark) 907, manufactured by BASF) are mixed, 0.1 part of Polyflow No75 (manufactured by Kyoeisha Chemical Co., Ltd.) is added as a surfactant, and dissolved in diethylene glycol dimethyl ether as a solvent. It was set as the solution whose solid content concentration is 20 mass%. The blocking material (B-2) was prepared by filtering this solution through a filter having a pore size of 0.5 μm.

(Manufacture and evaluation of liquid crystal display devices)
In the liquid crystal display device 100 of Example 1, the blocking material 110 was formed by screen printing using the blocking material (B-1) containing polyorganosiloxane, but in the liquid crystal display device 100 of Example 2, the side chain It formed by the photolithographic method using the blocking material (B-2) which is a radiation sensitive resin composition containing a type fluorine resin. About others, the liquid crystal display device 100 was manufactured similarly to Example 1, and VHR evaluation and thermal reliability evaluation of the sealing material peripheral pixel were performed similarly to Example 1 about the manufactured liquid crystal display device 100.

  As a result, the VHR characteristic in this example was “excellent” and the thermal reliability was “good”. From this result, even when the blocking material 110 is formed using a radiation-sensitive resin composition containing a fluorine-based resin having a fluorine-containing group in the side chain, the same as when the polyorganosiloxane of Example 1 is used. Furthermore, it was confirmed that liquid repellency with respect to the liquid crystal aligning agent was exhibited, and good characteristics were obtained by suppressing contact between the liquid crystal aligning film and the sealing material 105.

[Example 3]
In Example 3, the blocking material 110 of the liquid crystal display device 100 shown in FIG. 4 (the liquid crystal display device corresponding to the second embodiment) was manufactured using the blocking material (B-2) prepared in Example 2, and the performance Evaluation was performed. The uneven patterns of the first blocking material 110a and the second blocking material 110b were formed using a photolithography method using a halftone mask. After forming an uneven pattern on the first blocking material 110a and the second blocking material 110b, a liquid crystal alignment film was formed inside the blocking material 110 in the same manner as in Example 1. In addition, the post-baking process at the time of alignment film formation corresponds to the heating process of the blocking material 110. Next, the sealing material 105 is applied on the concave and convex patterns of the first blocking material 110a and the second blocking material 110b, and the liquid crystal alignment films 109 and 111 are arranged so as to face each other, and a pair of substrates is bonded via the sealing material 105. Combined. About others, the liquid crystal display device 100 was manufactured similarly to Example 1, and VHR evaluation and thermal reliability evaluation of the sealing material peripheral pixel were performed similarly to Example 1.

  As a result, the VHR characteristic of the liquid crystal display device 100 of this example was “excellent” and the thermal reliability was “good”. From this result, even when the sealing material 105 is formed so as to overlap the blocking material 110, the blocking material 110 and the blocking material 110 can be formed by forming an uneven pattern in a region overlapping the sealing material 105 of the blocking material 110 in plan view. It was confirmed that good characteristics were obtained by increasing the contact area with the sealing material 105 and improving the adhesion between them.

[Example 4]
In Example 1, the liquid crystal alignment film was formed by photo-alignment treatment, but in Example 4, the liquid crystal alignment film 100 was formed by rubbing treatment to form the liquid crystal display device 100 shown in FIGS. A corresponding liquid crystal display device was manufactured and performance evaluation was performed.

(Preparation of liquid crystal aligning agent)
A solution containing the polyamic acid (PA-2) obtained in Synthesis Example 5 and the polyamic acid (PA-3) obtained in Synthesis Example 6 were combined with PA-2: PA-3 = 20: 80 (mass ratio). Thus, it was dissolved in an NMP / BCS mixed solution (mass ratio 50:50) to obtain a solution having a solid content concentration of 4.2 mass%. After sufficiently stirring the solution, a liquid crystal aligning agent (AL-2) was prepared by filtering using a filter having a pore size of 1 μm.
(Manufacture and evaluation of liquid crystal display devices)
Example 1 except that the liquid crystal aligning agent (AL-2) was used as the liquid crystal aligning agent and the coating film obtained using the liquid crystal aligning agent was rubbed to develop liquid crystal aligning properties. Similarly, the liquid crystal display device 100 of FIG. 3 was manufactured, and the VHR evaluation and the thermal reliability evaluation of the pixels around the sealing material were performed in the same manner as in Example 1.
As a result, the VHR characteristics of the liquid crystal display device 100 obtained in this example were “excellent” and the thermal reliability was “good”. From this result, it was confirmed that good characteristics could be obtained even when liquid crystal alignment was imparted to the alignment film by rubbing instead of photo-alignment.

  However, for the liquid crystal display device 100 manufactured in Example 4, the alignment unevenness was observed when the liquid crystal alignment around the sealing material was visually observed. The reason for this is not necessarily clear, but by performing the rubbing process in a state in which the blocking material 110 is formed, the level difference of the blocking material 110 causes unevenness in the rubbing strength with respect to the liquid crystal alignment film near the blocking material. it is conceivable that.

[Comparative Example 1]
In Example 1, the blocking material 110 is disposed between the region where the liquid crystal alignment film is formed and the region where the sealing material 105 is formed. In the liquid crystal display device of Comparative Example 1, as shown in FIG. The sealing material 105 was formed on the liquid crystal alignment film without forming the blocking material 110. Other than that, a liquid crystal display device was manufactured in the same manner as in Example 1, and VHR evaluation and thermal reliability evaluation of pixels around the sealing material were performed in the same manner as in Example 1 for the manufactured liquid crystal display device.

  As a result, in the liquid crystal display device of Comparative Example 1, the VHR characteristics were “impossible” and the thermal reliability was “good”. From this result, the configuration in which the liquid crystal alignment film and the sealing material 105 overlap without forming the blocking material 110 becomes insufficient in the adhesion between the sealing material 105 and the liquid crystal alignment film, and the sealing material 105 and the liquid crystal It is presumed that the infiltration of moisture from the interface with the alignment film allowed local VHR reduction.

[Comparative Example 2]
In the liquid crystal display device 100 of Example 1, the blocking material 110 was formed by screen printing using polyorganosiloxane, but in the liquid crystal display device of Comparative Example 2, Teflon (registered trademark, polytetrafluoroethylene) was used. The blocking material 110 was formed by an air spray method. About others, while manufacturing a liquid crystal display device similarly to Example 1, VHR evaluation and thermal reliability evaluation of the sealing material periphery pixel were performed similarly to Example 1 about the manufactured liquid crystal display device.

  As a result, the VHR characteristic of the liquid crystal display device of Comparative Example 2 was “excellent” and the thermal reliability was “bad”. From this result, when Teflon was used for the blocking material 110, although the result equivalent to the Example was obtained about the VHR characteristic, thermal reliability was inferior to the Example. The reason for this is not always clear, but because Teflon has a high coefficient of linear expansion, the dimensions of the blocking material under high-temperature and high-humidity tests change, and display irregularities derived from cell gaps appear in the vicinity of the sealing material of liquid crystal display devices. It is thought that.

  Table 1 below shows the VHR evaluation, thermal reliability, and alignment unevenness evaluation results of the peripheral pixels of the sealing materials of Examples 1 to 4 and Comparative Examples 1 and 2 described above. In Table 1, the item “arrangement / shape” indicates the positional relationship between the blocking material 110 and the sealing material 105 and the shape of the opposing surface of the blocking material.

  As shown in Table 1, the liquid crystal display devices 100 of Examples 1 to 4 in which the blocking material 110 is formed using a silicon-based resin or a side chain type fluorine-based resin have favorable VHR characteristics and thermal reliability. there were. On the other hand, in the comparative example 1 which did not form the blocking material 110, the VHR characteristic was inferior to the Example. Moreover, the thermal reliability of the comparative example 2 which formed the blocking material 110 using Teflon was inferior to the Example.

  DESCRIPTION OF SYMBOLS 100 ... Liquid crystal display device 101 ... 1st glass substrate, 102 ... TFT substrate, 103 ... 2nd glass substrate, 104 ... Opposite substrate, 105 ... Sealing material, 106 ... Liquid crystal layer, 109 ... 1st alignment film, 110 ... Blocking 110a ... first blocking material, 110b ... second blocking material, 111 ... second alignment film

Claims (10)

The peripheral portions of the first substrate and the second substrate that are arranged opposite to each other are bonded together via a sealing material, and the liquid crystal display device includes a liquid crystal layer between the first substrate and the second substrate,
On at least one of the first substrate and the second substrate, a liquid crystal alignment film formed in a region inside the sealing material;
On the substrate on which the liquid crystal alignment film is formed, the sealing material and the liquid crystal alignment film are disposed in a non-contact state between the edge of the substrate and the edge of the liquid crystal alignment film. And a blocking material,
The liquid crystal display device in which the blocking material is formed using a silicon-based resin or a fluorine-based resin having a fluorine-containing group having 1 to 40 carbon atoms in a side chain.   The method for manufacturing a liquid crystal display device according to claim 1, wherein the silicon-based resin is at least one of polysiloxane and polysilazane.   The liquid crystal display device according to claim 1, wherein the fluororesin is a resin having a fluoroalkyl group having 1 to 12 carbon atoms in a side chain. The blocking material includes a first blocking material formed on the first substrate, and a second blocking material formed on the second substrate,
The sealant is interposed between the first blocking material and the second blocking material in a state of being in contact with the first blocking material and the second blocking material. The liquid crystal display device according to item.   5. The liquid crystal display device according to claim 4, wherein the contact surface between the first blocking material and the sealing material and the contact surface between the second blocking material and the sealing material have uneven patterns having different film thicknesses. A manufacturing method of a liquid crystal display device in which peripheral portions of a first substrate and a second substrate that are arranged to face each other are bonded together with a sealant, and a liquid crystal layer is provided between the first substrate and the second substrate. And
Forming a blocking material on at least one of the first substrate and the second substrate so as to surround a display region of a central portion of the substrate;
After forming the blocking material, forming a liquid crystal alignment film in the display area;
Bonding the first substrate and the second substrate through the sealing material disposed outside the display region after the liquid crystal alignment film is formed,
The manufacturing method of the liquid crystal display device with which the said blocking material is formed using the fluorine-type resin which has a silicon-type resin or a C1-C40 fluorine-containing group in a side chain.   The manufacturing method of the liquid crystal display device of Claim 6 which forms the said liquid crystal aligning film by performing a photo-alignment process to the coating film formed using the liquid crystal aligning agent.   The method for manufacturing a liquid crystal display device according to claim 6, wherein the blocking material is formed by a photolithography process. The step of forming the blocking material is a step of forming the blocking material on each of the first substrate and the second substrate,
The step of bonding the first substrate and the second substrate is performed between the first blocking material formed on the first substrate and the second blocking material formed on the second substrate. The step of bonding the first substrate and the second substrate through the sealing material so that the sealing material is in a state of being in contact with the first blocking material and the second blocking material, The manufacturing method of the liquid crystal display device as described in any one of Claims 6-8. The blocking material is formed using a radiation sensitive resin composition containing a polymer having an acid dissociable group and an acid generator,
The manufacturing method of the liquid crystal display device of Claim 9 including the process of heating the said blocking material or irradiating the said blocking material with radiation after formation of the said blocking material.

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