TWI434112B - Support substrate of liquid crystal panel and method of manufacturing the same - Google Patents

Description

Carrier substrate of liquid crystal display panel and manufacturing method thereof

The present invention relates to a carrier substrate for a liquid crystal display panel and a method of fabricating the same.

The liquid crystal display panel has advantages such as thinness, light weight, and low power consumption, and is widely used in electronic devices such as Office Automation Equipment and mobile phones. The liquid crystal display panel is configured by sealing a liquid crystal between two substrates bonded via a sealant, applying a voltage to the liquid crystal to control the alignment of the liquid crystal, and modulating the light transmitted through the liquid crystal to display an image.

A method of injecting liquid crystal between the substrates includes a liquid crystal injection method and a liquid crystal dropping method. In the liquid crystal injection method, an injection port for injecting a liquid crystal is provided in a part of a seal formed on a substrate, and after bonding the two substrates, liquid crystal is injected from the injection port. On the other hand, in a typical liquid crystal dropping method, first, liquid crystal is dropped onto the inside of a sealing member provided on any of the substrates, and then the substrate is superposed on the other substrate under reduced pressure, and then returned to atmospheric pressure, thereby returning to atmospheric pressure. The substrates are bonded to each other, whereby liquid crystals are sealed between the substrates. Since the liquid crystal dropping method can enclose the liquid crystal in a shorter time than the liquid crystal injection method, it is effective in terms of improving productivity and the like. Further, in the liquid crystal dropping method, there is a method in which the substrates are bonded to each other by pressurization. However, in order to make the substrates more closely bonded, it is preferred that the former utilizes a method of using a gas pressure difference, and thus the former method has recently been widely used.

However, in recent years, with the development of electronic devices, there has been a strong demand for high definition, large screen, and the like of liquid crystal display panels. In order to improve the display quality of the liquid crystal display panel, it is important to keep the gap of the substrate, that is, the cell gap, in the liquid crystal panel in which the liquid crystal is sealed. However, when the air pressure difference is utilized, the pressure-reduced state is maintained inside the seal, and there is no force for pressing the substrate on the outer side of the seal. Therefore, there arises a problem that the inner and outer substrates of the sealing member are deformed, the cell gap becomes uneven, the sealing member is damaged, and the liquid crystal flows from the inside of the liquid crystal panel to the outside, resulting in deterioration of display quality.

Therefore, as a method of reducing the deformation of the substrate, for example, in Japanese Laid-Open Patent Publication No. Hei 11-326922, the following proposal is made to provide an annular second seal in such a manner as to surround the seal member in the outer side of the first seal member filling the liquid crystal. The two substrates are overlapped under reduced pressure and the first sealing member is filled with liquid crystal, and then the two substrates are opened under atmospheric pressure. At this time, since the inside of the second sealing member is kept under a reduced pressure at atmospheric pressure, the two substrates are bonded by the difference in air pressure.

However, in Japanese Laid-Open Patent Publication No. Hei 11-326922, there is a problem that when the overlapped substrates are returned to atmospheric pressure from a reduced pressure, the first sealing member and the sealed liquid crystal are attracted to be reduced. The reduced pressure region between the second seal in the pressed state and the first seal, thus causing damage to the first seal and leakage of the liquid crystal. Therefore, in Japanese Laid-Open Patent Publication No. 2002-122871, a proposal is made to arrange a double-layered seal at a predetermined interval from the first seal member so that the opening portions thereof are joined to form a second seal member. Thus, when returning to atmospheric pressure from a reduced pressure, The second seal is decompressed, and the area where the first seal and the second seal are collapsed is atmospheric pressure. Therefore, the first seal member is not attracted to the second seal member side, so that the problem of liquid crystal leakage is solved. Further, the substrate can be pressed from both sides by the stress generated by the difference in the air pressure between the two, so that the deformation of the substrate is also suppressed. Further, a method of preventing deformation of a substrate and preventing damage of the sealing member is proposed, for example, in Japanese Laid-Open Patent Publication No. 2002-328382, in which a first sealing member and an annular second sealing member are provided when the substrates are overlapped with each other. They do not touch each other.

However, in the method of bonding the substrates to each other by the difference in air pressure, as described in Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2002-328382, It is difficult to properly control the air pressure difference. Therefore, there are the following problems: the substrate is deformed, the seal is severely damaged, the cell gap becomes uneven, the cell gap itself cannot be formed, and the like. Further, in any of the above methods, after the bonded substrate is returned to the atmospheric pressure, the inside of the second sealing member is maintained in a reduced pressure state, and the substrate is deformed at a later stage. If the substrate is deformed as described above, the liquid crystal entering the first sealing member may be different, the shape of the first sealing member may be deformed, or the liquid crystal may leak. At this time, the quality of the liquid crystal display panel is significantly degraded, and depending on the degree, the function may not be realized.

Therefore, an object of the present invention is to provide a carrier substrate for a liquid crystal display panel, and a method of manufacturing the same, the carrier substrate of the liquid crystal display panel can prevent liquid crystal from impinging on the first sealing member and the first sealing member, and lowering the substrate The deformation, thereby making the cell gap uniform.

The present inventors have actively studied and found that the above problems can be solved by optimizing the pattern of the second sealing member, thereby completing the present invention.

That is, the above problems can be solved by using the carrier substrate of the liquid crystal display panel of the present invention.

[1] A carrier substrate for a liquid crystal display panel, comprising: two substrates bonded by a sealant; one or two or more display regions located between the two substrates, and having a first seal without an end point The liquid crystal is sealed in the first sealing member, and the non-closed region is located between the two substrates, outside the display region, and is determined by the second sealing member having the broken portion.

[2] The carrier substrate of the liquid crystal display panel according to [1], wherein an interval between one end and the other end of the disconnection portion is 0.1 mm or more and 20 mm or less.

[3] The carrier substrate of the liquid crystal display panel according to [1] or [2], wherein the second sealing member is formed by a combination of straight lines.

[4] The carrier substrate of the liquid crystal display panel according to [1] to [3], wherein the second sealing member comprises a curved line.

[5] The carrier substrate of the liquid crystal display panel according to [1] to [4], wherein the disconnection portion is a line formed by a straight line or a curved line.

[6] The carrier substrate of the liquid crystal display panel according to [1] to [5], wherein the second seal has a line width of 0.2 mm or more and 4.0 mm or less.

In addition, the above problem can utilize the carrying of the liquid crystal display panel of the present invention. The method of manufacturing the substrate is solved.

[7] A method for manufacturing a carrier substrate of a liquid crystal display panel, wherein a carrier substrate of a liquid crystal display panel is bonded by bonding two opposing substrates via a sealant, comprising the steps of: (a1) pairing the two substrates; a step of coating the first encapsulant to surround the pixel array region to form a frame-shaped display region; (b1) applying a second seal to the two of the two substrates in a partially broken state a step of forming a non-closed region; (c) a step of dropping liquid crystal into said display region; (d) providing a second frame forming said non-closed region on an outer side of said first frame forming said display region, and a step of overlapping the two substrates under pressure reduction without contacting the first frame with the second frame; (e) a step of returning the two stacked substrates to atmospheric pressure from a reduced pressure; and (f) a step of hardening the first sealant and the second sealant after the substrates are bonded to each other.

[8] A method for manufacturing a carrier substrate of a liquid crystal display panel, wherein a carrier substrate of a liquid crystal display panel is bonded by bonding two opposing substrates via a sealant, comprising the steps of: (a2) pairing the two substrates; Or both, the first encapsulant is applied to surround the pixel array region to form a frame-like display region; (b2) to either or both of the two substrates a step of applying a second sealant to form a non-closed region; (c) a step of dropping a liquid crystal into the display region; (d) providing an outer side of the first frame forming the display region a second frame of the non-closed region, wherein the first frame is not in contact with the second frame, and the two substrates are overlapped under reduced pressure; (e) the two overlapping substrates are restored from a reduced pressure And (f) a step of curing the first sealant and the second sealant after bonding the substrates to each other.

[9] The method of manufacturing a carrier substrate of a liquid crystal display panel according to [7] or [8], comprising the step of heating the two stacked substrates.

[10] The method for manufacturing a carrier substrate of a liquid crystal display panel according to [7], wherein in the step (f), the two substrates that are overlapped are at least 40 ° C and less than the above The sealing agent is cured by heating at a temperature of a nematic-isotropic phase transition temperature of the liquid crystal for 1 minute to 120 minutes.

[11] The method for manufacturing a carrier substrate of a liquid crystal display panel according to [10], further comprising the following step (g) after the step (f): heating the two stacked substrates to be equal to or higher than the liquid crystal The step of the nematic-isotropic phase transition temperature.

[12] The method for producing a carrier substrate of a liquid crystal display panel according to any one of [7], wherein the first sealant is measured by an E-type viscometer at 25 ° C and 1.0 rpm. The viscosity is greater than or equal to 20 Pa. s and less than or equal to 500 Pa. s.

[13] The method for producing a carrier substrate of a liquid crystal display panel according to any one of [7], wherein the first sealant is measured by an E-type viscometer at 80 ° C and 1.0 rpm. Viscosity exceeds 500 Pa. s.

[14] The method for producing a carrier substrate of a liquid crystal display panel according to any one of [7] to [13] wherein the first sealant has a viscosity at 25 ° C and 0.5 rpm as measured by an E-type viscometer. The ratio of η1 to the viscosity η2 at 25 ° C and 5.0 rpm, that is, the thixotropic index η1/η2 is 1.0 or more and 5.0 or less.

[15] The method for producing a carrier substrate of a liquid crystal display panel according to [7] to [14] wherein the first sealant contains a thermal radical generating agent, and a 10-hour half-life temperature of the thermal radical generating agent The temperature of 30 hours C to 80 ° C is defined as the temperature at which the concentration of the thermal radical generator is half when the thermal decomposition reaction is carried out for 10 hours at a fixed temperature.

According to the present invention, it is possible to provide a carrier substrate of a liquid crystal display panel having a uniform cell gap.

1. Carrier substrate of liquid crystal display panel and liquid crystal display panel

In the present invention, after bonding two substrates, the first sealing member defining the display region is referred to as a main sealing member, and the second sealing member defining a region other than the display region is referred to as a dummy seal. Further, the substrate on which the main seal and the dummy seal are formed is used as a carrier substrate of the liquid crystal display panel, and is cut along the outer periphery of the main seal, and a portion from which the dummy seal is removed is referred to as a liquid crystal display panel. In addition, sometimes the LCD panel is simple. It is called a liquid crystal panel or panel.

In general, a liquid crystal display panel can use a glass substrate in which a thin film transistor (TFT) or the like is formed in a matrix, and a substrate in which a color filter, a black matrix, or the like is formed. . Examples of the material of the substrate include polycarbonate, polyethylene terephthalate, polyethersulphone, or polymethyl methacrylate (PMMA). ) and glass. In the present invention, a glass substrate is preferred. Further, the opposing faces of the respective substrates may be subjected to an alignment treatment using an alignment film. The alignment film is not particularly limited, and for example, a well-known alignment film containing an organic alignment agent or an inorganic alignment agent can be used.

1 is a view showing an outline of a carrier substrate 10 of a first liquid crystal display panel of the present invention. The carrier substrate 10 of the liquid crystal display panel includes a substrate 11, a main seal 14, and a dummy seal 15. The main seal 14 and the dummy seal 15 are disposed between the two substrates. In addition, in the figure, if it is not necessary, the pattern of the upper substrate in the two substrates is omitted, and only the lower substrate 11 is shown. Further, in order to simplify the drawing, members formed on the substrate such as an alignment film, a thin film transistor, a wiring, a color filter, a black matrix, and the like are omitted, and the liquid crystal sealed between the two substrates is also omitted.

The main seal 14 is an endless seal provided to surround the pixel array region, defining a display area. The display area is an area surrounded by a main seal in which pixels are arranged. The so-called pixel refers to the smallest unit that constitutes a picture or image; the so-called pixel array area refers to The areas constituting the pixels of the liquid crystal display panel are arranged.

The line width of the main sealing member 14 differs depending on the size of the target liquid crystal display panel, etc., and the liquid crystal is sealed so as not to leak to the outside, preferably from 0.2 mm to 4.0 mm. One or more primary seals 14 are formed on the substrate. When a plurality of main seals are formed on one substrate, the interval D1 between the main seal 14 and the adjacent other main seal 14 is preferably 0.5 mm or more and 30.0 mm or less. Thereby, the workability when the carrier substrate of the liquid crystal display panel is cut along the outer periphery of each main seal can be improved, and the flatness of the panel can be maintained.

Moreover, an auxiliary seal line may be provided between the respective main seals 14. The function of the auxiliary sealing line is to prevent the cutting operation from being defective and to enlarge the crack of the substrate when the liquid crystal display panel is cut. At this time, the interval between one main seal 14 and the adjacent auxiliary seal line is preferably 0.5 mm or more and 30.0 mm or less. One or more auxiliary sealing lines may be provided between each of the main seals 14. When a plurality of auxiliary seal lines are provided between the respective main seals 14, the mutual spacing is preferably 0.5 mm or more and 30.0 mm or less.

The dummy seal 15 is located outside the main seal 14 and has a broken portion 15a at a portion thereof. The non-closed region is defined by the dummy seal 15 having the broken portion 15a. The dummy seal 15 may be linear or curved, or a combination of the two. The disconnection portion 15a is an opening that connects the inner side A1 and the outer side A2 of the dummy seal 15. As will be described in more detail below, in general, the two substrates are brought back to atmospheric pressure after being superposed under a reduced pressure of several hundred Pa (Pa) to several thousand Pa. At this time, the disconnection portion 15a is brought into a state of being decompressed. A1, the pressure difference of A2 which is lower than A1 or under atmospheric pressure is gradually relieved. Therefore, a predetermined cell gap can be obtained, the substrate is not deformed, and a uniform cell gap is formed. The disconnection portion 15a may be not only the opening shown in Fig. 1, but also a conduit formed by two of a straight line or a curved line. In addition, the line-shaped disconnection portion will be described below.

When the superposed substrates are returned to atmospheric pressure from a reduced pressure, the speed at which the air pressure difference between A1 and A2 is gradually relaxed can be controlled by the interval D2 of the disconnecting portions 15a. The interval D2 of the broken portion 15a is preferably 0.1 mm or more and 20 mm or less. The interval D2 is the interval between the one end and the other end of the seal of the non-joining portion of the disconnecting portion 15a, and is the interval between the starting point 16a and the ending point 16b in Fig. 1 . By appropriately setting the interval D2, a predetermined cell gap can be obtained. Further, if the interval D2 is appropriately set, the difference in air pressure between A1 and A2 can be eliminated in a few seconds to several minutes, so that a uniform cell gap can be obtained without deforming the substrate.

The line width of the bonded dummy seal 15 is preferably 0.2 mm or more and 4.0 mm or less, more preferably 0.5 mm or more and 2.0 mm or less. This makes it possible to form a sufficient reduced pressure zone for obtaining the cell gap, and is also economically advantageous.

As described in the present embodiment, when the dummy seal 15 is provided to surround the main seal 14, it is preferable to form at least one or more disconnecting portions 15a. When the disconnection portion 15a is formed, the installation position is not particularly limited. When a plurality of disconnection portions 15a are formed, it is preferable to adjust the set position depending on whether the number of settings is even or odd. For example, when the disconnection portion 15a When the number of settings is an even number, it is preferable to arrange symmetrically with the center of the dummy seal 15. Further, when the number of installations is an odd number, an even number of disconnection portions 15a may be provided under the above-described conditions, and the other disconnection portion 15a may be provided at an arbitrary position.

In order to easily cut the liquid crystal display panel and further maintain the flatness of the panel, the interval D3 between the main seal 14 and the dummy seal 15 is preferably 0.5 mm or more and 30.0 mm or less. D3 represents the distance between the dummy seal 15 closest to the main seal 14 and the main seal 14.

When the substrates are bonded to each other, the broken portions 15a may be joined by the sealant collapse. However, since the bonded portion is extremely thin, it is easily broken by the difference in air pressure at the time of returning to atmospheric pressure from a reduced pressure. Therefore, the effect of the present invention can be achieved even in this case.

In the present invention, the dummy seal having the broken portion is not limited to the above embodiment. Hereinafter, a carrier substrate of a liquid crystal display panel having a dummy seal of the above-described configuration will be described with reference to the drawings. In any of the drawings shown below, the carrier substrate of the liquid crystal display panel after bonding the glass substrates to each other is a plan view seen from the upper portion. As described above, in order to simplify the drawing, the glass substrate located on the upper portion, the alignment film on the substrate, and the liquid crystal between the two substrates are omitted. Further, unless otherwise specified, the interval D1 between the adjacent main seals, the interval D2 of the broken portions, and the interval D3 between the main seal and the dummy seal all conform to the conditions described in FIG.

2 is a schematic view of a carrier substrate of a second liquid crystal display panel of the present invention. On the carrier substrate of the liquid crystal display panel, four dummy seals 32 are provided on the outer circumference of the four main seals 31 formed on the substrate 30. Virtual secret On the seal member 32, a disconnecting portion 33 having a predetermined size is formed on the side of the main seal member 31, respectively. As described above, when a plurality of dummy seals 32 are provided, it is preferable that the force of attracting the substrate generated when the substrates are bonded is uniform on the substrate surface. It is therefore preferred to provide an even number of dummy seals that are symmetrically disposed through the centerline passing through the center of the substrate. The shapes of the dummy seals 32 may all be the same or different from each other, or may be the same or different. In order to prevent the substrate from being deformed and to form a uniform cell gap, the distance D4 between the side of the main seal 31 of the dummy seal 32 after the bonded substrate and the outer portion thereof may be 0.5 mm or more and 30.0 mm or less. Japanese Patent Publication No. 2002-328382 discloses that the dummy seal is damaged, and therefore it is preferable to set the line width to be equal to or greater than 1.5 times the main seal. However, in the embodiment of the present invention, the disconnecting portion 33 is provided, and the dummy seal is not damaged. Therefore, in the present invention, as long as the line width of the dummy seal 32 is greater than or equal to 0.7 times the line width of the main seal 31 and less than 1.5 times, the amount of the sealant can be reduced, so that it is economically advantageous. .

3 is a schematic view of a carrier substrate of a third liquid crystal display panel of the present invention. On the carrier substrate of the liquid crystal display panel, two dummy seals 42 are provided on the outer sides of the six main seals 41 formed on the substrate 40. The disconnection portion 43 is symmetrically formed on each of the dummy seals 42 with reference to the main seal 41. The interval D4 between the side of the main seal 41 of the dummy seal 42 after the bonding of the substrate and the outer portion thereof is the same as described above.

4 is a schematic view showing a carrier substrate of a fourth liquid crystal display panel of the present invention. A line-shaped disconnecting portion A is formed on the dummy seal 52 of the substrate 50. As described above, if the dummy seal 52 having the line-like disconnection portion A is provided On the outer circumference of the main seal 51, when the superposed substrate is returned to atmospheric pressure from a reduced pressure, the relaxation of the air pressure difference becomes slower than in the case where the non-pipeline disconnection portion is provided. 5 is a schematic view of a carrier substrate of a fifth liquid crystal display panel of the present invention. As shown in FIG. 5, a dummy seal 62 having two or more duct-shaped disconnecting portions B may be provided on the outer circumference of the main seal 61 of the substrate 60. When a plurality of broken portions B are provided, it is preferable to arrange them symmetrically as much as possible at the center of the main seal 61. When the line-like broken portions A and B are formed, the interval D2 of the above-mentioned broken portions is equal to the average distance between the seals forming the pipes. The interval D2 of the disconnection portion is D2' in Fig. 4 and D2" in Fig. 5. The length of the line-shaped disconnection portion is not particularly limited, but air resistance may occur in the disconnection portion, so it is preferable that Consider the air resistance to determine its length.

Fig. 6 is a schematic view showing a carrier substrate of a sixth liquid crystal display panel of the present invention. As shown in FIG. 6, the dummy seal 72 is provided with two broken portions 73. Each of the disconnection portions 73 is symmetrically provided at the center of the substrate 70. The breaking portion 73 can be disposed after cutting the sealing member 72 at the desired position after forming the dummy seal 72 without the end point; or the outer side of each of the main sealing members 71 to surround the main sealing member 71 from the starting point Formed to the end point. Moreover, it can also be applied to the same shape by means of screen printing or the like.

2. Method for manufacturing a carrier substrate of a liquid crystal display panel

The method for manufacturing a carrier substrate of a liquid crystal display panel of the present invention is preferably produced by: (a1) applying a first encapsulant to each of the two substrates so as to surround the pixel array region. To form a frame-like display area (b1) a step of applying a second sealant in a partially broken state to form a non-closed region to any one of the two substrates; (c) a step of dropping a liquid crystal into the display region; (d) providing a second frame forming the non-closed region on the outer side of the first frame forming the display region, and overlapping the two substrates under reduced pressure without contacting the first frame with the second frame And (e) a step of restoring the superposed two substrates to atmospheric pressure under reduced pressure; and (f) a step of hardening the first encapsulant and the second encapsulant after bonding the substrates to each other.

The step (a1) may be the step (a2) of the step of applying a first sealant to surround the pixel array region to form a frame-shaped display region for either or both of the substrates. . Further, the above step (b1) may be the step (b2) of applying a second sealant in a partially broken state to either or both of the above substrates to form a non-closed region. Hereinafter, in order to simplify the description, the manufacturing methods of (a1) and (b1) will be described unless otherwise specified.

Fig. 7 is a view for explaining a method of manufacturing a carrier substrate of a liquid crystal display panel of the present invention. In Fig. 7, the state before the two substrates are bonded is shown.

In the step (a1), the first sealant is applied to each of the two substrates so as to surround the pixel array region, thereby forming a frame-shaped display region. The application of the first encapsulant in such a manner as to surround the pixel array region means that the first encapsulant is coated to include the pixel array region of the liquid crystal display panel. area. The first frame 21 formed in the above manner becomes a main seal after bonding the substrate.

In the step (b1), the second sealant is applied to the two substrates in a partially broken state to form a non-closed region. The second frame 22 formed in the above manner becomes a dummy seal.

After the substrates are bonded to each other, the positions of the respective seals are adjusted so as to be spaced apart by a predetermined interval. In FIG. 7, in order to simplify the drawing, only one of the plurality of first frames 21 is marked with an element symbol, and other symbols are omitted.

The coating method of the sealant can be a well-known technique, and is not particularly limited. A preferred method is coating using a dispenser, and coating using screen printing. When manufacturing a small liquid crystal display panel, it is preferable to use screen printing by the viewpoint of improving productivity. As the sealant, a mixed sealant in which an ultraviolet curable resin and a thermosetting resin are mixed is usually used. The sealant is used not only for forming a frame but also as an adhesive for bonding the two substrates ' at a fixed interval. The sealants used in forming the respective frames do not need to be the same, and different types can be used depending on the use and the like. Preferred sealants in the present invention are described in detail below.

In the present invention, the frame formed by applying the sealant may be formed on any of the two substrates or may be formed on the two substrates. The combination of the first frame formed by applying the first sealant and the second frame coated with the second sealant includes, for example, five types of patterns as described below. The first pattern is that all of the first frame and the second frame are disposed on one of the substrates. The second pattern is that all the first frames are disposed on one of the substrates, and the A second frame is provided on the other substrate. The third pattern is that all the first frames are disposed on one substrate, and the second frame is disposed on the two substrates. The fourth pattern is that the first frame is disposed on the two substrates, and all the second frames are disposed on one of the substrates. The fifth pattern is that the first frame and the second frame are disposed on the two substrates. Moreover, the frame formed on the two substrates also includes a case where one frame forming an area is provided on the two substrates.

The method of disposing the disconnection portion 23 is not particularly limited. For example, when the sealant for forming the dummy seal is applied to the substrate 11 along the outer circumference of the first frame 21, coating may be performed from the start point to the end point, and the start point and the end point are different from each other, thereby forming The broken portion 23. Alternatively, a portion of the frame that becomes the portion of the broken portion 23 may be removed after the frame having no end point is provided by applying the sealant for forming the dummy seal. When a part of the frame is removed, it can be easily removed by using a jig made of plastic or SUS stainless steel or the like for removing the residue.

In the step (c), an appropriate amount of the liquid crystal 24 is dropped onto the inside of each of the first frames 21. The liquid crystal is usually dropped under atmospheric pressure. It is preferable that the minute liquid crystal 24 is dropped according to the size of the first frame 21 to be accommodated in the first frame 21. Therefore, it is possible to prevent the capacity of the dropped liquid crystal 24 from exceeding the capacity of the first frame 21 after the bonding and the space surrounded by the substrate, thereby applying an excessive pressure to the first frame 21, so that the main seal formed by the first frame 21 is difficult to receive. damage.

In the step (d), the substrate 11 of the liquid crystal 24 is dropped, and is superposed on the other substrate 27 under reduced pressure. The above overlap can be performed using, for example, a vacuum bonding device. The apparatus is not particularly limited as long as it can overlap the two substrates under reduced pressure. The substrate is such that the first frame 21 and the second frame 22 are not in contact with each other The ways overlap. As described above, in order to overlap the substrate without contacting the first frame 21 and the second frame 22, it is preferable that both the first frame 21 and the second frame 22 are provided on the same substrate. At this time, it is preferable that the spacer 28 is previously spread on the substrate 27 as shown in FIG. The spacers 28 can effectively maintain uniform cell gaps, and generally use spherical bismuth bismuth oxide particles. Further, the sealant 28 may be contained in the sealant. The type and size of the spacers 28 can be appropriately selected depending on the intended cell gap.

Between the substrates which were overlapped under reduced pressure, it was returned to atmospheric pressure from the reduced pressure in the step (e). The substrates thus overlapped are as shown in FIG. At this time, the region (A1) located on the inner side of the dummy seal 15 and on the outer side of the main seal 14 is in a decompressed state, and thus a difference in air pressure is generated between the region (A2) outside the dummy seal 15. Therefore, the two substrates are pressed from the two outer sides. At this time, the atmosphere self-breaking portion 15a slowly enters A2, and the decompressed state in A2 is close to the surrounding air pressure (the air pressure of A1). After the appropriate time has elapsed, the difference in air pressure between the two disappears, so that a uniform cell gap can be formed without deforming the substrate. Moreover, since it is not necessary to continue to apply unnecessary pressure to the substrate thereafter, the flatness of the substrate can be ensured.

The relaxation rate of the air pressure difference between A1 and A2 can also be controlled by recovering the pressure of the environment in which the substrate is placed from the reduced pressure to the atmospheric pressure. Further, the relaxation speed of the air pressure difference can be controlled by controlling the interval between the disconnection portion 15a and the speed of returning to the atmospheric pressure.

Thereafter, in the step (f), the sealant between the substrates is hardened. It can be hardened by irradiating an electron beam, ultraviolet light, visible light, or the like, or by heating. The hardening conditions can be appropriately selected depending on the composition of the sealant. In addition, When a liquid crystal display panel having a small display area is manufactured, the ratio of the light shielding portion is increased by the wiring of the black matrix or the cross-cut seal, so that it is preferable to perform hardening by heating. The black matrix is determined by a photoresist, and surrounds the three primary colors of light constituting the color filter, that is, R (red) G (green) B (blue) light, and has a lattice shape. Moreover, the means for irradiating ultraviolet rays or heating is not particularly limited. Examples of the heating device include an oven, a hot plate, and a hot press.

In order to prevent the offset between the substrates during heating, a temporary joint may be performed in advance. The method of temporary joining is not particularly limited, and well-known techniques can be used. For example, a photocurable temporary bonding agent may be applied, and the substrates may be superimposed and then irradiated with light. Further, a light curing agent or the like may be applied to the outer periphery of the first frame 21, and then the substrates may be superimposed and then irradiated with light. Further, the second frame 22 may be formed by a sealant containing a photoradical polymerization initiator to perform temporary bonding.

In the above step (f), the superposed substrate is heated at a temperature of 40 ° C or higher and less than the nematic-isotropic phase transition temperature of the liquid crystal for 1 minute to 120 minutes to cure the sealant. When the sealant is cured in the above manner, deformation of the sealing portion, leakage of the liquid crystal to the sealing portion, or leakage of the sealant component to the liquid crystal display panel having a small liquid crystal portion can be obtained. Such a liquid crystal display panel has excellent reliability. The sealing portion refers to a sealing pattern formed of a sealant, and the liquid crystal portion refers to a portion filled with liquid crystal. The nematic-isotropic phase transition temperature of the liquid crystal (abbreviated as "NI temperature") means a temperature at which the liquid crystal changes from a nematic phase to an isotropic phase which does not exhibit liquid crystallinity. The NI temperature also depends on the type of liquid crystal, typically 70 ° C ~ 90 ° C. The above hardening is also called "Not less than NI hardening." The symbol "~" indicates the value including both ends.

In the liquid crystal display panel manufactured by the hardening step of the NI, the mechanism of deformation of the sealing portion, leakage of the liquid crystal to the sealing portion, or leakage of the sealant component to the liquid crystal portion is presumed as follows.

The case where the liquid crystal material is filled in the liquid crystal portion and is in contact with the uncured sealant will be described as an example. The liquid crystalline substance in the nematic state has properties similar to those of crystals, and thus is difficult to be compatible with the sealant. Therefore, even if the liquid crystal portion is in direct contact with the sealant, the sealant component, particularly the uncured organic component, is hardly eluted into the liquid crystal. On the other hand, if the liquid crystalline substance is in an isotropic state, the properties of the liquid crystal are lost and the order of the molecules is almost completely disturbed, so that it becomes easy to be compatible with the sealant. Further, when the liquid crystalline material is in an isotropic state, the volume is rapidly expanded, so that when the liquid crystal portion is in direct contact with the sealant, the degree of adhesion between the two is improved. Therefore, the components of the sealant, in particular the uncured organic component, tend to bleed out to the liquid crystal portion. Further, when the liquid crystalline material is in the isotropic phase, the fluidity is improved, so that it is easy to enter the sealing portion. Therefore, by curing the sealant at a temperature of 40 ° C or more and less than the NI temperature, it is possible to suppress elution of the sealant component, particularly the uncured organic component, to the liquid crystal portion or the liquid crystal molecules to the seal portion. However, its mechanism is not limited to this.

Further, when the viscosity of the sealant at the time of heat curing is too low, there is a problem that liquid crystal easily leaks to the sealing portion. This phenomenon is caused not only by the "good compatibility" between the liquid crystal and the sealant as described above, but also because the seal portion is deformed or broken due to the liquid crystal after the seal is softened. However, in the hardening process of NI, due to the lower temperature, it has the following advantages: It is difficult to cause a decrease in the viscosity of the sealant, and it is difficult for the liquid crystal to leak to the sealing portion.

In the hardening process less than NI, the lower limit of the temperature is 40 ° C or more. If the temperature is less than 40 ° C, the difference from the room temperature becomes small, and it becomes difficult to control the reaction temperature. Further, if the lower limit temperature is high, the curing reaction of the sealant is easily promoted, so the lower limit temperature is preferably 60 °C. The upper limit of the above temperature is not particularly limited as long as it is less than the NI temperature. However, the liquid crystal generally used has a NI temperature of 70 ° C to 90 ° C, so it is preferred that the upper limit of the hardening temperature is less than 90 ° C.

In the hardening process of NI, the hardening time is preferably from 1 minute to 120 minutes. When the hardening time falls within the above range, the sealant can be sufficiently hardened and the production efficiency is also excellent. The hardening time is particularly good for 30 minutes to 90 minutes.

After the hardening of the NI, it is preferred that the sealant is completely cured, but it is only hardened to a certain level. The level of the hardening means that when the superposed substrate is heated to a temperature equal to or higher than the NI temperature of the liquid crystal, the sealant component does not bleed out into the liquid crystal, or the liquid crystal does not immerse into the level of the sealing portion. For example, when the sealant contains a compound having a polymerizable group such as a propylene group, the hardening level of the above-mentioned sealant is preferably "the residual ratio of the polymer group" is 60% or less.

The "residual ratio of the polymerizable group" is defined as the ratio of the amount of the polymerizable base in the sealant after the hardening of the NI to the amount of the polymerized base in the sealant before the hardening of the NI, and indicates the degree of the hardening reaction. index of. Examples of the polymerizable group include a propylene group, a methacryl fluorenyl group, and an epoxy group.

The residual ratio of the polymer group can be, for example, substantially less than the hardening of the NI Under the same conditions, the curing calorific value obtained by heating the sealant of the present invention was determined. It is preferable to use a differential scanning calorimeter (DSC) in the measurement. That is, the uncured sealant of the present invention was heated under the same conditions as the hardening of less than NI using DSC, and the calorific value x measured during the period was determined. On the other hand, the uncured sealant of the present invention is heated under conditions in which the sealant is completely cured (for example, at 150 ° C for 1 hour), and the calorific value y measured at this time is obtained. The residual ratio of the polymer group is determined by using the following formula (1) using x and y.

Residual rate of polymerized base (%) = (1-x/y) × 100 (1)

When the sealant used in the present invention contains a large amount of a compound having a propenyl group or a methacryloyl group (referred to collectively as "(meth)acryl group"), as long as the (meth)acryl group remains The rate is less than or equal to 60%. The sealant contains a large amount of a compound having a (meth)acryl group, and indicates that the amount of the polymerizable functional group contained in the sealant accounts for 50% or more of the (meth)acryl group.

After the hardening of the NI, step (g) may be provided: a step of heating the substrate to a temperature equal to or higher than the above-mentioned NI temperature (also referred to as "post-hardening"). Thereby, the sealant can be surely cured. Further, in the step (g), if the liquid crystal is temporarily heated to re-align the isotropic phase, that is, the liquid crystal is annealed, the performance of the liquid crystal can be improved, which is preferable. Before the step (g), the sealant has hardened to a certain level. Therefore, even if the liquid crystal becomes an isotropic phase in the step (g), it is difficult for the sealant component to bleed out to the liquid crystal portion, and it is difficult for the liquid crystal to infiltrate into the sealing portion. Therefore, the temperature and hardening in step (g) The time and the like are not particularly limited and may be appropriately determined depending on the type of liquid crystal and the sealant to be used.

As shown in FIG. 1, the state of the carrier substrate of the liquid crystal display panel manufactured by the present invention is such that the two substrates are tightly bonded by the respective sealing members. Moreover, even if the substrates are bonded to each other by the air pressure difference, a large air pressure difference does not occur, and even if a large air pressure difference is generated, the state does not continue, so that the substrate is not deformed, and each main seal The cell gap of the piece is also uniform. Therefore, if the bonded substrate is cut at a predetermined interval along the outer circumference of the main seal, a liquid crystal display panel having excellent quality can be obtained.

3. Sealant

The viscosity of the first sealant for forming the main seal at 25 ° C and 1.0 rpm measured by an E-type viscometer is preferably 20 Pa or more. s and less than or equal to 500 Pa. s. If the viscosity is less than 20 Pa. s, the seal is easy to expand on the substrate. If the seal is expanded as described above, it may cause the thickness of the dropped liquid crystal to be larger than the thickness of the sealant applied to the substrate to form the main seal. Therefore, the liquid crystal contacts the overlapping substrate before the sealing agent, so that the liquid crystal may reach the outer surface of the first frame on the substrate surface, and it is difficult to seal the liquid crystal. On the other hand, if the above viscosity exceeds 500 Pa. s, even if it is desired to use a pressure difference to bond the substrate, it is difficult to bring the sealant to a predetermined thickness, so that it is difficult to adjust the cell gap to a good extent. As can be seen from the above, the above viscosity is preferably 20 Pa or more. s and less than or equal to 250 Pa. s, better than 70 Pa. s and less than or equal to 210 Pa. s. Such a sealant can ensure moderate fluidity even when it is not at a high temperature, and therefore, any of a screen printing method and a dispensing method of a dispenser can be used. In the method, the applicability of the sealant was good. Further, such a sealant easily reaches a predetermined thickness when the substrate is bonded, so that the substrate is less likely to be deformed, and it is also difficult to cause liquid crystal leakage. Further, the coatability in the present invention is an index indicating the ease of applying a sealant to a substrate. When the viscosity of the first sealant is within this range, when the carrier substrate of the liquid crystal display panel is manufactured by the production method of the present invention, it is easy to form the sealant at a predetermined interval and to adjust the cell gap well, which is preferable.

In addition, the viscosity of the first sealant at 80 ° C, 1.0 rpm is preferably greater than 500 Pa. s. The viscosity at 80 ° C means that the above composition is placed in a cup of an E-type rotational viscometer, heated to 80 ° C at a temperature increase rate of 5 ° C / min., and then placed at 80 ° C for 5 minutes, and then according to the above method The measured viscosity. In general, when the thermosetting resin is cured by heat, the viscosity of the resin is once lowered, and as the hardening reaction progresses, the viscosity is again increased. Generally, when manufacturing a liquid crystal display panel, the sealing agent is heated and hardened after superposing a board|substrate mutually. Heating is usually carried out at a temperature ranging from about 40 ° C to about 150 ° C. Therefore, if the sealant as described above is used, the sealant can maintain a high viscosity, and thus does not cause problems such as leakage of the liquid crystal to the sealing portion. The viscosity at 80 ° C, 1.0 rpm, more preferably 10 ³ Pa. s~10 ⁹ Pa. s, especially good is 10 ³ Pa. s~10 ⁷ Pa. s. Moreover, the measurement limit of the E-type rotational viscometer is usually about 780 Pa when using rotor number 5. s. Therefore, assume that the viscosity at 80 ° C, 1.0 rpm exceeds 780 Pa. In the case of s, it is preferred to carry out the measurement using a parallel plate method. When the measurement is carried out by the parallel plate method, a viscoelastic type measuring instrument such as RheoStress RS150 (manufactured by HAAKE) can be used, and measurement can be carried out according to the standard method of the model.

Further, the thixotropy index of the sealant of the present invention is preferably 1.0 or more and 5.0 or less, more preferably 1.1 or more and 5.0 or less, particularly preferably 1.2 or more and 2.5 or less. The thixotropic index refers to the ratio (η1/η2) of the viscosity η1 at 25 ° C, 0.5 rpm, and the viscosity η 2 at 5.0 rpm measured by an E-type viscometer at 25 ° C. That is, the thixotropic index is the ratio of the viscosity measured at a lower shear rate to the viscosity measured at a higher shear rate. Fluids with a higher thixotropic index have a high viscosity at low shear rates but a low viscosity at high shear rates. Therefore, the above-mentioned sealant has a low viscosity when applied in a high shear rate environment, and the coatability of the sealant to the substrate can be improved. On the other hand, when the liquid crystal leaks to the coated main seal, the sealant is in an environment of low shear speed. The above-mentioned sealant has a high viscosity in a low shear rate environment, so that liquid crystal does not easily leak to the sealing portion. The viscosity of the sealant is an E-type rotational viscometer (for example, a DVT-III ULTRA model manufactured by BROOKFIELD, and a CP-52 cone with a radius of 12 mm and an angle of 3 ∘). The plate type sensor is a value measured after the sealant is left at a predetermined temperature for 5 minutes.

From the viewpoint of obtaining the above viscosity and strength, it is preferred that the sealant contains (1) an acrylic resin, (2) one or more epoxy groups and a (meth) propylene group in one molecule. ) Acrylic modified epoxy resin, (3) filler. The sealant may additionally suitably contain (4) a thermal radical generator, (5) an epoxy resin, (6) a latent epoxy hardener, (7) a photoradical polymerization initiator, and (8) a thermoplastic polymerization. Things, and (9) other additive. When heat is used to harden the sealant, it is preferred to use (4) a thermal radical generator; and when light is used to harden the sealant, it is preferred to use (7) a photoradical polymerization initiator. . Further, a thermal radical generating agent and a photoradical polymerization initiator may be used in combination to cure the sealant by light and heat. (2) A (meth)acrylic modified epoxy resin having one or more epoxy groups and a (meth)acryl group in one molecule is referred to as a "modified epoxy resin".

The sealant can be arbitrarily produced by mixing the above components as long as the effects of the present invention are not impaired. For the above mixing, for example, a well-known kneading machine such as a double-wrist mixer, a drum kneader, a twin-axis extruder, a ball mill kneader, or a planetary mixer can be used. The kneading temperature is uniformly kneaded in order to prevent gelation, and the temperature of the sealant during kneading is preferably set to 15 ° C to 35 ° C. The obtained mixture is preferably subjected to filtration using a filter as needed, and then subjected to vacuum defoaming treatment, and further stored in a state of being sealed and filled in a glass bottle or a polymer container. Further, when the type, molecular weight, mixing ratio, particle size, type, mixing ratio, or amount of the additive used in the compound used in the compound contained in the sealant are adjusted, the viscosity of the sealant can be adjusted.

Hereinafter, preferred components of the present invention will be described in detail.

(1) Acrylic resin The acrylic resin contained in the sealant means an acrylate and/or methacrylate monomer or an oligomer thereof. Examples of such compounds include the following compounds.

Diacrylate and/or two of polyethylene glycol, propylene glycol, polypropylene glycol, etc. Methacrylate; di(2-hydroxyethyl)isocyanurate diacrylate and / or dimethacrylate; 1 mole of neopentyl glycol addition of 4 moles or more than 4 moles Diacrylate and/or dimethacrylate of the diol obtained after ethylene oxide or propylene oxide; after adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A Diacrylate and/or dimethacrylate of the obtained diol; 3 molars obtained by adding 3 moles or more of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane a di- or tri-acrylate of an alcohol and/or a di- or tri-methacrylate; a diol obtained by adding 4 moles or more than 4 moles of ethylene oxide or propylene oxide to 1 molar bisphenol A Diacrylate and/or dimethacrylate; tris(2-hydroxyethyl)isocyanurate triacrylate and/or trimethacrylate; trimethylolpropane triacrylate and/or top three Acrylate, or oligomer thereof; pentaerythritol triacrylate and/or trimethacrylate, or oligomer thereof; polypentate of dipentaerythritol and/or polymethyl Acrylate; tris(propyleneoxyethyl)isocyanurate; caprolactone modified tris(propyleneoxyethyl)isocyanurate; caprolactone modified tris(methacryloyloxyl) Base ethyl)isocyanurate; polyacrylate and/or polymethacrylate of alkyl-modified dipentaerythritol; polyacrylate and/or polymethacrylate of caprolactone-modified dipentaerythritol; hydroxyl group Neopentyl glycol diacrylate and/or dimethacrylate; caprolactone modified hydroxypivalic acid neopentyl glycol diacrylate and/or dimethacrylate; ethylene oxide modification Phosphate acrylate and/or dimethacrylate; ethylene oxide modified alkylated phosphate acrylate and/or dimethacrylate; neopentyl glycol, trimethylolpropane, pentaerythritol oligoacrylate And / or oligomeric methacrylate and the like.

Examples of the acrylic resin include a resin which is completely (meth)acrylated by reacting all of the epoxy groups of the epoxy resin with (meth)acrylic acid.

Examples of the epoxy resin used at this time include: cresol varnish type epoxy resin, phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy Resin, trisyl alcohol type epoxy resin, trisphenol type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, and biphenyl type epoxy resin.

The number average molecular weight of the acrylic resin contained in the sealant is preferably from 300 to 2,000. Since the solubility and diffusibility of the acrylic resin in the liquid crystal are lowered, the display quality of the manufactured liquid crystal display panel is improved. Moreover, the compatibility with (5) epoxy resin is also improved. The number average molecular weight of the acrylic resin can be measured, for example, by gel permeation chromatography (GPC) using polystyrene as a standard. Several types of the above-mentioned acrylic resin may be combined in the sealant. It is preferred to use a water washing method or the like to increase the purity of the acrylic resin contained in the sealant.

(2) modified epoxy resin The modified epoxy resin is a compound having both a (meth)acryl group and an epoxy group in one molecule. Examples of such a compound include: reacting an epoxy resin such as a bisphenol type epoxy resin or a novolac type epoxy resin with (meth)acrylic acid or phenyl methacrylate, for example, under a basic catalyst. The resulting resin. Such a modified epoxy resin has both an epoxy group and a (meth)acryl group in the resin skeleton, and thus the liquid crystal sealing agent (1) C The olefinic resin is excellent in compatibility with the epoxy resin (5) to be described later. Therefore, a cured product having a high glass transition temperature (Tg) and excellent adhesion can be obtained.

Examples of the epoxy resin which is a raw material for the modified epoxy resin include a cresol varnish type epoxy resin, a phenol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and the like. A phenol methane type epoxy resin, a trisphenol type epoxy resin, a trisphenol type epoxy resin, a dicyclopentadiene type epoxy resin, and a biphenyl type epoxy resin. Further, it is preferred to use a molecular distillation method, a cleaning method, or the like to increase the purity of the modified epoxy resin.

The ratio of the (1) acrylic resin to the (2) modified epoxy resin contained in the sealant of the present invention is an arbitrary value. For example, the sealant of the present invention may contain no (2) modified epoxy resin but only (1) acrylic resin. At this time, a sealant which makes it difficult for the liquid crystal to leak to the sealing portion can be obtained. Further, the sealant of the present invention may contain only (1) an acrylic resin and only (2) a modified epoxy resin. At this time, a sealant having a good adhesive strength can be obtained by using a combination with an epoxy hardener. Further, the sealant of the present invention may contain (1) an acrylic resin and (2) a modified epoxy resin. At this time, the ratio (weight ratio) of the contents of the two resins is preferably acrylic resin 10 to 70: modified epoxy resin 90 to 30, more preferably acrylic resin 20 to 50: modified epoxy Resin 80~50. Thereby, the adhesion reliability of the sealant can be improved. When mixing (1) acrylic resin and (2) modified epoxy resin, it may also be called "resin unit".

(3) Filler The filler refers to a filler added to control the viscosity of the sealant, to improve the strength of the sealant, to control the linear expansion property, and the like. Fill in Filling can improve the bonding reliability of the sealant. The filler is not particularly limited as long as it is of a type generally used in the field of electronic materials. Examples of such fillers include inorganic fillers and organic fillers. Examples of the inorganic filler include: calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum citrate, bismuth citrate, iron oxide, titanium oxide, aluminum oxide (Alumina), zinc oxide, cerium oxide, potassium titanate, Kaolin, talc, glass beads, sericite active white clay, bentonite, aluminum nitride, and tantalum nitride. Examples of the organic filler include polymer particles having a softening point temperature exceeding 120 ° C as measured by a ring and ball method [JACT test method: RS-2]. Specific examples of such polymer particles include fine particles of polystyrene and a copolymer copolymerized with a monomer copolymerizable therewith, polyester fine particles, polyurethane fine particles, and gum fine particles.

Among them, the filler is preferably an inorganic filler. The reason for this is that the linear expansion coefficient of the sealant can be lowered to maintain the sealant in a good shape. In particular, cerium oxide or talc has an advantage of being difficult to transmit ultraviolet rays.

The shape of the filler is not particularly limited, and may be any of a regular shape such as a spherical shape, a plate shape, and a needle shape, or an irregular shape. The average primary particle diameter of the filler is preferably 1.5 μm or less, and the specific surface area thereof is preferably 1 m ² /g to 500 m ² /g. The reason for this is that if the average primary particle diameter and the specific surface area of the filler are within the above range, the sealant containing the filler is excellent in the balance between thixotropy and viscosity. The average primary particle diameter of the filler can be measured by a laser diffraction method disclosed in JIS Z8825-1. Further, the specific surface area measurement can be measured by the BET method disclosed in JIS Z8830.

The content of the filler in the sealant relative to 100 parts by weight of the resin unit The amount is preferably from 1 part by weight to 50 parts by weight, more preferably from 10 parts by weight to 30 parts by weight. When the content of the filler is within the above range, the above thixotropic index is easily controlled to be within 1.0 to 5.0.

Further, it is preferred that the sealant contains two or more kinds of the above fillers. Specifically, two or more types of fillers having different types of materials are used in combination, or two or more types of fillers having the same material and different average particle diameters (the difference in average particle diameter is 0.3 μm or more) are used in combination. material.

(4) Thermal radical generator The thermal radical generating agent refers to a compound which generates a radical after heating, that is, a compound which absorbs thermal energy and decomposes to generate a radical species. Such a thermal radical generator can be preferably applied to the case where the sealant is hardened by heating. In order to achieve a balance between viscosity stability and hardenability of the sealant, the content of the thermal radical generating agent in the sealant is preferably from 0.01 part by weight to 3.0 parts by weight with respect to 100 parts by weight of the resin unit.

The 10-hour half-life temperature of the thermal radical generator is preferably from 30 ° C to 80 ° C, more preferably from 50 ° C to 70 ° C. The 10-hour half-life temperature is a temperature at which the thermal radical generating agent reaches a half of the original value when the thermal radical generating agent is subjected to a thermal decomposition reaction at a constant temperature for 10 hours in an inert gas. In general, a thermal radical generator having a low 10-hour half-life temperature is liable to generate radicals at a relatively low temperature, and thus the sealant containing the same is easily hardened even at a low temperature. On the contrary, a thermal radical generator having a high 10-hour half-life temperature is less likely to generate radicals, and thus the sealant containing the same has low hardenability. Therefore, if the thermal radical generator is 10 When the hour half-life temperature is within the above range, the viscosity stability and the hardenability can be well balanced.

In particular, when the 10-hour half-life temperature of the thermal radical generator is within the above range, the hardening of the sealant can be promoted in the hardening process less than NI, which is preferable.

The 10-hour half-life temperature can be obtained by the following method. When the thermal decomposition reaction is expressed by a linear equation, the following formula (2) holds.

Ln(C ₀ /C _t )=kd×t (2) C ₀ : initial concentration of thermal radical generator C _t : concentration of thermal radical generator after time t kd: thermal decomposition rate constant t: reaction time The half life is the time at which the concentration of the thermal radical generator becomes half, that is, the time at which C _t = C ₀ /2 is established. When the half life of the thermal radical generator is time t, the following formula (3) holds.

Kd=(1/t). Ln2 (3)

On the other hand, when the temperature dependence of the velocity constant is expressed by the Arrhenius equation, the following formula (4) holds.

Kd=Aexp(-ΔE/RT) (1/t). Ln2=Aexp(-△E/RT) (4) A: Frequency factor △ E: Activation energy R: Gas constant (8.314 J/mol. K) T: Absolute temperature (K)

The values of kd and ΔE are disclosed in J. Brandrup et al., Polymer Handbook (4th Edition), 1st, Pages II-1 to II-69, WILEY-INTERSCIENCE (1999) (Polymer Hand Book fourth edition volum 1, II-1~II-69). As described above, when t = 10 hours, the 10-hour half-life temperature T can be obtained.

As the thermal radical generating agent, a well-known type can be used, and examples thereof include an organic peroxide, an azo compound, a substituted ethane compound, and the like. Among the organic peroxides, it is preferably classified into a ketone peroxide, a peroxyketal, an oxyperoxide, a dialkyl peroxide, a peroxyester, a decyl peroxide, and a peroxydicarbonate. As the compound, a well-known type can be appropriately selected.

Examples of organic peroxides are shown below. The numbers in parentheses indicate the 10-hour half-life temperature (refer to the Wako Pure Chemicals Catalog, the API CORPORATION catalog, and the Polymer Handbook above). Examples of the ketone peroxides include methyl ethyl ketone peroxide (109 ° C), cycloethyl ketone peroxide (100 ° C), and the like.

Examples of peroxyketals include the following compounds.

1,1-bis(trihexylperoxy)-3,3,5-trimethylcyclohexane (87 ° C), 1,1-bis(trihexylperoxy)cyclohexane (87 ° C ), 1,1-bis(t-butylperoxy)cyclohexane (91 ° C), 2,2-bis(t-butylperoxy)butane (103 ° C), 1,1-( Third amyl peroxy)cyclohexane (93 ° C), 4,4-bis(t-butylperoxy)-n-butyl valerate (105 ° C), 2,2-bis (4,4- Di-t-butylperoxycyclohexyl)propane (95 ° C).

Examples of the hydroperoxides include the following compounds.

Hydrogen peroxide to menthane (128 ° C), diisopropylbenzene peroxide (145 ° C), 1,1,3,3-tetramethylbutyl hydroperoxide (153 ° C), cumene hydroperoxide (156 ° C), tert-butyl hydroperoxide (167 ° C).

Examples of the dialkyl peroxide include the following compounds.

α,α-bis(t-butylperoxy)diisopropylbenzene (119 ° C), dicumyl peroxide (116 ° C), 2,5-dimethyl-2,5-double (p. Tributylperoxy)hexane (118 ° C), tert-butyl cumene peroxide (120 ° C), third amyl peroxide (123 ° C), di-tert-butyl peroxide (124 ° C), 2,5-dimethyl-2,5-bis(t-butylperoxy)-3-hexene (129 ° C).

Examples of the peroxyesters include the following compounds.

Peroxyphenyl neodecanoate (37 ° C), peroxy neodecanoic acid-1,1,3,3-tetramethylbutyl ester (41 ° C), peroxy neodecanoic acid - third hexyl ester ( 45 ° C), peroxy neodecanoic acid - tert-butyl ester (46 ° C), peroxy neodecanoic acid - third amyl ester (46 ° C), peroxidic pivalic acid - third hexyl ester (53 ° C), Oxidized pivalic acid-third butyl ester (55 ° C), pivalic acid-p-pentyl ester (55 ° C), peroxy-2-ethylhexanoic acid-1,1,3,3-tetramethyl Butyl ester (65 ° C), 2,5-dimethyl-2,5-bis(2-ethylhexylperoxy)hexane (66 ° C), hexanoic acid-Third hexyl peroxide group-2 - ethyl ester (70 ° C), hexanoic acid-t-butylperoxy-2-ethyl ester (72 ° C), hexanoic acid-third amyl peroxy-2-ethyl ester (75 ° C), third Butylperoxy isobutyrate (82 ° C), third hexylperoxyisopropyl monocarbonate (95 ° C), tert-butylperoxy maleic acid (96 ° C), third amyl Peroxy-n-octanoate (96 ° C), third amyl peroxyisodecanoate (96 ° C), tert-butylperoxy-3,5,5-trimethylhexanoate (97) °C), tert-butylperoxy laurate (98 ° C), tert-butyl peroxy Isopropyl monocarbonate (99 ° C), tert-butylperoxy-2-ethylhexyl monocarbonate (99 ° C), a third hexyl peroxybenzoate (99 ° C), 2,5-dimethyl-2,5-bis(benzylidene peroxy)hexane (100 ° C), Tripentylperoxyacetate (100 ° C), third amyl peroxybenzoate (100 ° C), t-butyl peroxyacetate (102 ° C), tert-butyl Oxybenzoic acid ester (104 ° C).

Examples of the diinthyl peroxides include the following compounds.

Diisobutyl hydrazino peroxide (33 ° C), bis-3,5,5-trimethyl ethinyl peroxide (60 ° C), dilauroyl peroxide (62 ° C), disuccinic acid peroxidation (66 ° C), benzoyl peroxide (73 ° C).

Examples of the peroxydicarbonates include the following compounds.

Di-n-propyl peroxydicarbonate (40 ° C), diisopropyl peroxydicarbonate (41 ° C), bis (4-tert-butylcyclohexyl) peroxydicarbonate (41 ° C), two -2 Ethylhexyl peroxydicarbonate (44 ° C), third amyl peroxypropyl carbonate (96 ° C), third amyl peroxy-2-ethylhexyl carbonate (99 ° C).

Examples of the azo-based thermal radical generator include a water-soluble azo-based thermal radical generator, an oil-soluble azo-based thermal radical generator, and a polymer azo-based thermal radical generator.

Examples of the water-soluble azo-based thermal radical generating agent include the following compounds.

2,2'-azobis[2-(2-imidazolin-2-yl)propane]disulfate dihydrate (46 ° C), 2,2'-azobis[N-(2-carboxyl) 2-methylpropionamidine hydrate (57 ° C), 2,2'-azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane} Dihydrochloride (60 ° C), 2,2'-azobis(1-imino-1-tetrahydropyrrole 2-ethylpropane) dihydrochloride (67 ° C), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propanamide] (87 ° C), 2, 2'-Azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (44 ° C), 2,2'-azobis(2-methylpropionamidine) dihydrochloride (56 ° C), 2,2'-azobis[2-(2-imidazolin-2-yl)propane] (61 ° C), 2,2'-azobis {2-methyl-N-[ 1,1-bis(hydroxymethyl)-2-hydroxyethyl]propanamine} (80 ° C).

Examples of the oil-soluble azo-based thermal radical generating agent include the following compounds.

2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) (30 ° C), dimethyl-2,2'-azobis(2-methylpropionate) ) (66 ° C), 1,1 '-azobis(cyclohexane-1-carbonitrile) (88 ° C), 1,1 '-[(cyano-1-methylethyl)azo] Indoleamine (104 ° C), 2,2'-azobis(N-cyclohexyl-2-methylpropanamide) (111 ° C), 2,2'-azobis (2,4-dimethyl Valeronitrile) (51 ° C), 2,2'-azobis(2-methylbutyronitrile) (67 ° C), 2,2'-azobis[N-(2-propenyl)-2-methyl Propionamide] (96 ° C), 2,2'-azobis(N-butyl-2-methylpropionamide) (110 ° C).

Examples of the polymer azo-based thermal radical generator include a polymer azo-based thermal radical generator containing a polydimethyl siloxane unit, and a polymer azo-based thermal liberation containing a polyethylene glycol unit. Base generator.

The above-mentioned thermal radical generating agent may be arbitrarily combined in the sealant.

(5) Epoxy resin Epoxy resin refers to a compound having one or more epoxy groups in the molecule but no (meth) propylene group. Preferable examples of the epoxy resin contained in the sealant include the following chemicals: An aromatic polyvalent glycidyl ether compound obtained by reacting an aromatic diol represented by bisphenol A, bisphenol S, bisphenol F, bisphenol AD, etc. with epichlorohydrin (hereinafter, for example, bisphenol A) The raw material resin is referred to as "bisphenol A type epoxy resin"; the diol obtained by modifying the above aromatic diols with ethylene glycol, propylene glycol or alkanediol, and epichlorohydrin An aromatic polyvalent glycidyl ether compound; a novolac type polyvalent glycidyl ether compound obtained by reacting a novolak resin derived from phenol or cresol with formaldehyde with epichlorohydrin. Alternatively, a novolac type polyvalent glycidyl ether compound obtained by reacting a polyphenol represented by a polyalkenylphenol or a copolymer thereof with epichlorohydrin, and a glycidyl ether compound of a benzene dimethylphenol resin.

Among them, the epoxy resin is preferably: cresol varnish type epoxy resin, phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin , a trisphenol type epoxy resin, a trisphenol type epoxy resin, a dicyclopentadiene type epoxy resin, a diphenyl ether type epoxy resin, or a biphenyl type epoxy resin.

The sealant may contain only one type of epoxy resin, and may also contain a plurality of epoxy resins.

The epoxy resin contained in the sealant is preferably a softening point of 40 ° C or more and a weight average molecular weight of 1000 to 10,000 as measured by a ring and ball method. Since such an epoxy resin has low solubility and diffusibility to liquid crystals, the display characteristics of the liquid crystal display panel produced therefrom are good. Further, since the epoxy resin has high compatibility with the above acrylic resin, the density can be increased. The bonding reliability of the sealant. The weight average molecular weight of the epoxy resin can be measured, for example, by gel permeation chromatography (GPC) using polystyrene as a standard. It is preferred to subject these epoxy resins to high purity treatment by a molecular distillation method or the like.

(6) Potential epoxy hardener A latent epoxy hardener means that even after being mixed in an epoxy resin, the epoxy resin is hardened in a state in which the resin is normally stored (at room temperature, under visible light, etc.), but after encountering heat or light, A hardener that hardens the epoxy resin. If the sealant contains a latent epoxy hardener, the thermosetting property is improved. The latent epoxy hardener of the present invention may be of a well-known type. In order to improve the viscosity stability of the sealant, it is preferably a melting point or a latent epoxy having a softening point temperature of 100 ° C or higher as measured by the ring and ball method. hardener.

Examples of preferred latent epoxy hardeners include: organic acid diterpenoids, imidazoles, imidazole derivatives, dicyanodiamine, and aromatic amines. These compounds may be used singly or in combination of two or more. In particular, a liquid crystal sealing agent containing an amine-based latent curing agent having a melting point or a softening point temperature of 100 ° C or more as measured by the ring and ball method is extremely excellent in viscosity stability at room temperature. Therefore, the liquid crystal sealing agent containing such an amine-based latent curing agent can be easily applied to a substrate by using a screen printing or dispenser, and is suitable for use in a carrier substrate for manufacturing a liquid crystal display panel. When coating by a screen printing or dispenser, it is necessary to place the liquid crystal sealing agent in the apparatus for a long time, and therefore the liquid crystal sealing agent must have high storage stability.

Examples of such an amine-based latent curing agent include the following combinations Things.

Dicyanodiamines such as dicyanodiamine (melting point 209 ° C).

An organic acid diterpene such as diammonium adipate (melting point: 181 ° C) or 1,3-bis(decylcarboxyethyl)-5-isopropylhydantoin (melting point: 120 ° C).

2,4-Diamino-6-[2'-ethylimidazolium-1'-yl]-ethyltriazine (melting point 215 ° C ~ 225 ° C), 2-phenylimidazole (melting point 137 ° C ~ 147 ° C) Imidazole derivatives.

The content of the latent epoxy hardener in the sealant is preferably from 2 parts by weight to 30 parts by weight relative to 100 parts by weight of the resin unit. The reason for this is that the viscosity stability and the adhesion reliability of the sealant can be improved. It is preferred to subject the above-mentioned latent epoxy curing agent to high purity treatment by a water washing method, a recrystallization method or the like.

(7) Photoradical polymerization initiator The sealant of the present invention may also contain a photoradical polymerization initiator. The photoradical polymerization initiator refers to a compound which generates a radical due to light. When a photo-radical polymerization initiator is contained in the sealant, when the liquid crystal panel is manufactured, photo-curing can be used to temporarily harden the sealant to facilitate handling. A photoradical polymerization initiator can be used in a well-known type. Examples of such photoradical polymerization initiators include: benzoin compounds, acetophenones, benzophenones, thioxanthones, α-mercaptodecyl esters, Phenylglyoxylates. Classes, benzils, diphenyl sulfide compounds, mercaptophosphine oxide compounds, benzoin, benzoin ethers, and anthraquinones.

Photoradical polymerization in a sealant relative to 100 parts by weight of resin unit The content of the initiator is preferably from 0.1 part by weight to 5.0 parts by weight. When the content is 0.1% by weight or more, the curability of the resin composition after light irradiation can be improved, and when the content is 5.0 parts by weight or less, the stability when applied to a substrate is good. .

(8) Thermoplastic polymer The thermoplastic polymer used in the present invention is a polymer compound which is softened by heating and can be formed into a desired shape, and has a softening point temperature of 50 to 120 ° C as measured by a ring and ball method (JACT test method: RS-2). It is preferably 60 to 80 ° C. The sealant containing such a thermoplastic polymer is melted at the time of thermosetting, and is compatible with each component such as an acrylic resin, a modified epoxy resin, and an epoxy resin contained in the sealant. Therefore, it is possible to suppress a decrease in the viscosity of the sealant during heating, and it is possible to prevent the liquid crystal from leaking from the seal. The content of the thermoplastic polymer in the sealant is preferably from 1 part by weight to 30 parts by weight relative to 100 parts by weight of the resin unit. In order for the liquid crystal sealing agent to exhibit good compatibility, the average particle diameter of the thermoplastic polymer is usually in the range of 0.05 μm to 5 μm, preferably in the range of 0.07 μm to 3 μm.

The thermoplastic polymer can be used as long as it is of a well-known type. Among them, it is preferred to make the (meth) acrylate monomer, and the monomer copolymerizable with the monomer, in a ratio of 50% by weight to 99.9% by weight: 50% by weight to 0.1% by weight (more preferably 60%) Weight percent ~ 80 weight percent: a ratio of 20 weight percent to 40 weight percent) copolymer obtained by copolymerization. The copolymer is preferably a copolymer obtained by emulsion polymerization or suspension polymerization or the like.

Examples of the (meth) acrylate monomer include: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl acrylate, 2-ethyl (meth) acrylate Hexyl ester, amyl (meth)acrylate, hexadecyl (meth)acrylate, octadecyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxy (meth)acrylate A monofunctional (meth) acrylate monomer such as ethyl ester, 2-hydroxyethyl (meth) acrylate or glycidyl (meth) acrylate. Among them, the raw material monomer of the thermoplastic polymer is preferably methyl (meth)acrylate, butyl acrylate or 2-ethylhexyl methacrylate. The above compounds may be used singly or in combination.

Examples of the monomer copolymerizable with the (meth) acrylate monomer include acrylamide, an acid monomer, an aromatic vinyl compound, a conjugated diene, and a polyfunctional monomer.

Specific examples of the acid monomer include (meth)acrylic acid, itaconic acid, and maleic acid. Specific examples of the aromatic vinyl compound include styrene and a styrene derivative. Specific examples of the conjugated diene include 1,3-butadiene, 1,3-pentadiene, isoprene, 1,3-hexadiene, and chloroprene. Specific examples of the polyfunctional monomer include divinylbenzene and diacrylate.

These monomers may be used singly or in combination.

(9) Other additives The sealant of the present invention may contain an additive other than the above. Examples of such additives include coupling agents such as decane coupling agents, chain transfer agents, ion trapping agents, ion exchangers, leveling agents, pigments, dyes, plasticizers, conductive particles, hardening retarders, and antifoaming agents. .

[Examples]

The examples are shown below, but the invention is not limited thereto. Therefore, materials, manufacturing methods, and the like can be appropriately changed without departing from the invention. In addition, "%" and "part" disclosed below mean "% by weight" and "parts by weight" unless otherwise specified.

[Example 1: Production of carrier substrate of liquid crystal display panel of Fig. 1] The following components were mixed to prepare a sealant a.

[sealant a]

The above bisphenol A type epoxy resin modified diacrylate is used after the following purification treatment.

A bisphenol A type epoxy resin modified diacrylate (3002A manufactured by Kyoeisha Chemical Co., Ltd., molecular weight 600) was dissolved in toluene. The solution was washed repeatedly with ultrapure water.

The above methacrylic acid modified epoxy resin was synthesized in the following manner.

To a 500 ml four-necked flask equipped with a stirrer, an air tube, a thermometer, and a cooling tube, a bisphenol F-type epoxy resin (Epotohto YDF-8170C: manufactured by Tohto Kasei Co., Ltd.) 160 g, methyl 43 g of acrylic acid and 0.2 g of triethanolamine were used to prepare a mixture. The mixture was placed in a stream of dry air and heated and stirred at 110 ° C for 5 hours to form a methacrylic modified epoxy resin. The mixture containing the methacrylic acid modified epoxy resin was washed 12 times with ultrapure water. The methacrylic modified epoxy resin is isolated from the washed mixture by a conventional method.

The above filler was a spherical cerium oxide (C. Foster S-30 manufactured by Nippon Shokubai Co., Ltd.; an average primary particle diameter of 0.3 μm and a specific surface area of 11 m ² /g).

The above epoxy resin was an o-cresol varnish type solid epoxy resin (EOCN-1020-75 manufactured by Nippon Kayaku Co., Ltd., a softening point of 75 ° C and an epoxy equivalent of 215 g/eq as measured by the Ring and Ball method).

As the above-mentioned latent epoxy hardener, 1,3-bis(decylcarboxyethyl)-5-isopropylhydantoin (Amicure VDH manufactured by Ajinomoto Co., Ltd., melting point: 120 ° C) was used.

As the photoradical polymerization initiator, 1-hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184: manufactured by Ciba Specialty Chemicals Co., Ltd.) was used.

As the above thermoplastic polymer, methacrylic acid-alkyl copolymer fine particles (F-325 manufactured by Japan Zeon Co., Ltd., average primary particle diameter: 0.5 μm) were used.

As the above additive, a decane coupling agent (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.) was used.

After mixing the above components by a stirrer, the mixture was kneaded using a three-roll mill until the solid raw material was 4.8 μm or less, thereby obtaining a composition. Then use a filter with a pore size of 10 μm (MSP-10-E10S: manufactured by ADVANTEC Co., Ltd.) This composition was filtered, and then subjected to planetary stirring and vacuum defoaming treatment, thereby obtaining a sealant a. The viscosity of sealant a at 25 ° C is 325 Pa at 0.5 rpm. s, 238 Pa at 1.0 rpm. s, 155 Pa at 5 rpm. s. Moreover, the thixotropic index is 2.1. In addition, the viscosity of the sealant is an E-type rotary viscometer (manufactured by BROOKFIELD: Digital Rheometer type DV-III ULTRA), and a CP-52 type cone and plate type with a radius of 12 mm and an angle of 3 degrees is used. The tester was measured at 0.5 rpm, 1.0 rpm, and 5.0 rpm. The viscosity of the sealant was measured after placing the sealant at a predetermined temperature for 5 minutes. For example, the viscosity measured after leaving the sealant at 25 ° C for 5 minutes is used as the viscosity of the sealant at 25 ° C.

A spherical spacer having a diameter of 4.8 μm was added to the sealant a, and a sealant for drawing (hereinafter simply referred to as "sealant") was prepared. Using the sealant, the carrier substrate 10 of the liquid crystal display panel shown in Fig. 1 was produced as follows.

First, a sealant was applied to one substrate 11 using a dispenser (Hitachi Industrial Equipment Co., Ltd.) to have a line width of 250 μm and a cross-sectional area of 5000 μm ² to form four ((longitudinal 2, horizontal 2). The first frame 21 (see Fig. 7) having a length of 25.0 mm and a width of 25.0 mm.

A glass substrate (110.0 mm in length, 100.0 mm in width, and 0.7 mm in thickness) coated with ITO (Indium Tin Oxide) and an alignment film was used for the two substrates. Further, the voltage application portion is provided on the glass substrate, and the lighting test can be performed without cutting the panel. Further, an angle on the opposite side of the voltage application portion on the glass substrate is provided with an orifice. The orifice refers to the positioning mark used when bonding the substrate.

The second frame 22 is formed by applying a sealant so as to surround the four first frames 21 with the left side of the substrate as a starting point.

Nine drops of liquid crystal 24 (liquid crystal MLC-11900-000 manufactured by Merck Co., Ltd.) were dropped into each of the first frames 21 to have a filling ratio of 110% (see Fig. 7). Thereafter, using a vacuum bonding apparatus (manufactured by Shin-Etsu Engineering Co., Ltd.), the position of the orifice is aligned so that a voltage is applied to the substrate on which the liquid crystal is dropped and another substrate having the same shape, and then the panel display is performed, and then the pressure is reduced. It overlaps. Further, the substrate was bonded after returning to atmospheric pressure under reduced pressure. The line width of the bonded main seal and dummy seal is 1 mm.

The interval D1 between the adjacent main seal members 14 formed by bonding the two substrates was 9.0 mm. The interval D2 of the disconnecting portion 15a after the two substrates are bonded is 9.0 mm, and the interval D3 between the disconnecting portion 15a and the main sealing member 14 after the two substrates are bonded is 9.0 mm, and the end face and the dummy side of the voltage applying portion side of the substrate 11 are The distance L1 (not shown) of the seal 15 is 20.0 mm.

When the substrate was observed with an optical microscope, the filling of the liquid crystal in the main seal 14 was observed. As a result, the liquid crystal is completely filled in the main seal 14. Next, the overlapped substrate was irradiated with ultraviolet rays of 2000 mJ/cm ² and then heated at 120 ° C for 1 hour to cure the sealant. Thus, the carrier substrate 10 of the liquid crystal display panel in which four liquid crystal panels are formed can be obtained. The heat treated seal has a line width of 1.0 mm.

Next, the damage of the main seal of the carrier substrate 10 of the liquid crystal display panel produced was observed and evaluated. And along the outer circumference of the main seal 14 After the liquid crystal display panel was cut out, the liquid crystal display panel was taken as a sample, and the flatness was observed and evaluated. Each evaluation method is as follows.

[damage of main seal] The carrier substrate 10 of the produced liquid crystal display panel was observed with an optical microscope. At this time, it was evaluated in four levels: when the main seal on each liquid crystal display panel was not damaged and the liquid crystal did not have an impact on the seal line, it was recorded as ◎, and when the impact was observed but the main seal was not broken, it was recorded as ○ When the main seal is damaged, it is recorded as △. When the main seal has two or more breaks, it is recorded as ×.

[Flatness of panel] The liquid crystal display panel produced was used as a sample, and the in-plane distribution of the gap interval in the main seal on the sample was measured using a cell gap inspection device (manufactured by Otsuka Electronics Co., Ltd.). And it is evaluated in three levels: when any one of the maximum value and the minimum value of the interval is not in the range of 5 μm ± 0.2 μm, it is denoted as ×, and when the maximum value and the minimum value of the interval are all within the range of 5 μm ± 0.2 μm When the difference between the maximum value and the minimum value is 0.1 μm or more, it is denoted as Δ, and when the average value of the interval is in the range of 5 μm ± 0.2 μm and the difference between the maximum value and the minimum value is less than 0.1 μm, it is denoted as ○.

[Embodiment 2: Manufacturing of carrier substrate of liquid crystal display panel of Fig. 1] In the same manner as in the first embodiment, a sealant was applied onto one substrate 11, and four (longitudinal 2, horizontal 2) first frames 21 were formed. Next, the sealant is applied so as to surround the four panels on the left side of the substrate, thereby forming the second frame 22. The second frame 22 is a ring-shaped substantially quadrangular shape. The seal on one of the straight portions of the quadrilateral is cut to a width of about 10 mm to form a broken portion.

Next, four drops of liquid crystal 24 (liquid crystal MLC-11900-000 manufactured by Merck Co., Ltd.) were dropped into each of the first frames 21 so that the filling ratio became 105%. Thereafter, using a vacuum bonding apparatus (manufactured by Shin-Etsu Engineering Co., Ltd.), the substrate 11 into which the liquid crystal is dropped, and another substrate 27 having the same shape are overlapped under a reduced pressure atmosphere, and then opened to atmospheric pressure, thereby bonding the substrates. .

Each of the bonded seals has a line width of 1 mm. The interval D1 is 30 mm, and D2, D3, and L1 are the same as in the first embodiment.

In the same manner as in Example 1, the filling of the liquid crystal in the main sealing member was observed, and it was found that the main sealing member was completely filled with the liquid crystal. Next, the sealant was cured in the same manner as in Example 1, and a carrier substrate of a liquid crystal display panel in which four liquid crystal panels were formed was obtained. The heat treated seal has a line width of 1 mm.

[Embodiment 3: Manufacturing of a carrier substrate of the liquid crystal display panel of Fig. 2] A screen printing machine (manufactured by Tokai Seiki Co., Ltd.) was used in the same manner as in the first embodiment, and a first frame was provided on one substrate. The first frame has a line width of 200 μm and a cross-sectional area of 5000 μm ² . The second frame shown in Fig. 2 is formed in the same manner. The shape of the second frame is a rectangle having a length of 10 mm and a width of 55 mm, and a broken portion is formed in a part thereof. The second frame has a line width of 140 μm and a cross-sectional area of 3500 μm ² .

Next, two drops of liquid crystal (liquid crystal MLC-11900-000 manufactured by Merck Co., Ltd.) were dropped into each of the first frames so that the filling ratio became 110%. this Thereafter, the steps up to the curing of the sealant by heating were the same as in Example 1.

The bonded D1 is 3.0 mm, D2 is 0.2 mm, and D3 is 2.0 mm. The heat-treated main seal 31 has a line width of 1.0 mm, and the dummy seal 32 has a line width of 0.7 mm.

In the same manner as in Example 1, the filling of the liquid crystal was observed by an optical microscope, and it was found that the inside of the main sealing member 31 was completely filled with liquid crystal.

[Embodiment 4: Manufacturing of carrier substrate of liquid crystal display panel of Fig. 3] In the same manner as in the third embodiment, as shown in Fig. 3, six (vertical 3, horizontal 2) first frames are provided on one substrate. . Each of the first frames has a shape of 25.0 mm in length, 30.0 mm in width, and a line width of 200 μm and a cross-sectional area of 5000 μm ² . Also, as shown in FIG. 3, two second frames are formed. The shape of the second frame is a rectangle having a length of 85 mm and a width of 10 mm, and is provided with a broken portion. The second frame has a line width of 140 μm and a cross-sectional area of 3500 μm ² .

Next, four drops of liquid crystal (liquid crystal MLC-11900-000 manufactured by Merck Co., Ltd.) were dropped into each of the first frames to have a filling ratio of 115%. Using a vacuum bonding apparatus (manufactured by Shin-Etsu Engineering Co., Ltd.), the substrate on which each frame was formed, another substrate having the same shape and coated with a spherical spacer having a diameter of 4.8 μm was superposed under reduced pressure, and then opened to atmospheric pressure. Next, the substrate is bonded.

D1 is 3.0 mm, D2 is 0.2 mm, and D3 is 2.0 mm.

When the bonded substrate was observed by an optical microscope, it was found that the liquid crystal was filled in the main sealing member 41. Thereafter, the bonded substrate was irradiated with ultraviolet rays at 2000 mJ/cm ² and then heated at 120 ° C for 1 hour. The heat treated seal has a line width of 1.0 mm.

[Embodiment 5: Manufacturing of carrier substrate of liquid crystal display panel of Fig. 1] The following sealing agent b was used in place of the sealant a, and after the two substrates were bonded to each other, the ultraviolet rays were not irradiated, but immediately heated at 120 ° C for 1 hour, except that the same procedure as in Example 1 was carried out. A carrier substrate of a liquid crystal display panel.

[sealant b] The following compound was mixed to prepare a sealant b. Among them, the above thermal radical generating agent used was 2,2'-azobis(2-methylpropionic acid) dimethyl ester (V-601 manufactured by Wako Pure Chemical Industries, Ltd.; a 10-hour half-life temperature of 66 ° C). Further, the same as the compound used in the sealant a except for the thermal radical generator.

The above components were premixed by a stirrer, and the mixture was further kneaded by a three-roll mill until the solid raw material was 4.8 μm or less, thereby obtaining a composition. Next, the composition was filtered with a filter having a pore size of 10 μm (MSP-10-E10S manufactured by ADVANTEC Co., Ltd.), and then subjected to planetary stirring and vacuum defoaming treatment to prepare a sealant b. The viscosity of the sealant b obtained in the above manner at 25 ° C, 191 Pa at 0.5 rpm. s, 160 Pa at 1.0 rpm. s, 136 Pa at 5 rpm. s, the thixotropic index is 1.4. Moreover, the viscosity measured by an E-type rotary viscometer at 80 ° C exceeded 780 Pa. s, so the viscosity measured by the parallel plate method (RheoStress RS150, manufactured by HAAKE) is 9.00 E+05 Pa. s.

[Embodiment 6: Fabrication of a carrier substrate of the liquid crystal display panel of Fig. 1] The sealant b was used in place of the sealant a, and after the substrates were bonded to each other, the substrate was heated without being irradiated with ultraviolet rays, and immediately heated at 120 ° C for 1 hour, and the carrier of the liquid crystal display panel was produced in the same manner as in Example 2. Substrate.

[Embodiment 7: Fabrication of a carrier substrate of the liquid crystal display panel of Fig. 2] The sealant b was used in place of the sealant a, and after the substrates were bonded to each other, the substrate was heated without being irradiated with ultraviolet rays, and immediately heated at 120 ° C for 1 hour, and the load of the liquid crystal display panel was produced in the same manner as in Example 3. Substrate.

[Embodiment 8: Fabrication of a carrier substrate of the liquid crystal display panel of Fig. 3] The sealant b was used instead of the sealant a, and after the substrates were bonded to each other, the ultraviolet ray was not irradiated, but immediately heated at 120 ° C for 1 hour, and the load of the liquid crystal display panel was produced in the same manner as in Example 4. Substrate.

[Comparative Example 1: Fabrication of Carrier Substrate of Liquid Crystal Display Panel of FIG. 8] A frame having a length of 70 mm and a width of 70 mm was formed on the substrate 76 as a first frame, that is, a main seal 77. Further, a second frame, that is, an annular dummy seal 78, which is the same shape as the main seal 77 but different in magnification, is formed in such a manner as to surround the main seal 77. When each frame was formed, the same sealant as in Example 1 was used. The second frame is arranged in such a manner that the distance D3 between the main seal 77 and the dummy seal 78 reaches 5 mm after the substrates are bonded to each other. Thereafter, 25 drops of liquid crystal (liquid crystal MLC-11900-000 manufactured by Merck Co., Ltd.) were dropped into each of the first frames so that the filling ratio became 100%. Next, the substrate on which the liquid crystal was dropped, and another substrate having the same shape and coated with a spherical spacer having a diameter of 4.8 μm were stacked under reduced pressure, and then opened to atmospheric pressure, thereby bonding the substrates. . At this time, the liquid crystal is filled in the main seal 77. Next, after irradiating ultraviolet rays at 2000 mJ/cm ² , it was heated at 120 ° C for 1 hour. The heat treated seal has a line width of 1.0 mm. The production conditions other than the above were the same as in the first embodiment.

[Comparative Example 2: Manufacturing of carrier substrate of liquid crystal display panel of Fig. 9] Using the same sealant as in Example 1, a frame of 30 mm in length and 30 mm in width was formed on the substrate 80 as a first frame, that is, a main seal 81. Similarly, a frame having four short sides of 20 mm and a long side of 30 mm is formed as a second frame, that is, a dummy seal 82, on the outer side of the first frame around the first frame. Moreover, on the diagonal extension line of the first frame, four circular second frames having a diameter of 30 mm are formed. The second frame is formed as a circular portion 83 after the substrate is overlapped. The arrangement of the first frame and the second frame is adjusted such that the interval D3 between the main seal 81 and the dummy seal 82 after the two substrates are bonded reaches 10 mm.

Next, nine drops of liquid crystal (liquid crystal MLC-11900-000 manufactured by Merck Co., Ltd.) were dropped into each of the first frames so that the filling ratio became 100%. Next, the substrate on which the liquid crystal was dropped and another substrate having the same shape were superposed under reduced pressure, and then a pressure of 0.1 N/mm ² was applied to fill the liquid crystal into the first frame. Thereafter, the pressure was returned to atmospheric pressure under reduced pressure, whereby the substrate was bonded, and then irradiated with ultraviolet rays of 2000 mJ/cm ² and then heated at 120 ° C for 1 hour. In addition, the manufacturing conditions of the carrier substrate of the liquid crystal display panel other than the above were the same as those in the first embodiment.

[Comparative Example 3: Fabrication of Carrier Substrate of Liquid Crystal Display Panel of FIG. 10] Using the same encapsulant as in Example 1, two frames of 30 mm in length and 30 mm in width were formed on the substrate 90 as the first frame, that is, Main seal 91. Similarly, six rectangular frames having a long side of 30 mm and a short side of 10 mm are formed as the annular second frame, that is, the dummy seal 92. The second frame is disposed on the outer side of the periphery of the first frame so as to surround the first frame. When the sealant is applied, the first frame has a line width of 200 μm and a cross-sectional area of 5000 μm ² by using a dispenser (manufactured by Hitachi Industrial Equipment Co., Ltd.), so that the line width of the annular second frame is 400 μm. The cross-sectional area is 10000 μm ² . Further, the interval D1 between the main sealing members 91 after bonding the two substrates is 2 mm, and the interval D3 between the main sealing member 91 and the dummy sealing member 92 is 10 mm.

Next, nine drops of liquid crystal (liquid crystal MLC-11900-000 manufactured by Merck Co., Ltd.) were dropped into each of the first frames to increase the filling ratio. Next, the substrate on which the liquid crystal was dropped, and another substrate having the same shape and having a spherical spacer having a diameter of 4.8 μm were superposed under a reduced pressure atmosphere, and then opened to atmospheric pressure, thereby bonding the substrates to each other. . At this time, the filling of the liquid crystal was observed by an optical microscope, and it was found that the liquid crystal completely filled the four corners in the main seal 91. After irradiating ultraviolet rays of 2000 mJ/cm ² , it was heated at 120 ° C for 1 hour.

[Comparative Example 4: Manufacturing of carrier substrate of liquid crystal display panel of Fig. 8] The sealant b was used instead of the sealant a, and after the substrates were bonded to each other, the substrate was heated without being irradiated with ultraviolet rays, and immediately heated at 120 ° C for 1 hour, and the load of the liquid crystal display panel was produced in the same manner as in Comparative Example 1. Substrate.

[Comparative Example 5: Manufacturing of carrier substrate of liquid crystal display panel of Fig. 9] The sealant b was used in place of the sealant a, and after the substrates were bonded to each other, the ultraviolet ray was not irradiated, but immediately heated at 120 ° C for 1 hour, and the load of the liquid crystal display panel was produced in the same manner as in Comparative Example 2. Substrate.

[Comparative Example 6: Manufacturing of carrier substrate of liquid crystal display panel of Fig. 10] A liquid crystal display panel was produced in the same manner as in Comparative Example 3 except that the sealant b was used instead of the sealant a, and the substrates were bonded to each other without being irradiated with ultraviolet rays, but immediately heated at 120 ° C for 1 hour. Carrying the substrate.

[Embodiment 9: Manufacturing of carrier substrate of liquid crystal display panel of Fig. 1] The following components were kneaded by a three-roll mill until the solid raw material was 5 μm or less. Next, the composition was filtered with a filter having a pore size of 10 μm (MSP-10-E10S, manufactured by ADVANTEC Co., Ltd.), and then subjected to vacuum defoaming treatment to obtain a sealant c.

The same compound as in Example 1 was used for the bisphenol A type epoxy resin modified diacryl resin and the filler.

The acrylic modified epoxy resin was synthesized in the following manner.

In a 500 ml four-necked flask equipped with a stirrer, an air tube, a thermometer, and a cooling tube, a bisphenol F-type epoxy resin (Epotohto YDF-8170C, manufactured by Tohto Kasei Co., Ltd.) 160 g, 36 g of acrylic acid, and triethanolamine 0.2 g were charged. , to obtain a mixture. Next, the mixture was heated and stirred at 110 ° C for 5 hours under a stream of dry air to cause an acrylic modified epoxy resin. The mixture containing the acrylic modified epoxy resin was washed 12 times with ultrapure water. The acrylic modified epoxy resin is isolated from the washed mixture by a conventional method.

As the thermal radical generator, Lupasol 575 (manufactured by API Corporation) having a 10-hour half-life temperature of 75 ° C was used.

The viscosity of the sealant c obtained in the above manner at 25 ° C was 260 Pa at 0.5 rpm. s, 180 Pa at 1.0 rpm. s, 120 Pa at 5 rpm. s. The sealant has a viscosity at 80 ° C of 650 Pa at 1.0 rpm. s.

Further, the viscosity of the sealant at 80 ° C was measured by a parallel plate method (RheoStress RS150: manufactured by HAAKE) to be 3.5E+05 Pa. s. The thixotropy index is 2.2.

Using the obtained sealant, a carrier substrate of a liquid crystal display panel was produced in the same manner as in Example 5. Here, the sealant c was used instead of the sealant b, and in the step of heating the bonded substrate, it was heated at 70 ° C for 30 minutes and then heated at 120 ° C for 60 minutes. Liquid crystal used (MLC-11900-000: manufactured by Merck) The NI temperature is 3 ° C. Therefore, "heating at 70 ° C" means heating at less than NI temperature, which corresponds to the above-described hardening of less than NI.

The carrier substrate of the liquid crystal display panel obtained in the above manner was used for the following evaluation.

[Resistance of sealant] According to the shape of the sealing material of the carrier substrate of the liquid crystal display panel, the deformation of the sealing member, the leakage of the liquid crystal to the sealing portion, and the leakage of the sealant component to the liquid crystal portion (collectively referred to as "reliability of the sealant") are evaluated. The evaluation indicators are as follows.

[ratio of the maximum width to the minimum width of the seal]%=[Minimum width of the seal]/[Maximum width of the seal]×100 The above ratio is greater than or equal to 95%: ○ 50% or more and less than 95%: △ Less than 50%: ×

[Residual rate of polymerizable groups in the sealant after hardening of NI] The 10 mg sealant prepared in the above manner was subjected to thermal analysis by DSC (manufactured by SII Co., Ltd.) in the following manner, and the residual ratio of the polymerizable group in the sealant after hardening of NI was not measured.

First, the uncured sealant was heated from room temperature to 70 ° C at a rate of 55 ° C / min. Then, it was kept at 70 ° C for 30 minutes, and the amount of heat x emitted during the period was determined.

Then, the uncured sealant was heated from room temperature to 150 ° C at a rate of 55 ° C / min. Then, it was kept at 150 ° C for 1 hour to determine the period. The heat y emitted inside. When the calorific value at the time of the 100% hardening reaction of the sealant is y, the residual ratio of the polymerizable group in the sealant after curing of NI is not obtained by (1-x/y) × 100.

[Embodiment 10: Fabrication of a carrier substrate of the liquid crystal display panel of Fig. 1] The sealant d was prepared in the same manner as in Example 9 using the following ingredients.

The same compound as in Example 9 was used for the bisphenol A type epoxy resin modified diacryl resin, the acrylic modified epoxy resin, and the filler.

As the thermal radical generator, 1-azobis(2,4-cyclohexane-1-carbonitrile) (V-40, manufactured by Wako Pure Chemical Industries, Ltd.) was used. The thermal free radical generator had a 10-hour half-life temperature of 88 °C.

The epoxy resin was an o-cresol varnish type solid epoxy resin (EOCN-1020-75, manufactured by Nippon Kayaku Co., Ltd., having a softening point of 75 ° C and an epoxy equivalent of 215 g/eq as measured by the Ring and Ball method).

As the latent epoxy hardener, 1,3-bis(decylcarboxyethyl)-5-isopropylhydantoin (Amicure VDH, manufactured by Ajinomoto Co., Ltd., melting point: 120 ° C) was used.

The viscosity of the sealant d obtained in the above manner at 25 ° C is 0.5 450 Pa at rpm. s, 275 Pa at 1.0 rpm. s, 180 Pa at 5 rpm. s. The sealant has a viscosity at 80 ° C of 760 Pa at 1.0 rpm. s.

Further, the viscosity of the sealant at 80 ° C was measured by a parallel plate method (RheoStress RS150: manufactured by HAAKE) to be 3.5E+05 Pa. s. The thixotropic index is 2.5.

A carrier substrate of a liquid crystal display panel was produced and evaluated in the same manner as in Example 9 except that the sealant d was used instead of the sealant c.

[Embodiment 11: Fabrication of a carrier substrate of the liquid crystal display panel of Fig. 1] A carrier substrate of a liquid crystal display panel was produced and evaluated in the same manner as in Example 9 except that the heating conditions for curing the sealant were 120 ° C for 60 minutes. The residual amount of the polymerizable group in the sealant after heating at 120 ° C for 60 minutes can be determined by the following method.

The uncured sealant was heated from room temperature to a temperature of 55 ° C/min to 120 ° C. Then, it was kept at 120 ° C for 1 hour, and the amount of heat x emitted during the period was determined.

Then, the uncured sealant was heated from room temperature to 150 ° C at a rate of 55 ° C / min. Then, it was kept at 150 ° C for 1 hour, and the amount of heat y emitted during the period was determined. When the calorific value at the time of the 100% hardening reaction of the sealant is y, the residual amount of the polymerizable group in the sealant after heating at 120 ° C for 60 minutes is determined by (1-x/y) × 100.

[Embodiment 12: Fabrication of a carrier substrate of the liquid crystal display panel of Fig. 1] The evaluation was carried out in the same manner as in Example 10 except that the heating conditions for curing the sealant were 120 ° C for 60 minutes.

The results of each evaluation are shown in Tables 1 to 3.

According to the results of the first to eighth embodiments and the comparative example 1 to the comparative example 6, it is understood that when a dummy seal having a broken portion is provided outside the main seal, the two substrates can be bonded without deforming the substrate. At this point, the primary seal will not be damaged. On the other hand, when a closed dummy seal is provided, it is difficult to suppress deformation of the substrate, and it is also observed that the main seal is broken. Therefore, the quality of the carrier substrate of the liquid crystal display panel cannot be prevented from deteriorating.

By comparing Examples 9 and 10 with Examples 11 and 12, it is understood that the carrier substrate of the liquid crystal display panel manufactured by the first curing step has more excellent reliability.

[Industrial availability]

The liquid crystal display panel obtained by the carrier substrate of the liquid crystal display panel of the present invention can prevent the arrangement of the sealing member from being displaced, and the main sealing member is not damaged. Further, by reducing the deformation of the substrate, the cell gap can be made uniform, and therefore, when mounted on an office machine or a mobile phone, etc., it is possible to provide very excellent display quality.

The present application claims priority based on the application filed on May 14, 2007, JP 2007-128220, and the application filed on June 22, 2007, JP 2007-165679. The contents disclosed in the specification and the drawings are all incorporated in the specification of the present application.

10‧‧‧Loading substrate of liquid crystal display panel

11, 30, 40, 50, 60, 70, 76, 80, 90‧‧‧ substrates

14, 31, 41, 51, 61, 71, 77, 81, 91‧‧‧ main seals

15, 32, 42, 52, 62, 72, 78, 82, 92‧‧‧ dummy seals

15a, 23, 33, 43, 73, B‧‧‧ broken parts

Starting point of 16a‧‧

16b‧‧‧ End

21‧‧‧ first box

22‧‧‧ second box

24‧‧‧LCD

27‧‧‧Other substrate

28‧‧‧ spacers

83‧‧‧ Round Department

A1‧‧‧ inside

A2‧‧‧ outside

D1, D2, D3, D4, D2', D2" ‧ ‧ interval

1 is a schematic view of a carrier substrate of a first liquid crystal display panel of the present invention.

2 is a schematic view of a carrier substrate of a second liquid crystal display panel of the present invention.

3 is a schematic view of a carrier substrate of a third liquid crystal display panel of the present invention.

4 is a schematic view showing a carrier substrate of a fourth liquid crystal display panel of the present invention.

Fig. 5 is a schematic view showing a carrier substrate of a fifth liquid crystal display panel of the present invention.

Fig. 6 is a schematic view showing a carrier substrate of a sixth liquid crystal display panel of the present invention.

FIG. 7 is a view showing an example of a method of manufacturing a carrier substrate of a liquid crystal display panel of the present invention.

8 is a schematic view of a carrier substrate of a liquid crystal display panel used in a comparative example.

9 is a schematic view of a carrier substrate of a liquid crystal display panel used in a comparative example.

Fig. 10 is a schematic view showing a carrier substrate of a liquid crystal display panel used in a comparative example.

11‧‧‧Substrate

21‧‧‧ first box

22‧‧‧ second box

23‧‧‧Disconnection Department

24‧‧‧LCD

27‧‧‧Other substrate

28‧‧‧ spacers

Claims (14)

A carrier substrate for a liquid crystal display panel, comprising: two substrates bonded by a sealant; one or two or more display areas between the two substrates, determined by a first seal having no end points And the inside of the first sealing member is sealed in a liquid crystal manner; and a non-closed region is located between the two substrates outside the display region, and is determined by a second sealing member having a broken portion. Wherein the disconnection portion is a pipeline formed by a straight line or a curved line. The carrier substrate of the liquid crystal display panel of claim 1, wherein the interval D2 of the disconnection portion of the second seal is 0.1 mm or more and 20 mm or less. The carrier substrate of the liquid crystal display panel of claim 1, wherein the second sealing member is formed by a combination of straight lines. The carrier substrate of the liquid crystal display panel of claim 1, wherein the second sealing member comprises a curved line. The carrier substrate of the liquid crystal display panel of claim 1, wherein the second seal has a line width of 0.2 mm or more and 4.0 mm or less. A method for manufacturing a carrier substrate of a liquid crystal display panel, which is a method for manufacturing a carrier substrate of a liquid crystal display panel manufactured by bonding two opposing substrates via a sealant, comprising: (a1) pairing the two substrates Applying a first encapsulant in such a manner as to surround the pixel array region, thereby forming a frame-shaped display region (b1) a step of applying a second sealant in a partially broken state to form a non-closed region for any of the two substrates; (c) dropping into the display region a step of liquid crystal; (d) providing a second frame forming the non-closed area on an outer side of the first frame forming the display area, and not reducing the first frame and the second frame Depressing a step of overlapping the two substrates; (e) repeating the steps of returning the two stacked substrates from under reduced pressure to atmospheric pressure; and (f) after bonding the substrates to each other, a sealing agent and a step of hardening the second sealant, wherein a portion of the broken line in the step (b1) is a broken portion formed in the second frame in the step (d), The broken portion is a pipe formed by a straight line or a curved line. A method for manufacturing a carrier substrate of a liquid crystal display panel, which is a method for manufacturing a carrier substrate of a liquid crystal display panel manufactured by bonding two opposing substrates via a sealant, comprising: (a2) pairing the two substrates Or both, a first encapsulant is applied to surround the pixel array region to form a frame-shaped display region; (b2) to either or both of the two substrates a step of applying a second sealant to form a non-closed region; (c) a step of dropping a liquid crystal into the display region; (d) providing, on an outer side of the first frame forming the display area, a second frame forming the non-closed area, and not bringing the first frame into contact with the second frame to decompress under pressure a step of overlapping the two substrates; (e) a step of returning the overlapped two substrates to atmospheric pressure under reduced pressure; and (f) after the substrates are bonded to each other, the first sealant and a step of hardening the second sealant, wherein a portion of the broken line in the step (b2) is a broken portion formed in the second frame in the step (d), the broken line The part is a line formed by a straight line or a curve. The method of manufacturing a carrier substrate of a liquid crystal display panel according to claim 6 or 7, wherein the step (f) comprises the step of heating the two stacked substrates. The method for manufacturing a carrier substrate of a liquid crystal display panel according to Item 6 or 7, wherein in the step (f), the two substrates that are overlapped are at 40 ° C or higher, and The first sealant and the second sealant are cured by heating to a temperature of a nematic-isotropic phase transition temperature of the liquid crystal for 1 minute to 120 minutes. The method for manufacturing a carrier substrate of a liquid crystal display panel according to claim 9, wherein after the step (f), the method further comprises the following step (g): heating the two stacked substrates to be greater than A step equal to the nematic-isotropic phase transition temperature of the liquid crystal. The method for manufacturing a carrier substrate of a liquid crystal display panel according to claim 6 or 7, wherein the first sealant is of type E The viscosity of the viscometer measured at 25 ° C, 1.0 rpm is greater than or equal to 20Pa. s and less than or equal to 500Pa. s. The method for manufacturing a carrier substrate of a liquid crystal display panel according to claim 6 or 7, wherein the first sealant has a viscosity measured by an E-type viscometer at 80 ° C and 1.0 rpm. 500Pa. s. The method for manufacturing a carrier substrate of a liquid crystal display panel according to claim 6 or 7, wherein the first sealant has a viscosity of η1 and 25 at 25 ° C and 0.5 rpm as measured by an E-type viscometer. The ratio of the viscosity η2 at ° C and 5.0 rpm, that is, the thixotropic index η1/η2 is greater than or equal to 1.0 and less than or equal to 5.0. The method for manufacturing a carrier substrate of a liquid crystal display panel according to claim 9, wherein the first sealant contains a thermal radical generating agent, and the thermal radical generating agent has a 10-hour half-life temperature of 30 ° C. At ~80 ° C, the 10-hour half-life temperature is defined as the temperature at which the concentration of the thermal radical generator is half when the thermal decomposition reaction is carried out for 10 hours at a fixed temperature.