JP2008102303A - Display device manufacturing method and display device - Google Patents

Abstract

A manufacturing method of a display device having a spacer for making a gap between a first substrate and a second substrate constant, which can cope with simplification and miniaturization of a manufacturing process.
A photosensitive resin composition that generates and cures an acid or a base by irradiation with light on a surface of at least one of the first and second substrates that faces the other substrate has a predetermined thickness. The photosensitive resin composition layer 4 is formed, and the photosensitive resin composition layer 4 is selectively exposed through a mask 15 for selectively exposing at least a portion where a spacer is formed. A method for manufacturing a display device, comprising each step of forming a spacer in an exposed part by moving at least a part of the photosensitive resin composition in the exposed part to the exposed part and curing the photosensitive resin composition in the exposed part .
[Selection] Figure 2

Description

  The present invention relates to a method for manufacturing a display device such as a liquid crystal display device or an organic EL display and a display device, and more particularly to make a gap between first and second substrates facing each other constant. The present invention relates to a method for manufacturing a display device and a display device having a structure in which a protrusion is provided on the inner surface of at least one of the spacer and / or the first and second substrates.

  In a liquid crystal display device, liquid crystal is sealed between two substrates facing each other. In order to improve display quality, it is necessary to make the facing distance between two substrates, that is, the gap constant. Therefore, spacers are arranged in a region excluding the region where the pixels are formed in order to make the gap between the two substrates constant. For example, as disclosed in Patent Document 1, a spacer made of a synthetic resin or an inorganic material is disposed in a light shielding region of one substrate, and the spacer is in contact with the inner surface of the other substrate.

  Also, in the liquid crystal display device, in order to improve the viewing angle, a structure is known in which a liquid crystal alignment control protrusion for controlling the alignment of liquid crystal molecules is formed on the inner surface of at least one substrate at a portion in contact with the liquid crystal. Yes. Patent Document 2 discloses an example of a method for forming such protrusions. In Patent Document 2, protrusions are formed on a substrate by a photolithography method using a positive resist containing a naphthoquinone diazide compound and a novolac resin. Here, after forming the projection by photolithography, the projection having a desired inclined surface is formed by heating.

On the other hand, in Patent Document 3 below, a method of providing a protrusion on an electrode formed on a substrate of a liquid crystal display element using a negative resist mainly composed of an alkali-soluble resin, a photopolymerization initiator and a photopolymerizable monomer. Is disclosed.
Japanese Patent Laid-Open No. 62-134626 JP-A-7-92689 JP 2003-330011 A

  As described in Patent Document 1, conventionally, in order to keep the gap size constant, a spherical spacer made of a synthetic resin or an inorganic material is disposed in a light shielding region on the inner surface of one substrate, and the other substrate is laminated. As a result, the liquid crystal display device was assembled. Therefore, for example, the spacer material must be accurately arranged in the light-shielding region that does not affect the display such as the black matrix, and the manufacturing process has to be complicated. In particular, when the number of pixels is increased and the pixels are made smaller in order to increase the resolution, the light-shielding region where the spacer is arranged also becomes smaller. Accordingly, it has become more difficult to arrange the spacer with high accuracy in such a small light shielding region.

  On the other hand, in the method for forming a liquid crystal alignment control protrusion described in Patent Document 2, the protrusion is formed by a photolithography method using a positive resist, and the shape of the inclined surface is changed to a desired shape by heating. . However, the shape of the inclined surface of the protrusion may vary depending on the bottom width of the protrusion immediately after being formed by photolithography and the heating temperature. For this reason, the liquid crystal molecules have uneven alignment, which may cause display unevenness.

  In addition, in the photolithography method using a positive resist, there is a problem that the management of development conditions is complicated compared to the case of using a negative resist.

  On the other hand, in the protrusion forming method using the negative resist described in Patent Document 3, since the protrusion is formed on the electrode by photolithography, the tolerance of the developing condition is small when the bottom area of the protrusion is small. Also, the adhesion of the formed protrusions tended to decrease.

  An object of the present invention is to provide a method of manufacturing a display device in which a display element constituent material is disposed between opposing first and second substrates in view of the above-described state of the prior art, and the gap between the substrates is reduced. A display comprising a step for making it possible to easily and highly accurately form a protrusion such as a liquid crystal alignment control protrusion on the inner surface of at least one of the pair of substrates. An object of the present invention is to provide a device manufacturing method and a display device obtained by such a manufacturing method.

  According to the first invention of the present application, the first substrate, the second substrate disposed opposite to the first substrate with a gap, and the display element configuration disposed between the first and second substrates. A method of manufacturing a display device comprising a material and a plurality of spacers arranged between opposing surfaces of the first and second substrates to make the gap between the first and second substrates constant A photosensitive resin composition that generates an acid or a base by irradiation with light and cures the surface of at least one of the first and second substrates facing the other substrate. The photosensitive resin is applied via a mask for selectively exposing at least a portion where a spacer is formed on the photosensitive resin composition layer, and a step of applying a predetermined thickness to form a photosensitive resin composition layer. The composition layer is selectively exposed to reduce the photosensitive resin composition in the unexposed area. And moving the part to the exposure part, and curing the photosensitive resin composition in the exposure part to form the spacer in the exposure part, and the first substrate on which the plurality of spacers are formed, The display element configuration before the step of laminating the second substrate and the step of laminating the second substrate on the first substrate, or after the step of laminating the second substrate on the first substrate. Disposing a material on a surface of the first substrate facing the second substrate, and a method for manufacturing a display device. That is, in the first invention, the spacer is formed by selectively exposing the photosensitive resin composition layer, moving the photosensitive resin composition in the unexposed area to the exposed area, and curing it.

  Preferably, after the step of forming the photosensitive resin composition layer having the predetermined thickness, a part of the region other than the region where the spacer is formed is selectively exposed as a second exposure portion, and the second A step of forming protrusions by moving at least a part of the photosensitive resin composition in the unexposed area to the exposed area and further curing it. In this case, by selectively exposing the second exposed portion, not only the spacer but also the protrusion is formed by the curing of the photosensitive resin composition.

  In the first invention, preferably, a mask having first and second light transmitting portions having different light transmittances is used as the mask, and the spacer and the protrusion are simultaneously used in the same selective exposure step. It is formed. In this case, both the spacer and the protrusion can be formed by performing only one exposure process, and the manufacturing process can be further simplified.

  In the first invention, the selective exposure for forming the spacer and the selective exposure for forming the protrusion may be performed by a plurality of exposure steps. In this case, the respective exposure conditions may be selected according to the shapes and dimensions of the spacers and protrusions. Therefore, spacers and protrusions having desired shapes can be formed with high accuracy.

  In the first invention, preferably, the display element constituent material is a liquid crystal, and the protrusion is a liquid crystal alignment control protrusion provided for controlling the alignment of liquid crystal molecules. In this case, the alignment of the liquid crystal molecules is controlled by the liquid crystal alignment control protrusion, and a liquid crystal display device having a wide viewing angle can be easily provided by adjusting the shape of the inclined surface of the protrusion, for example.

  According to the second invention of the present application, the first substrate, the second substrate disposed with a gap so as to face the first substrate, and the first substrate and the second substrate are disposed. And a display device constituent material, wherein a plurality of protrusions are formed on at least one inner surface of the first and second substrates. At least one of the substrates facing the other substrate is exposed to light to generate an acid or base and apply a photosensitive resin composition to a predetermined thickness to form a photosensitive resin composition layer. A step of selectively exposing the photosensitive resin composition layer, moving at least a part of the photosensitive resin composition in an unexposed portion to an exposed portion, further curing, and forming protrusions on the exposed portion. And a step of laminating the first substrate and the second substrate with a gap therebetween. And arranging the display element constituent material on the first substrate before the step of laminating the first and second substrates or before the step of laminating the first and second substrates. A method for manufacturing a display device is provided. That is, the second invention is characterized in that protrusions are formed in the exposed portion by selective exposure / curing of the photosensitive resin composition.

  When the photosensitive resin composition used in the first and second inventions is selectively exposed after being applied to a predetermined thickness, at least part of the photosensitive resin composition in the unexposed area is exposed. It has the feature that it moves to a part. And hardening progresses in an exposure part and the hardened | cured material part thicker than the application | coating thickness of the initial photosensitive resin composition is formed. The specific photosensitive resin composition that is cured as described above will be described more specifically in “Best Mode for Carrying Out the Invention” described later.

  In the second invention, preferably, the display element constituent material is a liquid crystal, and the protrusions are liquid crystal alignment control protrusions for controlling the alignment of liquid crystal molecules. In this case, the liquid crystal alignment control protrusion is easily formed by the above selective exposure, thereby providing a liquid crystal display device having a wide viewing angle easily and reliably by simply adjusting the surface shape of the protrusion. be able to.

  In the first and second inventions, preferably, as the photosensitive resin composition, a curable resin that is cured by the action of an acid or a base, and a photoacid or photobase generator that generates an acid or a base by irradiation with light The photosensitive resin composition containing is used. In this case, only by performing selective exposure, the photosensitive resin composition in the unexposed area moves to the exposed area, and curing proceeds in the exposed area, so that the spacers and / or protrusions are reliably formed. Is done.

  In the present invention, preferably, the photosensitive resin composition further contains an acid or base proliferating agent that produces an acid or base proliferatively by the action of the acid or base. In this case, the acid or base proliferating agent proliferates the acid or base during selective exposure, so that curing in the exposed area can be promoted and the photosensitive resin in the unexposed area The composition can be quickly moved to the exposed area.

  Although it does not specifically limit about the said curable resin, Preferably, a novolak-type epoxy oligomer is used. The photoacid or photobase generator is not particularly limited. Preferably, a photobase generator represented by the following formula (1) is used, and the acid or base proliferator is preferably A base proliferating agent represented by the following formula (2) is used.

  The display device according to the present invention is obtained by the method for manufacturing a display device according to the present invention. As such a display device, in addition to the liquid crystal display device, the first facing each other like an organic EL display is used. , And various display devices in which a display element constituent material is disposed between the second substrates.

  According to the first invention, the photosensitive resin composition layer is applied to a surface of at least one of the first and second substrates facing the other substrate so as to have a predetermined thickness. Then, the portion where the spacer is to be formed is selectively exposed using a mask, the photosensitive resin composition in the unexposed area is moved to the exposed area, and the photosensitive resin composition is cured in the exposed area. Therefore, a spacer is formed in the exposed portion by curing of the photosensitive resin composition.

  Therefore, the spacer can be easily and highly accurately formed by simply applying the photosensitive resin composition to a predetermined thickness and selectively exposing it. Spacers can be formed reliably and easily simply by adjusting the light transmitting area of the mask. For example, even when downsizing of the display device is promoted, the spacers can be reliably formed in a narrow spacer forming area. And can be formed easily. Accordingly, the manufacturing process of the display device can be simplified, the cost of the display device can be reduced, and the display density can be increased and the display device can be downsized.

  In the method for manufacturing a display device according to the second invention, an acid or a base is generated by light irradiation on the surface of at least one of the first and second substrates facing the other substrate, and cured. After the photosensitive resin composition is applied to a predetermined thickness, the photosensitive resin composition is selectively exposed so that the portion where the protrusion is formed becomes an exposed portion, and at least part of the photosensitive resin composition in the unexposed portion is exposed. Projections are formed in the exposed area by moving to the exposed area and curing. Accordingly, since the protrusions can be formed by exposure and selective exposure of the photosensitive resin composition, the manufacturing process can be simplified.

  In addition, it is possible to easily adjust the size of the projections and the interval between the plurality of projections by adjusting the region through which the light of the mask transmits, so that small projections can be formed in a very small region with high accuracy. It becomes possible. Therefore, not only can the cost be reduced by simplifying the manufacturing process, but also it is possible to easily cope with an increase in display density and a reduction in the size of the display device.

  Hereinafter, the present invention will be clarified by describing specific embodiments of the present invention with reference to the drawings.

  With reference to FIGS. 1A and 1B and FIGS. 2A to 2C, a method of manufacturing a display device according to an embodiment of the present invention will be described.

  In the present embodiment, the liquid crystal display device 1 shown in FIG. In the liquid crystal display device 1, the first substrate 2 and the second substrate 3 are opposed to each other with a gap G therebetween. RGB color filters 4 to 6 are arranged on the surface of the first substrate 2 facing the second substrate 3, that is, on the lower surface side. The color filter 4 is a red color filter, the color filter 5 is a green color filter, and the color filter 6 is a blue color filter, and these are disposed above the pixel electrode 7 formed of a transparent electrode disposed below.

  The pixel electrode 7 is formed on the upper surface of the second substrate 3 at a position corresponding to each pixel. A large number of pixel electrodes 7 are arranged in a matrix on the upper surface of the second substrate 3. An alignment film 8 is formed so as to cover the pixel electrode 7. An alignment film 9 is also formed on the lower surface of the first substrate 2 so as to cover the color filters 4 to 6. A frame member 11 is provided to seal the space between the first and second substrates 2 and 3. A space surrounded by the first and second substrates 2 and 3 and the frame member 11 is filled with the liquid crystal 10.

  Further, in order to make the gap G between the first and second substrates 2 and 3 substantially constant in the entire region of the liquid crystal display device 1, a plurality of spacers 12 are arranged. Although not shown in FIG. 1A, a black matrix is formed in the light shielding area, and the spacer 12 is arranged in the light shielding area.

  Further, as shown in an enlarged view of the main part in FIG. 1B, a plurality of liquid crystal alignment control projections 13 are provided on the surface of the alignment film 9. By utilizing the inclined surface of the liquid crystal alignment control protrusion 13, the alignment of the liquid crystal molecules is dispersed, thereby widening the viewing angle.

  A feature of the manufacturing method of the present embodiment lies in the step of forming the spacer 12 and the liquid crystal alignment control protrusion 13. This will be clarified by more specifically describing the method for manufacturing the liquid crystal display device 1.

  First, as shown in FIG. 2A, a first substrate 2 is prepared. The first substrate 2 is a transparent substrate made of a transparent material such as glass. Color filters 4 to 6 are provided in a matrix on the upper surface of the first substrate 2. A photosensitive resin composition is applied to one surface of the first substrate 2 to a predetermined thickness so as to cover the color filters 4 to 6, thereby forming the photosensitive resin composition layer 14.

  The photosensitive resin composition layer 14 is made of a photocurable resin composition that generates and cures acid or base upon irradiation with light. As described later, when selectively exposed, the photosensitive resin composition layer 14 is exposed to light. The photosensitive resin composition moves to the exposed portion side, and the photosensitive resin composition is cured in the exposed portion.

  The process itself which forms the said photosensitive resin composition layer 14 in predetermined thickness can use a well-known appropriate coating method. Examples of the coating method include spin coating, spin & slit, slit coating, spray coating, dip coating, bar coating, ink jet, screen printing method, doctor blade method, casting method, and die coating method.

  After forming the photosensitive resin composition layer 14, selective exposure is performed using the mask 15. The mask 15 includes a light transmitting portion 15a that transmits light and a shielding portion 15b that shields light. The mask 15 is made of a light shielding material, and the light transmission portion 15a is formed by providing an opening. But the mask 15 may have the structure which laminated | stacked the light-shielding film in the area | region according to the light-shielding part 15b on the single side | surface of a translucent sheet | seat.

  The light transmitting portion 15a is located on the region where the spacer 12 is finally formed in the region where the photosensitive resin composition layer 14 is formed. In this state, the photosensitive resin composition layer 14 is irradiated with light from above through the mask 15. Therefore, the light transmitted through the light transmitting portion 15a is irradiated only to the region where the spacer is scheduled to be formed, and the portion where the spacer is formed becomes the exposed portion. The photosensitive resin composition constituting the photosensitive resin composition layer 14 generates an acid or base upon irradiation with light and cures. In this case, the photosensitive resin composition in the unexposed area is cured. It moves to the exposed part side where the light is advancing and has the property of being cured in the exposed part.

  Therefore, as shown in FIG. 2B, the photosensitive resin composition is exposed to the light and the unexposed photosensitive resin composition of the resin composition layer 14 moves to the exposed portion, and protrudes in the spacer formation region. To do. In this way, a plurality of protrusions 14a are formed.

  In the present embodiment, as shown in FIG. 2B, the second selective exposure is performed using the second mask 16. The second mask 16 includes a first light transmission part 16a, a second light transmission part 16b, and a light shielding part 16c. The first light transmission part 16 a is formed in the same manner as the first light transmission part 16 a of the mask 15. That is, it is located in the region where the spacer is formed. On the other hand, the second light transmission portion 16b is located in a portion where the liquid crystal alignment control protrusion 13 is provided.

  The light transmitting portions 16a and 16b are provided by forming through holes in the mask 16 made of a light shielding material. However, similarly to the first mask 15, the second mask 16 may be formed by laminating a light-shielding film for forming the light-shielding portion 16c on one surface of the light-transmitting sheet.

  A second exposure is performed through the second mask 16. In this case, the light is irradiated to the portion where the spacer 12 is formed and the portion where the protrusion 13 is formed. Accordingly, the curing further proceeds in the protruding portion 14a, and the photosensitive resin composition in the surrounding unexposed portion further moves toward the protruding portion 14a, and the curing proceeds. On the other hand, also under the light transmission part 16b, hardening progresses, the photosensitive resin composition of the surrounding unexposed part moves to a protrusion formation part, and hardening progresses. As a result, as shown in FIG. 2C, the protrusions 14a are further grown and hardened, whereby the spacers 12 are formed. In addition, a plurality of protrusions 13 are formed. In addition, most of the photosensitive resin composition in the unexposed area is formed with the spacer 12 and the plurality of protrusions 13 depending on the exposed area. The composition layer is dried and cured, and the alignment film 9 is formed.

  That is, the spacers 12 and the protrusions 13 are formed by performing the first and second selective exposures, in other words, by two-stage exposure. As described above, the two-step exposure has a larger aspect ratio of the spacer 12 than the protrusion 13, and therefore, it is necessary to irradiate light with sufficient intensity and time to form the spacer 12. It depends.

  The aspect ratio refers to the height dimension with respect to the horizontal dimension of the protruding portion.

  As described above, in the manufacturing process of the present embodiment, the alignment film 9 can be obtained simply by performing two-stage selective exposure after the photocurable resin composition layer 14 is formed to a predetermined thickness by an appropriate coating method. Then, the spacer 12 and the protrusion 13 can be formed. When the photolithography method is used, complicated development processing is required, but in the present embodiment, such development processing is not required. Therefore, the manufacturing process can be simplified. Moreover, the spacer 12 and the protrusion 13 having a desired shape can be easily and accurately formed only by devising the shape, size and arrangement of the light transmitting portions 15a, 16a and 16b of the masks 15 and 16. Therefore, in the liquid crystal display device 1, the smaller spacers 12 and the protrusions 13 can be formed with high accuracy and easily even when the pixels are made smaller and more accurate display is performed, or when the size is reduced. Can do.

  Next, after forming the spacer 12 and the protrusion 13 simultaneously with the alignment film 9, the first substrate 2 is laminated on the second substrate 3. Prior to the stacking process, the pixel electrode 7 and the alignment film 8 shown in FIG. 1A are formed in advance on the surface of the second substrate 3 facing the first substrate 2. At the time of lamination, the first and second substrates 2 and 3 are bonded via the frame member 11. Thereafter, the liquid crystal 10 is injected from the liquid crystal injection portion of the frame member 11, and the injection portion is sealed.

  Alternatively, prior to laminating the first and second substrates 2 and 3 with a gap G therebetween, the liquid crystal 10 is disposed on one inner surface of the first and second substrates 2 and 3, and then the other substrate is mounted. You may laminate. In this way, the liquid crystal display device 1 shown in FIG. 1A can be obtained.

  In the above-described embodiment, light is irradiated twice on the portion where the spacer 12 is formed in the two-stage selective exposure, but only the portion where the spacer 12 is formed is selectively selected using the first mask. Then, the second mask may be used to selectively expose only the portion where the protrusions 13 are formed. In that case, the first mask and the second mask may be formed so as to have a light transmitting portion corresponding to the size of the spacer and the protrusion formed in the cured portion, respectively.

  In the above embodiment, the two steps of selective exposure are performed to form the spacers 12 and the protrusions 13. However, for example, using the mask 21 shown in FIG. May be formed.

  In the mask 21, a first light transmission part 21a and a second light transmission part 21b, and a light shielding part 21c are provided. Here, the first light transmitting portion 21a is provided by providing an opening in the mask 21, and the light transmittance of the second light transmitting portion 21b of the mask 21 is higher than that of the first light transmitting portion 21a. However, unlike the light-shielding portion 21c, the light transmittance is sufficient to transmit light sufficient to form the protrusion 13 described above. In this way, by using the mask 21 having the first and second light transmission portions 21a and 21b having different light transmission portions, the spacer 12 and the protrusion 13 can be formed by performing only one selective exposure. Can do.

  In the mask 21, the first light transmission portion 21 a is an opening, but the first light transmission portion 21 a is not an opening but may be formed of a material that transmits light. The light transmittance of the first light transmission part 21a may be higher than that of the second light transmission part 21b.

  The second mask 21 has a light-shielding film attached to one side of a light-transmitting sheet such as glass in the light-shielding region 21c, and the light transmittance of the first and second light-transmitting portions 21a and 21b. However, it may have a structure in which different light-transmitting films are attached.

  In the method for manufacturing the liquid crystal display device 1 of the above embodiment, the spacers 12 and the protrusions 13 are formed on the upper surface of the alignment film 9 by selective exposure, but the protrusions are not provided as in the modification shown in FIG. Only the spacer 12 may be formed by the same method as in the above embodiment. That is, when the protrusion 13 is not required, the protrusion 13 may not be formed. Further, the protrusion 13 may be provided on the alignment film 9 by another method.

  In the second modification shown in FIG. 5A, the alignment film 31 is formed after the color filters 4 to 6 are formed on the first substrate 2. In the present modification, the protrusion 13 described above is formed integrally with the alignment film 31 on the alignment film 31. On the other hand, a spacer 32 made of a material different from that of the alignment film 31 is disposed on the alignment film 31. Thus, the spacer 32 made of another resin or an inorganic material may be prepared and fixed on the alignment film 31 regardless of the selective exposure of the photosensitive resin composition layer. That is, the spacer 32 may be formed according to a known spacer formation method.

  In this modification, selective exposure may be performed using the mask 33 shown in FIG. That is, the photosensitive resin composition is applied to have a predetermined thickness so as to cover the color filters 4 to 6 to form a photosensitive resin composition layer. Thereafter, exposure is selectively performed from above using the mask 33. In this case, the mask 33 includes a light transmission part 33a and a light shielding part 33b. The light transmission part 33a is located above the part where the protrusion 13 is formed. Therefore, when light irradiation is performed, the region located below the light transmitting portion 33a, that is, the region where the protrusion is formed becomes an exposed portion, and an acid or a base is generated in the photosensitive resin composition of the exposed portion, Curing proceeds. At the same time, the photosensitive resin composition in the unexposed area moves to the exposed area side. Accordingly, the thickness of the exposed portion is increased and hardened, and the protrusion 13 is formed. Also in this modification, since the protrusion 13 is formed by application of the photosensitive resin composition and selective exposure, it is easy and highly accurate only by adjusting the size and arrangement of the light transmitting portion 33a in the mask 33. The protrusion 13 can be formed on the surface.

  In addition to the selective exposure for creating spacers and / or protrusions, if necessary, it is preferable to finally irradiate the entire curable composition with light to cure the curable composition. Accordingly, after the projection is formed by selective exposure, the flattened film portion is in an uncured state, so that it can be cured and the whole can be uniformly cured.

  In the embodiments and modifications described above, the spacers and / or protrusions are formed by applying the specific photosensitive resin composition and performing selective exposure, so that the manufacturing process is simplified as described above. In addition, the liquid crystal display device can be reduced in size. In addition, this invention has the characteristics in the formation process of the said spacer and / or protrusion, The other process of the manufacturing method of a display apparatus can be performed in accordance with the conventionally well-known manufacturing method of a liquid crystal display device.

  In the above-described embodiment and modification, the method for manufacturing a liquid crystal display device has been described. However, the present invention is such that, for example, the first and second substrates facing each other, such as an organic EL display device, have a predetermined gap therebetween. The present invention can be applied to various manufacturing methods of display devices.

  Next, the specific photosensitive resin composition used in the present invention will be described.

  In the present invention, after applying the photosensitive resin composition to a predetermined thickness and forming the photosensitive resin composition layer, the photosensitive resin composition in the unexposed area moves to the exposed area by selective exposure, Curing proceeds in the exposed area. For this reason, the thickness increases at the exposed portion, and spacers and protrusions are formed. As long as the photosensitive resin composition moves from the unexposed area to the exposed area and rises in the exposed area so that the photosensitive resin composition can be cured, the photosensitive resin composition that can be used is particularly limited. It is not a thing. However, in the present invention, preferably, a photosensitive resin composition containing a curable resin that is cured by the action of an acid or a base, and a photoacid or base generator that generates an acid or a base by irradiation with light, more preferably. Further, a photosensitive resin composition further containing an acid or base proliferating agent that proliferately generates an acid or base by the action of an acid or base is used. If such a photosensitive resin composition is used, unlike the photolithography method, it is not necessary to perform development with a solvent or the like. Accordingly, not only can the environmental burden be reduced, but there is no need to perform a complicated development process and a drying process after development, and the manufacturing process can be greatly simplified.

  However, also in the present invention, when it is desired to remove the photosensitive resin composition in the unexposed portions other than the portions where the spacers and protrusions are formed, development may be performed using an alkaline solution or the like.

  The blending ratio of the curable resin is preferably in the range of 50 to 80% by weight with respect to 100% by weight of the photosensitive resin composition. If the curable resin is less than 50% by weight, a photoacid or photobase generator or an acid or base proliferating agent may be precipitated, and if it exceeds 80% by weight, the curability may be inferior.

  Although it does not specifically limit as said curable resin, An epoxy-type compound, an acrylate-type oligomer, an isocyanate-type oligomer etc. are mentioned, It uses preferably. Especially, since a crosslinking reaction advances efficiently by the effect | action of a base, an epoxy-type compound is used more preferable.

  The epoxy compound is not particularly limited, but is a novolak epoxy resin such as a BPF type epoxy resin, a BPA type epoxy resin, a BPF type epoxy resin, or a novolak type epoxy oligomer described in the catalog of Toto Kasei Co., Examples thereof include a flexible epoxy resin, an epicoat basic solid type described in the catalog of Yuka Shell Epoxy Co., an Epicoat Bis F solid type, and an EHPE alicyclic solid epoxy resin described in the Daicel Chemical Industries catalog.

  Furthermore, as said epoxy-type compound, it is the Denacol series EX-611, EX-612, EX-614, EX-614B, EX-614, EX-622, EX-512, EX which are the Nagase ChemteX catalog. -521, EX-411, EX-421, EX-313. EX-314, EX-321, EX-201, EX-211, EX-212, EX-252, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX- 832, EX-841, EX-861, EX-911, EX-941, EX-920, EX-721, EX-221, EM-150, EM-101, EM-103, YD- described in the catalog of Toto Kasei 115, YD-115G, YD-115CA, YD-118T, YD-127, 40E, 100E, 200E, 400E, 70P, 200P, 400P, 1500NP, 1600, 80MF, 100MF, which are Epolite series described in the Kyoeisha Chemical Company catalog Examples thereof include liquid epoxy resins such as 4000, 3002, 1500.

  Further, as the epoxy compound, Celoxide 2021, Celoxide 2080, Celoxide 3000 described in the catalog of Daicel Chemical Industries, which is an alicyclic epoxy compound, Epolide GT300, Epolide GT400, Epolide D-100ET, Epolide D-100OT, Epolide D Examples include liquid epoxy resins such as -100DT, Epolide D-100ST, Epolide D-200HD, Epolide D-200E, Epolide D-204P, Epolide D-210P, Epolide D-210P, Epolide PB3600, Epolide PB4700.

  Among the curable resins, novolac epoxy oligomers are more preferably used. The photosensitive resin composition according to the present invention contains a novolac epoxy oligomer (YDCN-701, Mw = 2100, Mw / Mn = 1.58, n≈10) represented by the following formula (3). Further preferred.

  The blending ratio of the photoacid or photobase generator is preferably in the range of 1 to 30% by weight with respect to 100% by weight of the photosensitive resin composition. If the photoacid or photobase generator is less than 1% by weight, the amount of acid or base generated may be too small. If it exceeds 30% by weight, the effect of adding the photoacid or photobase generator is obtained. May be excessive.

The photoacid generator used as the photoacid or photobase generator is not particularly limited, and examples thereof include onium salts. More specifically, diazonium, phosphonium, and iodonium salts such as BF ₄ ⁻ , PF ₆ ⁻ , SBF ₆ ⁻ , and ClO ₄ ^— , and other organic halogen compounds, organic metals, and organic halides can be used. .

  The photoacid generator is not particularly limited, but is triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethaneantimonate, triphenylsulfonium benzosulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, Sulfonium salt compounds such as dicyclohexyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, dicyclohexylsulfonylcyclohexanone, dimethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, iodonium salts such as diphenyliodonium trifluoromethanesulfonate, N-hydroxysuccinimide Such as trifluoromethanesulfonate. It is. These acid generators may be used alone or in combination of two or more. Furthermore, a known sensitizer can be used. Sensitizers suitable for the present invention include aromatic polycyclic compounds, porphyrin compounds, phthalocyanine compounds, polymethine dye compounds, merocyanine compounds, coumarin compounds, thiopyrylium compounds, pyrylium compounds, p-dialkylaminostyryl compounds, thioxanthene compounds, etc. However, the present invention is not limited to this.

  The photoacid generator is not particularly limited, but preferably, at least one compound selected from the group consisting of a more reactive onium salt, diazonium salt, and sulfonate ester is used.

  The photobase generator used as the photoacid or photobase generator is not particularly limited, but conventionally known o-nitrobenzyl type photobase generators, (3,5-dimethoxybenzyloxy) carbonyl type light. Examples include base generators, amyloxyimino group type photobase generators, dihydropyridine type photobase generators, and the like. Especially, since it is excellent in base generation | occurrence | production efficiency and the simplicity of a synthesis | combination, an o-nitrobenzyl type photobase generator is used preferably.

  In the photosensitive resin composition according to the present invention, since at least a part of the photosensitive resin composition in the unexposed part moves more efficiently in the exposed part, the photobase generator represented by the above-described formula (1) It is more preferable to contain.

  The photoacid or photobase generator that generates an acid or a base by irradiation with light preferably generates an acid or a base by applying heat. When the photoacid or photobase generator generates an acid or a base by applying heat, the acid or base can be generated by heat-treating the photosensitive resin composition.

  The mixing ratio of the acid or base proliferating agent is preferably in the range of 10 to 45% by weight with respect to 100% by weight of the photosensitive resin composition. If the acid or base proliferating agent is less than 10% by weight, the acid or base generated by the growth reaction may be too little, and if it exceeds 45% by weight, the acid or base proliferating agent may be precipitated.

  Examples of the acid proliferating agent used as the acid or base proliferating agent include benzyl sulfonate type, acetoacetate type, acetal type, diol monosulfonate type, and diol disulfonate type.

  Examples of the base proliferating agent used as the acid or base proliferating agent include difunctional, spherical polyfunctional oligomer, linear polymer, and siloxane type 9-fluorenyl carbamate derivatives. In the photosensitive resin composition according to the present invention, since at least a part of the photosensitive resin composition in the unexposed area moves more efficiently in the exposed area, the base proliferating agent represented by the above formula (2) is used. More preferably.

  The base proliferating agent represented by the above formula (2) is decomposed by a base proliferating reaction to newly generate an amine. Furthermore, the generated amine functions as a new catalyst, and a large number of amines are produced in a proliferative manner.

  In the above formula (2), X represents a hydrogen atom, a substituted alkyl group, or an unsubstituted alkyl group. Specific examples of X in formula (2) include a methyl group, an ethyl group, and a propyl group. X is preferably an unsubstituted alkyl group because a base proliferating reaction occurs effectively. Especially, since the steric hindrance in X becomes small and the base proliferation reaction is more likely to occur, X is more preferably an ethyl group.

  In the above formula (2), Z represents a substituted or unsubstituted alkylene chain. Specific examples of Z in formula (2) include a methylene chain, an ethylene chain, a propylene chain, and the like. Y is preferably an unsubstituted alkylene chain because the above-described base growth reaction occurs effectively. Among them, Y is more preferably a methylene chain because the steric hindrance in Y is reduced and the base growth reaction is more likely to occur more effectively.

  In formula (2) mentioned above, n shows the integer of 1-4. When the base proliferating agent represented by formula (2) has a plurality of 9-fluorenyl carbamate groups in the same molecule, the base proliferating reaction is more likely to occur more effectively by the catalytic action of the generated base. Therefore, in the above formula (2), n is preferably an integer of 3 or 4.

  Specific examples of the compound represented by the formula (2) described above include compounds represented by the following formulas (4) and (5).

  The base proliferating agent represented by the above formulas (4) and (5) has a plurality of 9-fluorenyl carbamate groups in the same molecule. Therefore, it has a feature that the base proliferation reaction easily proceeds by the catalytic action of the generated base. In the photosensitive resin composition according to the present invention, since at least a part of the photosensitive resin composition in the unexposed area moves more efficiently in the exposed area, the base proliferating agent represented by the above formula (4) is used. More preferably, it contains a base proliferating agent represented by the above formula (5).

  The base proliferating agent represented by the above formula (2), (4) or (5) is not particularly limited. For example, an addition reaction between fluorenyl methanol and an isocyanate derivative, or an acrylate monomer having a fluorenyl carbamate group. And a polythiol derivative. By appropriately using a tin catalyst in the former addition reaction, the above compound can be synthesized easily. In the latter addition reaction, the compound can be easily synthesized by appropriately using a base catalyst.

  In the photosensitive resin composition according to the present invention, since at least a part of the photosensitive resin composition in the unexposed area moves more efficiently to the exposed area, the novolak epoxy represented by the above-described formula (3) It is preferable to contain an oligomer, a photobase generator represented by the above formula (1), and a base proliferating agent represented by the above formula (5).

  The photosensitive resin composition according to the present invention preferably further contains a sensitizer. When the photosensitive resin composition contains a sensitizer, sensitivity is increased.

  The sensitizer is not particularly limited. For example, benzophenone, p, p′-tetramethyldiaminobenzophenone, p, p′-tetraethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene, pyrene, Perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro-4- Nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2-te t-butylanthraquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis (5 , 7-dimethoxycarbonylcoumarin) or coronene. These sensitizers may be used independently and 2 or more types may be used together.

  The blending ratio of the sensitizer is preferably in the range of 1 to 20% by weight in 100% by weight of the photosensitive resin composition. If the sensitizer is less than 1% by weight, the sensitivity may not be sufficiently increased. If the sensitizer exceeds 20% by weight, it may be excessive to increase the sensitivity.

  The photosensitive resin composition according to the present invention may further contain an appropriate solvent. Application | coating property can be improved by mix | blending a solvent with the photosensitive resin composition.

  Although it does not specifically limit as said solvent, Aromatic hydrocarbon compounds, such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, diethylbenzene; Cyclohexane, cyclohexene, dipentene, n-pentane, isopentane, n-hexane, isohexane, Saturated or unsaturated hydrocarbon compounds such as n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, isodecane, tetrahydronaphthalene, squalane; diethyl ether, di-n-propyl ether, di- Isopropyl ether, dibutyl ether, ethyl propyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibu Ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol methyl ethyl Ether, tetrahydrofuran, 1,4-dioxane, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate, ethylcyclohexane, methylcyclohexane, p-menthane, o Menthane, m-menthane; ethers such as dipropyl ether and dibutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone and cycloheptanone; Examples thereof include esters such as ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate, methyl cellosolve, ethyl acetate cellosolve, butyl cellosolve, ethyl lactate, propyl lactate, butyl lactate, isoamyl lactate, and butyl stearate. These solvents may be used alone or in combination of two or more.

  What is necessary is just to select the compounding ratio of the said solvent suitably so that it may apply uniformly, for example, when a photosensitive resin composition is applied on a board | substrate and a photosensitive resin composition layer is formed.

  The curable composition of the present invention may contain a silane coupling agent.

  The silane coupling agent plays a role of improving the adhesion between the curable composition of the present invention and the substrate. Such a silane coupling agent is not particularly limited, and conventionally known ones can be used. . Especially, what has an acryloxy group or a methacryloxy group as a functional group is preferable. By containing a silane coupling agent having an acryloxy group-waiting methacryloxy group as a functional group, the adhesion of the negative resist of the present invention to the substrate can be greatly improved.

  Examples of the silane coupling agent having an acryloxy group include 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane. Examples of the silane coupling agent having a methacryloxy group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltri An ethoxysilane etc. are mentioned. These silane coupling agents may be used independently and 2 or more types may be used together.

  In the curable composition of the present invention, the content of the silane coupling agent is not particularly limited, but when the total of the alkali-soluble resin and the polymerizable monomer is 100 parts by weight, the preferred lower limit is 0.1. Part by weight, the preferred upper limit is 15 parts by weight. If it is less than 0.1 part by weight, the adhesion to the substrate may be lowered. A more preferred lower limit is 1 part by weight, and a more preferred upper limit is 10 parts by weight.

  If necessary, other additives may be further added to the photosensitive resin composition used in the present invention. Such additives include fillers, pigments, dyes, leveling agents, antifoaming agents, antistatic agents, UV absorbers, pH adjusters, dispersants, dispersion aids, surface modifiers, plasticizers, plasticizers. Examples include accelerators and sagging inhibitors. Next, specific examples of the step of forming the spacers and / or protrusions, which are the characteristics of the present invention, by selective exposure of the photosensitive resin composition will be described.

(Example 1)
100 parts by weight of the novolak epoxy oligomer (YDCN-701) represented by the above formula (3), 10 parts by weight of the photobase generator (PBG) represented by the above formula (1), and the above formula ( 5 parts by weight of the base proliferating agent represented by 5) is diluted with 900 parts by weight of PEGMEA (propylene glycol-1-monomethyl ether-2-acetate): CHCl ₃ = 4: 5 solvent (weight ratio). Resin composition A was obtained.

  Next, a structure in which color filters 4 to 6 are formed on a glass substrate for forming a liquid crystal display device is prepared, and the above photosensitive property is formed on the upper surface of the substrate 2 to a thickness of 2 μm by spin coating. A photosensitive resin composition layer made of the resin composition A was formed.

Thereafter, the first selective exposure was performed using the mask 15 shown in FIG. In this case, the light transmission portion 15a is an area having a size of 8 μm × 8 μm where the spacer is formed. The light irradiation amount was 500 mJ / cm ² .

Thereafter, the second selective exposure was performed using the second mask 16 shown in FIG. The dimensions of the first light transmission part 16a were the same as those of the first light transmission part 15a, and the dimensions of the second light transmission part 16b were 3 μm × 3 μm. The light irradiation amount in the second selective exposure was set to 100 mJ / cm ² .

  As a result, a flattened film made of a cured product of the photosensitive resin composition having a thickness of 1.9 μm is formed, the spacer 12 protruding to a height of 2 μm from the upper surface of the flattened film, and a height of 0.3 μm Thus, the raised protrusion 13 could be formed.

(A), (b) is the schematic front sectional drawing of the liquid crystal display device manufactured by one Embodiment of this invention, and the partial notch expansion front sectional drawing which shows the principal part. (A) is typical front sectional drawing which shows the process of performing 1st selective exposure to the photosensitive resin composition layer in one Embodiment of this invention, (b) is 2nd selective exposure. It is typical front sectional drawing which shows the process to perform, (c) is typical front sectional drawing for demonstrating the spacer and protrusion which were published by selective exposure. Front sectional drawing which shows the mask used by the modification of this invention. The typical partial notch front sectional drawing for demonstrating the planarization film | membrane and spacer which were formed in the modification of this invention. (A), (b) is typical front sectional drawing for demonstrating the processus | protrusion formed on the planarization film | membrane in the further another modification of this invention, and the spacer prepared separately, (b) is Front sectional drawing which shows the mask used for forming the processus | protrusion shown to (a).

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Liquid crystal display device 2, 3 ... 1st, 2nd board | substrate 4-6 ... Color filter 7 ... Pixel electrode 8, 9 ... Orientation film 10 ... Liquid crystal 11 ... Frame material 12 ... Spacer 13 ... Protrusion 14 ... Photosensitive resin Composition layer 14a ... Projection 15 ... Mask 15a ... Light transmission part 15b ... Light shielding part 16 ... Mask 16a ... First light transmission part 16b ... Second light transmission part 21 ... Mask 21a ... First light transmission part 21b 2nd light transmission part 21c ... Light shielding part 31 ... Alignment film 32 ... Spacer 33 ... Mask 33a ... Light transmission part 33b ... Light shielding part G ... Gap

Claims (13)

A first substrate; a second substrate disposed opposite to the first substrate with a gap; a display element constituent material disposed between the first and second substrates; and the first and second substrates A plurality of spacers disposed between opposing surfaces of the first and second substrates in order to make the gap between them constant,
A photosensitive resin composition that generates an acid or a base by irradiation with light and cures at a predetermined thickness on a surface of at least one of the first and second substrates facing the other substrate. Applying and forming a photosensitive resin composition layer; and
The photosensitive resin composition layer is selectively exposed through a mask for selectively exposing at least a portion where a spacer is formed on the photosensitive resin composition layer, and the photosensitive resin composition in an unexposed portion is exposed. A step of forming the spacer in the exposed portion by moving at least part of the exposed portion to the exposed portion and curing the photosensitive resin composition in the exposed portion;
Laminating the second substrate on the first substrate on which the plurality of spacers are formed;
Before the step of laminating the second substrate on the first substrate, or after the step of laminating the second substrate on the first substrate, the display element constituting material is transferred to the second substrate of the first substrate. And a step of arranging the display device on a surface facing the substrate.   After the step of forming the photosensitive resin composition layer having the predetermined thickness, a part of the region other than the region where the spacer is formed is selectively exposed as a second exposure unit, and the second exposure unit The method for manufacturing a display device according to claim 1, further comprising forming a protrusion by moving at least a part of the photosensitive resin composition in the unexposed area to further curing.   3. The display device according to claim 2, wherein a mask having first and second light transmission portions having different light transmittances is used as the mask, and the spacer and the protrusion are simultaneously formed in the same selective exposure step. Manufacturing method.   The method for manufacturing a display device according to claim 2, wherein the selective exposure for forming the spacer and the selective exposure for forming the protrusion are performed by a plurality of exposure steps.   The display device manufacturing method according to claim 2, wherein the display element constituent material is a liquid crystal, and the protrusion is a liquid crystal alignment control protrusion provided to control alignment of liquid crystal molecules. Method. A first substrate, a second substrate disposed with a gap so as to face the first substrate, and a display element constituent material disposed between the first and second substrates, A method of manufacturing a display device in which a plurality of protrusions are formed on the inner surface of at least one of the first and second substrates,
A photosensitive resin composition is applied to a predetermined thickness for generating an acid or a base by irradiation with light on a surface of at least one of the first and second substrates facing the other substrate. And forming a photosensitive resin composition layer;
Selectively exposing the photosensitive resin composition layer, moving at least a part of the photosensitive resin composition in an unexposed area to an exposed area, and further curing the photosensitive resin composition layer to form protrusions in the exposed area; ,
Laminating the first substrate and the second substrate with a gap therebetween;
Placing the display element constituent material on the first substrate before the step of laminating the first and second substrates or before the step of laminating the first and second substrates. Device manufacturing method.   The method for manufacturing a display device according to claim 6, wherein the display element constituent material is liquid crystal, and the protrusions are liquid crystal alignment control protrusions for controlling the alignment of liquid crystal molecules.   As the photosensitive resin composition, a photosensitive resin composition containing a curable resin that is cured by the action of an acid or a base and a photoacid or a photobase generator that generates an acid or a base by irradiation with light is used. The manufacturing method of the display apparatus of any one of Claims 1-7.   The method for manufacturing a display device according to claim 8, wherein the photosensitive resin composition further contains an acid or a base proliferating agent that proliferately generates an acid or a base by the action of the acid or the base.   The method for manufacturing a display device according to claim 8, wherein the curable resin is a novolac epoxy oligomer. The method for manufacturing a display device according to claim 8, wherein the photoacid or photobase generator is a photobase generator represented by the following formula (1).

The method for manufacturing a display device according to claim 8, wherein the acid or base proliferating agent is a base proliferating agent represented by the following formula (2).

  The display apparatus obtained by the manufacturing method of the display apparatus of any one of Claims 1-12.

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