JP2011112838A - Method for producing spacer for liquid crystal display apparatus, ink for forming spacer, the liquid crystal display apparatus, and method for producing the apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink for forming a spacer, which can control the height of the spacer, and to provide a method for producing the spacer for a liquid crystal display apparatus by using the ink for forming the spacer, the liquid crystal display apparatus, and a method for producing the liquid crystal display apparatus. <P>SOLUTION: Liquid droplets of the ink for forming the spacer, which ink contains a resin and a solvent for dissolving the resin which effectively does not contain solid particles, are dropped on a substrate by an inkjet method, and the solvent is removed from the liquid droplets landed on the substrate to form the spacer at a predetermined position on the substrate; and the ink for forming the spacer for the liquid crystal display apparatus is such that the surface free energy of the hardened resin being the spacer is in the range of 26 or greater and 30 mJ/m<SP>2</SP>or less. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a spacer for a liquid crystal display device, a spacer forming ink, a liquid crystal display device, and a method for manufacturing the same.

  In recent years, a liquid crystal display device is used as a display device such as a monitor for a color television or a personal computer. In a liquid crystal display device, generally, a pair of transparent substrates having transparent electrodes and the like are arranged to face each other with a gap of 1 to 10 μm, and a liquid crystal layer is formed by enclosing a liquid crystal substance between the pair of substrates. It has a configuration. By applying an electric field to the liquid crystal layer through an electrode, the liquid crystal material is aligned, and the alignment of the liquid crystal material controls transmission / non-transmission of light from the backlight to display an image.

  If the thickness of the liquid crystal layer of the liquid crystal display device is non-uniform, display unevenness and contrast abnormality occur. Therefore, it is necessary to keep the gap between the substrates constant and make the thickness of the liquid crystal layer uniform. Therefore, conventionally, the gap between the substrates is made by a method in which beads such as silica particles, metal oxide particles, and thermoplastic resin particles having a uniform particle size distribution are spread on the substrates and these are arranged as spacers between the substrates. A method of keeping constant has been used.

  However, in the above-described conventional method using dispersed beads as spacers (particulate spacers), the beads are not fixed. Therefore, there is a problem in that the beads move due to vibration of the liquid crystal display device and display variation occurs. In addition, since it is difficult to accurately place beads at a desired position when spraying, the distribution tends to vary, and in some cases, beads are placed in the display area of the liquid crystal display device, and the beads are displayed. In some cases, it may cause display defects such as variations and light loss.

  Therefore, a method of forming a spacer on one substrate by a photolithography method using a photosensitive resin has been studied. According to this method, it is possible to form a resist pattern as a spacer at a desired position with high positional accuracy, and generally the adhesion force of the resist pattern to the substrate is relatively high. It can be considered that this can be improved in terms of alignment abnormality and contrast reduction.

  However, in the photolithography method, there is a lot of material loss in order to remove unnecessary portions after applying a photosensitive resin as a spacer material to the entire surface of the substrate, and multiple steps such as development and peeling are necessary. There is a problem that the manufacturing process becomes complicated. Further, it is necessary to prepare a plate for a photolithography method corresponding to each product, and there is a problem that the process is complicated in this respect as well. Furthermore, with the recent increase in size of liquid crystal display devices, uniform application of spacer materials and preparation of corresponding plates tend to be difficult.

  On the other hand, a method of arranging particulate spacers (beads) on a substrate by a method of printing ink containing particulate spacers on a substrate by an inkjet method has been studied (Patent Documents 1 to 4). According to the inkjet method, the spacer can be formed by a simple process as compared with the photolithography method. In addition, it is considered that the positional accuracy can be remarkably improved as compared with the method of spraying the particulate spacer. For example, an ink in which particulate spacers are dispersed in a solvent is locally printed by an ink jet method on a black matrix portion of a color filter that is a non-display area, and the solvent is evaporated from the printed ink, whereby black It is expected that it will be possible to selectively form particulate spacers on the matrix.

  However, according to the study by the present inventors, even when the particulate spacer is arranged on the substrate by the ink jet method, sufficient positional accuracy is not always necessary when forming a spacer of a high-definition liquid crystal display device. It became clear that was not obtained.

JP 11-316380 A Japanese Patent Laid-Open No. 2002-333631 JP 2004-13116 A JP 2003-295198 A

  When forming a spacer for a liquid crystal display device by removing the solvent from droplets consisting of an ink containing a resin and a solvent in which the resin is dissolved substantially free of solid particles, a spacer height control function is provided. Since it does not contain the particulate spacer, the spacer height is required to be controlled only by the cured resin after removing the solvent. However, even if the same ink is used, if the surface free energy of the substrate is different, the wettability of the ink is different and the spacer height varies. For this reason, in order to function as a spacer for a liquid crystal display device, a technique for controlling the height to an arbitrary value (about 2.5 to 5.0 μm) is required.

  Furthermore, in order to form the spacer within the non-display area of the liquid crystal display device, it is necessary to control the spacer diameter to an arbitrary value (about 5 to 50 μm). For this reason, it is necessary to control the spacer diameter / height value to an arbitrary value (1 to 20) as the spacer shape.

The inventors of the present invention have a sufficiently high position while having a sufficient height by setting the difference (A) between the surface tension of the ink and the surface free energy of the substrate within the range of −10 to 15 mJ / m ^2. It has already been found that it is possible to form a spacer in which the height variation is suppressed with accuracy. However, depending on the substrate, even when the value of A is set within the above range, it is clear that the ink does not spread sufficiently and the spacer diameter / height value may exceed 20 in some cases. It became.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a manufacturing method for forming a spacer with an ink containing a resin and a solvent that dissolves the resin, which does not substantially contain solid particles. The present invention provides a spacer forming ink that can control the height of the spacer. Another object of the present invention is to provide a method for producing a spacer for a liquid crystal display device using the spacer forming ink. Furthermore, an object of this invention is to provide the liquid crystal display device which has the spacer for liquid crystal display devices formed by the method, and its manufacturing method.

The present invention prints droplets made of an ink containing a resin and a solvent that dissolves the resin and substantially not containing solid particles on a substrate by an inkjet method, and removes the solvent from the droplets on the substrate. And a liquid crystal display device spacer forming ink for forming spacers arranged at predetermined positions on the substrate, wherein the surface free energy of the cured resin is 26 mJ / m ² or more and 30 mJ / m ² or less. The present invention relates to a spacer forming ink for a display device.

  Since the ink of the present invention can be printed by an inkjet method, a spacer for a liquid crystal display device can be easily formed. Moreover, since the ink does not substantially contain solid particles, the spacer for a liquid crystal display device can be formed with sufficiently excellent positional accuracy. Further, as the shape of the spacer, the value of the spacer diameter / height can be adjusted within a preferable range as the spacer for the liquid crystal display device.

The reason why the value of the spacer diameter / height can be adjusted within a preferable range as the spacer for the liquid crystal display device is as follows. That is, if the wettability of the ink with respect to the substrate is too high, the value of spacer diameter / height exceeds 20, and the spacer diameter becomes large, so that it is difficult to form a spacer in a desired printing region. The inventors adjust the spacer diameter / height value in the range of 1 to 20 when the surface free energy of the cured resin material dissolved in the ink is 26 mJ / m ² or more and 30 mJ / m ² or less. I found it possible.

  In the case of the conventional method of printing ink containing particulate spacers by the inkjet method, the uniformity of the ink interface (meniscus) shape at the tip of the inkjet nozzle is due to the presence of solid particles such as particulate spacers. The present inventors have inferred that, as a result, the flight of the ejected droplets is bent and the ejection speed is uneven. If the flying curve of the droplets or the discharge speed is not uniform, the landing position accuracy is lowered and satellites are generated. On the other hand, in the case of the present invention, while maintaining the good height accuracy by using the ink substantially free of solid particles and adjusting the surface free energy of the cured product of the resin dissolved in the ink. Possible to control the spacer shape.

  The surface tension of the ink at 25 ° C. is preferably 20 mN / m or more. The viscosity of the ink at 25 ° C. is preferably 50 mPa · s or less. By using the ink having such properties, it becomes easy to reduce the diameter of the droplets arranged on the substrate, and thus the size of the spacer formed. Making the spacers small is particularly important in a high-definition liquid crystal display device. Furthermore, according to the above ink, occurrence of clogging of the ink jet is suppressed, and better printability can be obtained.

The vapor pressure at 25 ° C. of the solvent in the ink is preferably less than 1.34 × 10 ³ Pa. Thereby, an increase in the ink viscosity due to the volatilization of the solvent is sufficiently suppressed, and the occurrence of clogging of the ink jet is further suppressed remarkably.

  The resin in the ink is preferably a thermosetting resin. Since the viscosity of the thermosetting resin before curing is relatively low, the viscosity of the ink is reduced by using the thermosetting resin, and a more stable ejection property can be obtained. In this case, the liquid crystal display device spacer is formed by heating the droplets on the substrate to remove the solvent from the droplets and curing the thermosetting resin.

  In this invention, it is preferable that the said thermosetting resin contains an epoxy resin and its hardening | curing agent. By appropriately selecting the type of epoxy resin or curing agent, the cured product constituting the spacer can have desired physical properties relatively easily. The epoxy resin is preferably a glycidyl etherified product of a condensate of a phenol compound and an aldehyde compound from the viewpoint of heat resistance and adhesiveness.

  When the ink of the present invention is filtered with a filter having an opening of 1 μm, it is preferable that the solid content to be filtered is less than 0.3 mass% with respect to the ink mass. Thereby, the position accuracy improvement of the spacer for liquid crystal display devices formed can be improved further.

In another aspect, the present invention relates to a method for manufacturing a spacer for a liquid crystal display device. The present invention prints droplets composed of an ink containing a resin and a solvent in which the resin is dissolved and substantially not containing solid particles on a substrate by an inkjet method, and removes the solvent from the droplets on the substrate, In the method of manufacturing a spacer for a liquid crystal display device in which a spacer disposed at a predetermined position on the substrate is formed, the liquid crystal display device in which the surface free energy of the cured resin is from 26 mJ / m ^{2 to} 30 mJ / m ² The present invention relates to a manufacturing method for a spacer.

The present invention also relates to a method of manufacturing a spacer for a liquid crystal display device, and adjusts the height of the spacer by changing the surface free energy of a cured resin within a range of 26 mJ / m ² or more and 30 mJ / m ² or less. The present invention relates to a method for manufacturing the spacer for a liquid crystal display device.
In the present invention, the height H of the spacer for a liquid crystal display device can be adjusted to a desired height (2.5 μm to 5.0 μm) by changing the solid content ratio after the ink is dried. The solid content ratio (%) after drying of the ink can be adjusted to an arbitrary value within a range where the viscosity at 25 ° C. is 50 mPa · s or less. Here, the solid content ratio of the ink can be derived from the following equation (1). In addition, the mass after drying in following formula (1) is a mass after drying an ink on 200 degreeC and the conditions for 30 minutes.
Solid content ratio (%) = (mass after drying / ink mass before drying) × 100 (1)

  In the present invention, the height H of the spacer for a liquid crystal display device can be adjusted by changing the amount of ink droplets. The amount of ink droplets is preferably 0.001 to 100 pL, more preferably 1 to 80 pL, and even more preferably 1 to 30 pL. As the amount of droplets increases, the diameter of the formed spacer tends to increase, and the restriction on the printing position tends to increase.

  In still another aspect, the present invention relates to a method of manufacturing a liquid crystal display device including a pair of substrates arranged opposite to each other, a liquid crystal layer disposed between the pair of substrates, and a spacer for a liquid crystal display device. The manufacturing method of the liquid crystal display device according to the present invention includes the step of forming the spacer for liquid crystal display device on at least one substrate by the manufacturing (forming) method of the spacer for liquid crystal display device according to the present invention.

  According to the manufacturing method of the present invention, a spacer for a liquid crystal display device having a spacer diameter / height value in the range of 1 to 20 and a sufficient height H can be obtained with sufficiently excellent positional accuracy and height accuracy. Can be formed. Moreover, such a spacer for a liquid crystal display device can be formed by a simple process.

  In still another aspect, the present invention relates to a liquid crystal display device. A liquid crystal display device according to the present invention includes a pair of substrates disposed to face each other, a liquid crystal layer disposed between the pair of substrates, and a spacer for a liquid crystal display device. The liquid crystal display device spacer is formed using the liquid crystal display device spacer forming ink according to the present invention.

  In the liquid crystal display device according to the present invention, spacers having a spacer diameter / height in the range of 1 to 20 and having a sufficient height H are arranged with sufficiently excellent positional accuracy and height accuracy. . For this reason, display defects such as display variations and light leakage can be sufficiently suppressed.

  According to the present invention, a spacer for a liquid crystal display device having a spacer diameter / height value in the range of 1 to 20 and a sufficient height H, and a sufficiently excellent positional accuracy and height accuracy is formed. An ink for forming a spacer for a liquid crystal display device can be provided. Moreover, this invention can provide the manufacturing method of the spacer for liquid crystal display devices using this ink, a liquid crystal display device provided with the spacer for liquid crystal display devices formed by this manufacturing method, and its manufacturing method.

  Further, the spacer height can be controlled to an arbitrary height, and the spacer for the liquid crystal display device can be formed with a sufficiently high positional accuracy by a simple process. That is, since a spacer having a desired height can be selectively formed in the non-display area of the liquid crystal display device with high accuracy, display defects such as display variations and light leakage of the liquid crystal display device are sufficiently suppressed. be able to.

  In addition, the conventional particulate spacer has a small contact area because it makes point contact with the substrate, whereas the spacer formed by the method of the present invention has a large contact area with the substrate, and the resin constituting the spacer. Since the adhesion to the substrate is generally good, good adhesion between the spacer and the substrate can also be obtained.

It is a schematic cross section which shows one Embodiment of the spacer for liquid crystal display devices formed on the board | substrate using the ink for spacer formation for liquid crystal display devices of this invention. It is a schematic cross section which shows another embodiment of the spacer for liquid crystal display devices formed on the board | substrate using the ink for spacer formation for liquid crystal display devices of this invention. FIG. 3 is a top view of the spacer of FIG. 2. It is a schematic cross section which shows one Embodiment of the liquid crystal display device of this invention.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of a spacer for a liquid crystal display device formed by the method for manufacturing a spacer for a liquid crystal display device of the present invention. The liquid crystal display device spacer 11 made of the resin layer 20 is provided on the substrate 23. Hereinafter, a manufacturing method (hereinafter, also referred to as a forming method) of the liquid crystal display device spacer 11 using the liquid crystal display device spacer forming ink of the present invention will be described.

  In the method for forming a spacer for a liquid crystal display device according to this embodiment, first, an ink containing a resin and a solvent and substantially free of solid particles is printed on a substrate 23 used in the liquid crystal display device by an ink jet method. Then, for example, the resin layer 20 can be formed by removing the solvent by heat treatment or the like. As a result, the liquid crystal display device spacer 11 made of the resin layer 20 can be formed on the substrate 23. The height H of the spacer 11 is preferably 2.5 to 5.0 μm, and the diameter of the spacer 11 is preferably 5 to 50 μm.

  As the ink jet method, for example, a general discharge method such as a piezo method that discharges a liquid by vibration of a piezo element or a thermal method that discharges a liquid by utilizing expansion of the liquid by rapid heating can be used. In order to carry out such an ink jet method, for example, a normal ink jet apparatus can be used.

  As a method for removing the solvent after the ink has landed on the substrate 23, for example, a heat treatment method in which the substrate is heated or hot air is blown can be employed. Such heat treatment can be performed, for example, at a heating temperature of 150 to 250 ° C. and a heating time of 0.2 to 1.0 hour. When a thermosetting resin is used as the resin, the resin can be cured after removing the solvent or simultaneously with removing the solvent.

  FIG. 2 is a schematic cross-sectional view showing another embodiment of a spacer for a liquid crystal display device formed on a substrate by the method for manufacturing a spacer for a liquid crystal display device of the present invention. The spacer 12 for a liquid crystal display device in which the resin layer 20 and the resin layer 22 are laminated in this order is provided on the substrate 23. Hereinafter, a method for forming the liquid crystal display device spacer 12 will be described.

  First, an ink containing a resin and a solvent and substantially free of solid particles is printed on the resin layer 20 formed on the substrate 23 of FIG. 1 by an inkjet method. That is, the spacer forming ink is printed at the same position as the position where the resin layer 20 is formed on the substrate 23. The ink may have the same composition as the ink used for forming the resin layer 20 or a different composition. As described above, the resin layer 22 can be formed on the resin layer 20 by printing the ink on the resin layer 20 and then removing the solvent in the same manner as when forming the resin layer 20. As a result, the liquid crystal display device spacer 12 in which the resin layer 20 and the resin layer 22 are laminated in this order on the substrate 23 as shown in FIG. 2 can be formed.

  FIG. 3 is a top view of the spacer 12 of FIG. The resin layer 22 is provided so as to cover the resin layer 20 (FIG. 2). Thus, the spacer forming ink of the present invention can be ejected one or more times in one forming region. Thereby, the spacer for liquid crystal display devices which can respond easily to the gap height of the liquid crystal layer in a wide range can be formed.

  Here, the board | substrate 23 is a board | substrate used for a liquid crystal display device, and can use the thing which has an electrode and an orientation layer, for example in the surface side in which the spacer 11 (12) for liquid crystal display devices is formed. The spacer forming ink is preferably discharged onto the surface of one of the two substrates facing each other in the liquid crystal display device, and the region where the spacer is disposed is a non-color matrix such as a black matrix of a color filter. It is preferably on the display area.

  In this embodiment, after the spacer forming ink is printed on the substrate 23, the heat treatment is performed to once form the resin layer 20. However, after the spacer forming ink is printed on the substrate 23, the heat treatment is performed. Instead, the resin for forming the spacer may be formed simultaneously by printing the spacer forming ink on the same position and then removing the solvent by heat treatment or the like. Further, a resin layer is further formed on the resin layer 22 by printing an ink containing a resin and a solvent and containing substantially no solid particles on the resin layer 22 to remove the solvent. Also good. As described above, by printing the ink over the resin layer 22 and removing the solvent, a spacer for a liquid crystal display device composed of three or more resin layers can be formed on the substrate 23.

  Next, the spacer forming ink used in the method for manufacturing the spacer for the liquid crystal display device will be described in detail. In the method for producing a spacer for a liquid crystal display device of the present invention, an ink containing a resin and a solvent in which the resin is dissolved and substantially free of solid particles is used. Here, “substantially does not contain” means that the content of solid particles having a particle diameter of 1.0 μm or more is less than 0.5% by mass with respect to the ink mass at room temperature (25 ° C.). Means that. The content of the solid particles is preferably less than 0.3% by mass, more preferably less than 0.05% by mass, and less than 0.01% by mass with respect to the ink mass. Is particularly preferred. By reducing the content of the solid particles, the landing position accuracy can be further improved.

  In the spacer forming ink of this embodiment, that is, the ink, it is preferable that the resin is uniformly dissolved in the solvent. Here, “the resin is uniformly dissolved” means that when the ink is filtered through a filter having an opening of 1 μm at room temperature, the solid content of the spacer to be filtered is 0 with respect to the ink mass. It means less than 3% by mass.

In the ink for forming a spacer for a liquid crystal display device according to the present invention, the surface free energy of the cured resin contained in the ink is 26 mJ / m ² or more and 30 mJ / m ² or less, and further 27 mJ / m ² or more. It is preferably 29 mJ / m ² or less. When the surface free energy is less than 26 mJ / m ² , the wettability of the ink on the substrate increases and the spacer diameter / height ratio exceeds 20, and the display area of the liquid crystal display device (color resist, TFT substrate in the CF substrate) In this case, the spacer resin protrudes on the area facing the color resist), and there is a risk that the display quality will deteriorate, and if it exceeds 30 mJ / m ² , the ratio of the polar term to the surface free energy will increase relatively. As a result, the wettability of the ink on the substrate increases, and there is a possibility that the display quality is similarly lowered.
The surface free energy is measured, for example, by measuring the contact angle of water, formamide, and glycerin resin at 25 ° C. with respect to the cured product using an automatic contact angle meter (trade name: DM500) manufactured by Kyowa Interface Chemical Co., Ltd. It can be calculated by the Kaelble-Uy method.
The resin or the ink containing the resin can be cured, for example, under conditions of a heating temperature of 150 to 250 ° C. and a heating time of 0.2 to 1.0 hour.
Further, the surface free energy of the cured product of the resin is changed within a range of 26 mJ / m ² or more and 30 mJ / m ² or less, and the height H of the spacer for the liquid crystal display device is set to a desired height (2.5 μm to 5 μm 0.0 μm).
The substrate on which the spacer is formed using the ink for forming a spacer for a liquid crystal display device of the present invention is not particularly limited. The surface free energy of the substrate on which the spacer is formed is usually 20 to 55 mJ / m ² , but by using a substrate that is ²⁰ to 30 mJ / m ² , the spacer diameter / height value is 1 to 1. It is easy and preferable to form a spacer for a liquid crystal display device having a sufficient height H within a range of 20 and having a sufficiently excellent positional accuracy and height accuracy.

  The spacer forming ink of the present embodiment preferably has a surface tension of 20 mN / m or more. When the surface tension of the spacer forming ink is less than 20 mN / m, the ink droplet tends to spread after landing on the base material, and there is a tendency that the spacer cannot be reliably formed in the non-display area having a narrow width of the liquid crystal display device. The surface tension of the spacer forming ink is more preferably in the range of 20 to 80 mN / m. This is because when the surface tension of the ink exceeds 80 mN / m, the ink jet nozzles tend to be clogged.

  The viscosity of the spacer forming ink of this embodiment is preferably 50 mPa · s or less at 25 ° C. If the viscosity of the spacer forming ink is 50 mPa · s or less, the occurrence of non-ejection nozzles during ink jet printing and the occurrence of nozzle clogging can be more reliably prevented. The viscosity of the spacer forming ink is more preferably 1 to 30 mPa · s at 25 ° C. By setting the ink viscosity within the above range, there is a tendency that the droplet diameter can be reduced and the landing diameter of the ink can be further reduced.

The vapor pressure at 25 ° C. of the solvent contained in the spacer forming ink is preferably less than 1.34 × 10 ³ Pa. With such a solvent, an increase in ink viscosity due to volatilization of the solvent can be suppressed. For example, when an ink having a vapor pressure of 1.34 × 10 ³ Pa or more is used, the ink droplets are easily dried, and it becomes difficult to eject the droplets from the nozzles of the inkjet head, resulting in clogging of the inkjet head. It tends to be easier. By making the vapor pressure of the solvent contained in the spacer forming ink less than 1.34 × 10 ³ Pa, the above-mentioned problems can be avoided. Note that a solvent having a vapor pressure of less than 1.34 × 10 ³ Pa and a solvent having a vapor pressure of 1.34 × 10 ³ Pa or more may be used in combination, but in that case, the vapor pressure is 1.34 × The mixing ratio of the solvent of 10 ³ Pa or more is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass or less, based on the mass of the total amount of the solvent. Various solvents can be used as long as the vapor pressure is in a desired range and the insulating resin is dispersed or dissolved.

Specific examples of the solvent having a vapor pressure of less than 1.34 × 10 ³ Pa at 25 ° C. include γ-butyrolactone, cyclohexanone, N-methyl-2-pyrrolidone, anisole, ethylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, triethylene glycol, Examples include ethylene glycol monomethyl ether, triethylene glycol dimethyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol dimethyl ether. Specific examples of the solvent having a vapor pressure at 25 ° C. of 1.34 × 10 ³ Pa or more include methyl ethyl ketone, methyl isobutyl ketone, toluene, isopropyl alcohol and the like. These solvents can be used alone or in combination of two or more.

  The content ratio of the solvent in the ink is not particularly limited, and it is preferable to appropriately adjust the ink so that the viscosity and the surface tension at 25 ° C. are within the above ranges. It is preferable to set it as 99 mass%.

  The resin contained in the ink may be any material as long as it is generally a material that exhibits electrical insulation and can provide adhesion to a substrate. For example, epoxy resin, phenol resin, polyimide resin, polyamide resin, polyamideimide resin , Silicone-modified polyamideimide resin, polyester resin, cyanate ester resin, BT resin, acrylic resin, melamine resin, urethane resin, alkyd resin, and the like, but are not particularly limited. You may use these individually by 1 type or in combination of 2 or more types.

  When a thermosetting resin is used as the resin, it is possible to remove the solvent and / or cure the resin by dissolving a monomer, an oligomer, or the like in a solvent as necessary, printing on the substrate, and then performing heat treatment. The spacer forming ink may contain a curing accelerator, a coupling agent, an antioxidant, a filler, and the like as necessary.

  It is preferable that a thermosetting resin contains an epoxy resin and its hardening | curing agent from a heat resistant viewpoint. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenol type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, glycidyl ester type epoxy resin, or Glycidyl etherified products of phenols, cresols, alkylphenols, catechol, bisphenol F, bisphenol A, bisphenol S and other phenols and aldehydes such as formaldehyde and salicylaldehyde, glycidyl etherified products of polyphenols, and hydrogenation thereof In view of heat resistance and adhesiveness, a glycidyl etherified product of a condensate of phenols and aldehydes is preferable. These epoxy resins may have any molecular weight, and several types can be used in combination.

  Examples of the curing agent used together with the epoxy resin include amines such as diethylenetriamine, triethylenetetramine, metaxylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine, and dicyandiamide; phthalic anhydride, tetrahydrophthalic anhydride, hexahydro Phthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, pyromellitic anhydride, trimellitic anhydride and other acid anhydrides, imidazole, 2-ethylimidazole, 2-ethyl-4- Methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 4,5-diphenylimidazole, -Methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethylimidazoline, 2-isopropyl Imidazoles such as imidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline; imidazoles whose imino group is masked with acrylonitrile, phenylene diisocyanate, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, melamine acrylate, etc. Phenols such as bisphenol F, bisphenol A, bisphenol S, and polyvinylphenol; phenol, cresol, Le Kill phenol, catechol, bisphenol F, bisphenol A, etc. condensates and their halides and aldehydes such as phenol with formaldehyde and salicylaldehyde, such as bisphenol S and the like. Among these, from the viewpoint of heat resistance and adhesiveness, a condensate of phenols and aldehydes is preferable. These compounds may have any molecular weight, and may be used alone or in combination of two or more.

  The content of the insulating resin in the ink is preferably adjusted so that the viscosity and surface tension of the ink at 25 ° C. are within the above ranges, but usually 1 to 50% by mass with respect to the ink mass. It is preferable that

  Next, the liquid crystal display device of the present invention will be described. The liquid crystal display device according to the present invention includes a pair of substrates arranged opposite to each other, a liquid crystal layer made of a liquid crystal material sealed between the pair of substrates, and a gap between the substrates in order to keep the thickness of the liquid crystal layer constant. And a spacer for a liquid crystal display device arranged. And the said spacer for liquid crystal display devices is formed in the desired position on the said board | substrate by the inkjet printing method using the spacer forming ink of the said this invention. Here, the spacer for the liquid crystal display device can be formed, for example, by applying a spacer forming ink to a desired position on the substrate by an ink jet printing apparatus and curing the resin and / or removing the solvent by heat treatment. it can.

  FIG. 4 is a schematic cross-sectional view showing an embodiment of the liquid crystal display device of the present invention. As shown in FIG. 4, the liquid crystal display device 1 has a pair of substrate members 6 a and 6 b disposed to face each other. The substrate member 6a includes an electrode 2a, a color filter 7, a substrate 3a, a retardation plate 8, and a polarizing plate 5a, which are stacked in this order. Moreover, the board | substrate member 6b consists of the electrode 2b, the board | substrate 3b, and the polarizing plate 5b, and these are laminated | stacked in this order. Further, a backlight 9 is disposed outside the polarizing plate 5b in the substrate member 6b. Further, alignment layers 17a and 17b are laminated on the side of the substrate members 6a and 6b where the electrodes 2a and 2b are formed. The liquid crystal layer 18 is sandwiched between the substrate members 6a and 6b via the alignment layers 17a and 17b. And the sealing material 13 is provided between the board | substrate members 6a and 6b in the peripheral part of the liquid-crystal layer 18, Thereby, the board | substrate members 6a and 6b are couple | bonded.

  In such a liquid crystal display device, as shown in FIG. 4, the liquid crystal display device spacer 10 is disposed at a predetermined position of the liquid crystal display device 1 in order to keep the thickness of the liquid crystal layer 18 constant. From the viewpoint of displaying a high-quality image, the liquid crystal display device spacer 10 is preferably disposed at a position other than the display dot portion which is a light transmitting portion.

  In addition, the liquid crystal display device spacers 10 are preferably arranged at equal intervals over the entire screen display area. Since the liquid crystal display device spacer 10 is formed by the ink jet printing method using the spacer forming ink of the present invention, the liquid crystal display device spacer 10 is disposed with sufficiently high positional accuracy over the entire area of the screen display. Display defects such as omission can be sufficiently suppressed.

  Such a liquid crystal display device removes the solvent by printing, on the alignment layer 17b provided on the substrate 3b, droplets made of ink containing a resin and a solvent and substantially not containing solid particles by an ink jet method. By doing so, it can be manufactured by a manufacturing method including a step of forming the spacer 10 for a liquid crystal display device. The spacer 10 for a liquid crystal display device can be adjusted to a desired height by forming the above-described ink by printing two or more times by an inkjet method.

  The substrate members 6a and 6b shown in FIG. 4 each have a structure in which the above-described layers are stacked, but it is not always necessary to stack all of them. The substrate members 6a and 6b may be further provided with an insulating layer, a black matrix layer, a buffer material layer, a TFT, and the like as necessary.

  As the electrodes 2a and 2b, transparent electrodes such as tin-doped indium oxide (ITO) can be used. Moreover, as a board | substrate 3a, 3b, a plastic plate, a glass plate, etc. can be illustrated. As the color filter 7, the retardation plate 8, the polarizing plates 5 a and 5 b, and the backlight 9, known ones can be used. The alignment layers 17a and 17b can also be formed using a known liquid crystal aligning agent.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention more concretely, this invention is not limited to a following example. In addition, the viscosity of the ink for spacer formation of each Example and Comparative Example was measured at 25 ° C. using a small vibration viscometer (trade name: CJV5000) manufactured by A & D Co., Ltd. The surface tension of the ink is measured at 25 ° C. using a fully automatic surface tension meter (trade name: CBVP-Z) manufactured by Kyowa Interface Chemical Co., Ltd., which is a surface tension measuring device by the Wilhelmy method (platinum plate method). did. The surface free energy of the substrate was measured by measuring the contact angle of water, formamide, and glycerin with respect to the substrate at 25 ° C. using an automatic contact angle meter (trade name: DM500) manufactured by Kyowa Interface Chemical Co., Ltd. Calculated by Uy method. The amount of solid content that is filtered off when the ink is filtered is filtered at room temperature using a 1 μm aperture filter, and the filtered solid content is dried at 200 ° C. for 1 hour. The mass was measured and determined.

(Preparation of ink 1)
Cresol novolac type epoxy resin (manufactured by Toto Kasei Co., Ltd., trade name: YDCN70), xylene-modified phenol novolac resin (trade name: XLC-LL, manufactured by Mitsui Chemicals), 1-cyanoethyl-2-phenylimidazole (Shikoku Chemical Industries) After a product made by Co., Ltd., trade name: 2PZ-CN) is dissolved in γ-butyrolactone (vapor pressure at 25 ° C .: 2.3 × 10 ² Pa) as a solvent, a silicone leveling agent (manufactured by Enomoto Kasei Co., Ltd.) Trade name: Disparon 1711) was added to prepare ink 1. In addition, the usage ratio (mass ratio) of each raw material and the solvent contained in the ink 1 is as shown in Table 1.

  The prepared ink 1 had a viscosity of 7.1 mPa · s, a surface tension of 45 mN / m, and a solid content to be filtered off was 0.001% by mass.

(Preparation of ink 2)
Ink 2 was prepared in the same manner as Ink 1 except that the ratios of the ink raw materials and the solvent used were changed as shown in Table 1.

  The prepared ink 2 had a viscosity of 7.3 mPa · s, a surface tension of 29 mN / m, and a solid content to be filtered off was 0.001% by mass.

(Preparation of ink 3)
Ink 3 was prepared in the same manner as ink 1 except that the ratios of the ink raw materials and the solvent used were changed as shown in Table 1.

  The prepared ink 3 had a viscosity of 7.3 mPa · s, a surface tension of 27 mN / m, and a solid content to be filtered off was 0.001% by mass.

(Preparation of ink 4)
Ink 4 was prepared in the same manner as ink 1 except that the ratios of the ink raw materials and the solvent used were changed as shown in Table 1.

  The prepared ink 4 had a viscosity of 7.3 mPa · s, a surface tension of 26 mN / m, and a solid content to be filtered off was 0.001% by mass.

(Preparation of ink 5)
Ink 5 was prepared in the same manner as ink 1 except that the ratios of the raw materials and the solvent used were changed as shown in Table 1.

  The prepared ink 5 had a viscosity of 7.2 mPa · s, a surface tension of 26 mN / m, and a solid content to be filtered off was 0.001% by mass.

(Preparation of ink 6)
Ink 6 was prepared in the same manner as ink 1 except that the ratios of the raw materials and the solvent used were changed as shown in Table 1 and a particulate spacer was added.

  The prepared ink 6 had a viscosity of 12.2 mP · s, a surface tension of 44 mN / m, and a solid content to be filtered off of 0.51% by mass.

Example 1
The ink 3 was filtered through a membrane filter having an opening of 1 μm to remove foreign matters, and supplied to a piezo-type inkjet apparatus (trade name: Nano Printer 1000, manufactured by Microjet Co., Ltd.) equipped with a head having a diameter of 50 μm.

(Printing of spacer forming ink, formation of spacer)
Using the inkjet apparatus, on the surface on which the alignment film of the glass plate (substrate) on which the alignment film for VA liquid crystal (vertical alignment) having a surface free energy of 30 mJ / m ² is formed, Spacer forming ink was printed at intervals of 150 μm with a droplet volume of 15 pL. After the ink was printed once, the substrate was quickly transferred onto a hot plate heated to 180 ° C. and dried and cured for 30 minutes to form a spacer.

(Evaluation of landing position accuracy)
The formed spacers were observed with a metallurgical microscope, and an image was taken in a state where one field of view includes a total of 80 spacers of 8 rows × 10 points. After that, the grid pattern image with a width of 50 μm previously created on this image is superimposed on the screen of a personal computer so that the center of an arbitrary spacer is an arbitrary intersection of the grid pattern. Was evaluated (n = 80). The evaluation results are as shown in Table 2.

<Evaluation criteria for landing position accuracy and satellite generation rate>
A: The ratio of the spacers arranged so that the center point of the spacer is located in the frame of the lattice is 98% or more. B: The ratio of the spacers arranged so that the center point of the spacer is located in the frame of the lattice is 98. %Less than

(Evaluation of adhesion)
After a commercially available cellophane tape was strongly pressure-bonded to the formed spacer, the cellophane tape was peeled off at once, and the presence or absence of the spacer was checked to evaluate the adhesion. The evaluation criteria for adhesion are as follows. The evaluation results of adhesion were as shown in Table 2.

<Adhesion evaluation criteria>
A: The spacer is not peeled off at all by the tape test.
B: At least a part of the spacer is peeled off by the tape test.

(Evaluation of spacer height)
The height of the formed spacer was measured with a three-dimensional non-contact surface shape measuring system (trade name: MM-3500) manufactured by Ryoka System Co., Ltd. (n = 96), and the average value and standard deviation of the measured values were obtained. .

(Evaluation of spacer diameter)
The diameter of the formed spacer was measured by observing with a microscope (n = 96).

(Surface free energy of cured ink (resin))
The surface free energy of the resin (cured product) contained in the ink is determined by using an automatic contact angle meter (trade name: DM500) manufactured by Kyowa Interface Chemical Co., Ltd. The contact angle was measured at 25 ° C. and then calculated by the Kaelble-Uy method.

(Example 2)
A spacer was formed on the substrate in the same manner as in Example 1 except that the ink 4 was used instead of the ink 3, and each evaluation was performed. The evaluation results are as shown in Table 2.

(Example 3)
A spacer is formed on the substrate in the same manner as in Example 1 except that the glass plate (substrate) is replaced with a glass plate (substrate) on which an alignment film for VA liquid crystal having a surface free energy of 25 mJ / m ² is formed. Each evaluation was performed.

Example 4
A spacer is formed on the substrate in the same manner as in Example 2 except that the glass plate (substrate) is replaced with a glass plate (substrate) on which an overcoat film having a surface free energy of 36 mJ / m ² is formed. Each evaluation was performed.

(Comparative Example 1)
A spacer was formed on the substrate in the same manner as in Example 1 except that the ink 1 was used instead of the ink 3, and each evaluation was performed. The evaluation results are as shown in Table 2.

(Comparative Example 2)
A spacer was formed on the substrate in the same manner as in Example 1 except that the ink 2 was used instead of the ink 3, and each evaluation was performed. The evaluation results are as shown in Table 2.

(Comparative Example 3)
A spacer was formed on the substrate in the same manner as in Example 1 except that the ink 5 was used instead of the ink 3, and each evaluation was performed. The evaluation results are as shown in Table 2.

(Comparative Example 4)
A spacer was formed on the substrate in the same manner as in Example 1 except that the ink 6 was used instead of the ink 3, and each evaluation was performed. The evaluation results are as shown in Table 2.

In Examples 1 to 4, in which the surface free energy of the cured resin is 26 mJ / m ² or more and 30 mJ / m ² or less, the spacer diameter / height value is in the range of 1 to 20, and the spacer height average value Was in the range of 2.5 to 5 μm, the landing position accuracy was good, and the adhesion to the substrate was also good.

  On the other hand, in Comparative Examples 1 to 3, the spacer diameter / height value was larger than 20, and the spacer height was as low as less than 2.5 μm. In Comparative Example 4, the landing position accuracy was poor.

DESCRIPTION OF SYMBOLS 1 ... Liquid crystal display device, 2a, 2b ... Electrode, 3a, 3b, 23 ... Substrate, 5a, 5b ... Polarizing plate, 6a, 6b ... Substrate member, 7 ... Color filter, 8 ... Phase difference plate, 9 ... Backlight, DESCRIPTION OF SYMBOLS 10, 11, 12 ... Spacer (spacer for liquid crystal display devices), 13 ... Sealing material, 17a, 17b ... Orientation layer, 18 ... Liquid crystal layer, 20, 22 ... Resin layer.

Claims (11)

A droplet made of an ink containing a resin and a solvent that dissolves the resin and substantially free of solid particles is printed on a substrate by an ink jet method, and the solvent is removed from the droplet on the substrate, and the substrate A spacer for a liquid crystal display device in which the spacer free ink for forming a spacer disposed at a predetermined position on the surface has a surface free energy of 26 mJ / m ² or more and 30 mJ / m ² or less of a cured product of the resin. Forming ink.   The ink for forming a spacer for a liquid crystal display device according to claim 1, wherein the surface tension of the ink at 25 ° C is 20 mN / m or more, and the viscosity of the ink at 25 ° C is 50 mPa · s or less. The ink for forming a spacer for a liquid crystal display device according to claim 1, wherein the solvent has a vapor pressure at 25 ° C. of less than 1.34 × 10 ³ Pa.   The resin is a thermosetting resin, the solvent is removed from the droplets by heating the droplets on the substrate, and the thermosetting resin is cured to form the liquid crystal display device spacer. The ink for spacer formation for liquid crystal display devices as described in any one of -3.   The ink for forming a spacer for a liquid crystal display device according to claim 4, wherein the thermosetting resin contains an epoxy resin and a curing agent thereof.   The ink for forming a spacer for a liquid crystal display device according to claim 5, wherein the epoxy resin is a glycidyl etherified product of a condensate of a phenol compound and an aldehyde compound.   When the ink is filtered with a filter having a mesh size of 1 µm, the amount of solids to be filtered is less than 0.3% by mass with respect to the mass of the ink. Ink for forming spacers for liquid crystal display devices. A droplet made of an ink containing a resin and a solvent that dissolves the resin and substantially free of solid particles is printed on a substrate by an ink jet method, and the solvent is removed from the droplet on the substrate, and the substrate In the method for manufacturing a spacer for a liquid crystal display device, wherein a spacer disposed at a predetermined position is formed, the surface free energy of the cured product of the resin is 26 mJ / m ² or more and 30 mJ / m ² or less. Manufacturing method. By changing the surface free energy of the cured product of the resin in the range 26 mJ / m ² or more 30 mJ / m ² or less of a liquid crystal display device manufacturing method for a spacer according to claim 8, wherein adjusting the height of the spacer.   10. A liquid crystal display device according to claim 8, wherein the liquid crystal display device includes a pair of substrates disposed opposite to each other, a liquid crystal layer disposed between the pair of substrates, and a spacer for a liquid crystal display device. A method for producing a liquid crystal display device, wherein the spacer for liquid crystal display device is formed on at least one of the substrates by a method for producing a spacer for a liquid crystal.   A liquid crystal display device comprising: a pair of substrates disposed opposite to each other; and a liquid crystal layer and a liquid crystal display device spacer disposed between the pair of substrates, wherein the liquid crystal display device spacer comprises: A liquid crystal display device formed using the ink for forming a spacer for a liquid crystal display device according to claim 7.

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