JP2011190303A - Oriented film-forming composition, oriented film, image display device and electronic equipment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oriented film which can effectively prevent the occurrence of color shading/density unevenness (particularly streaks) in a display image. <P>SOLUTION: The composition for forming an oriented film by the inkjet system includes a polyimide, γ-butyrolactone, a fluorine-based leveling agent, and the fluorine-based leveling agent is constituted by comprising a monomer of formula (1) (where A is a fluorine-free divalent connecting group; x is an integer of 0 or 1; R<SP>f</SP>is a 1-20C perfluoroalkyl group or a partially fluorinated alkyl such as -(CF<SB>2</SB>)<SB>6</SB>H which may be linear or branched or may have an oxygen-introduced main chain; and R<SP>1</SP>is H, CH<SB>3</SB>, Cl, F or a 3-16C fluorinated alkyl group) and a monomer of formula (2) (wherein B is a divalent connecting group; y is an integer of 0 or 1; R<SP>1</SP>is H, CH<SB>3</SB>, Cl or F; R<SP>2</SP>, R<SP>2'</SP>, R<SP>2"</SP>, R<SP>3</SP>, R<SP>3'</SP>, R<SP>3"</SP>, R<SP>4</SP>, and R<SP>4"</SP>are each a 1-20C alkyl group or a phenyl group; R<SP>4'</SP>is a 1-20C alkyl group, a phenyl group or a group represented by formula: CH<SB>2</SB>=CR<SP>1</SP>B<SB>y</SB>; l and n are each an integer of 0 or more; and m is an integer of 1 or more). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a composition for forming an alignment film, an alignment film, an image display device, and an electronic apparatus.

  Conventionally, as a method for forming an alignment film in a liquid crystal display device, a method by a flexographic printing method or a spin coating method has been generally used. However, in the flexographic printing method, the plate maintenance is complicated, and more ink is wasted because more than necessary ink is used to spread the alignment film forming material (ink) on the plate. was there. On the other hand, even in the spin coating method, although a large amount of ink is required, the material actually used for film formation is about 10% of the input material, and the remaining 90% is discarded. After all, there was a drawback that ink wasted a lot.

Against this background, in recent years, it has been proposed to use a droplet discharge method typified by an inkjet method as a method for forming an alignment film. The droplet discharge method can arrange a necessary amount of ink at a necessary location, so that waste of material (ink) is small, and therefore it is advantageous in terms of material cost. On the other hand, it has attracted particular attention in recent years because it has an advantage that an alignment film can be easily formed.
Generally, polyimide or the like is used as a constituent material of the alignment film (alignment film material). Further, the alignment film forming composition for forming the alignment film by the droplet discharge method (inkjet method) contains N-methylpyrrolidone or γ-butyrolactone as a solvent from the viewpoint of solubility of the alignment film material. The thing is used (for example, refer patent document 1).

  When forming an alignment film by an inkjet method using the composition for forming an alignment film as described above, if the viscosity of the composition for forming an alignment film is high, wetting and spreading to the substrate will deteriorate, so the solid content rate Therefore, it is necessary to use a composition for forming an alignment film having a relatively low value. However, in such a composition for forming an alignment film, a slight variation in the surface state of the substrate on which the alignment film is to be formed tends to cause film thickness unevenness. As a result, the alignment film formed is unwilling. In some cases, unevenness of thickness occurs, and unevenness of color and density (particularly, unevenness of stripes) occurs in the displayed image.

JP 2003-295195 A

  An object of the present invention is to provide an alignment film that can effectively prevent the occurrence of color unevenness and density unevenness (particularly streak unevenness) in a display image, and can be suitably used for forming the alignment film. An object of the present invention is to provide a composition for forming an alignment film, and to provide an image display device and an electronic apparatus provided with the alignment film.

Such an object is achieved by the present invention described below.
The composition for forming an alignment film of the present invention is a composition for forming an alignment film used for manufacturing an alignment film by an ink jet method,
It contains polyimide, γ-butyrolactone, and a fluorine-based leveling agent.
Accordingly, it is possible to provide an alignment film forming composition that can be suitably used for forming an alignment film that can effectively prevent the occurrence of color unevenness and density unevenness (particularly stripe unevenness) in a display image. it can.

これにより、表示画像における色むら・濃度むら（特に、すじむら）の発生をより効果的に防止することができる。また、配向膜形成用組成物の液滴の吐出安定性を特に優れたものとすることができ、配向膜の形成効率を特に優れたものとすることができる。 In the composition for forming an alignment film of the present invention, as the fluorine-based leveling agent, a fluorinated alkyl group-containing vinyl monomer f represented by the following formula (1) and an alkoxysilyl represented by the following formula (2) are used as monomer components. It is preferable to include a fluorine-silicon copolymer that includes the group-containing vinyl monomer s.

As a result, it is possible to more effectively prevent color unevenness and density unevenness (particularly streak unevenness) in the display image. Moreover, the ejection stability of the droplets of the composition for forming an alignment film can be made particularly excellent, and the formation efficiency of the alignment film can be made particularly excellent.

In the composition for forming an alignment film of the present invention, the fluorine-silicon copolymer preferably has a weight average molecular weight of 15,000 or more and 500,000 or less.
As a result, it is possible to more effectively prevent color unevenness and density unevenness (particularly streak unevenness) in the display image. Moreover, the ejection stability of the droplets of the composition for forming an alignment film can be made particularly excellent, and the formation efficiency of the alignment film can be made particularly excellent.

In the composition for forming an alignment film of the present invention, the fluorine-silicon copolymer preferably has a solubility parameter of 5 or more and 8 or less.
Thereby, the affinity with the other components in the composition for forming an alignment film of the fluorine-silicon copolymer can be made high, and the discharge stability of the droplet of the composition for forming an alignment film is particularly improved. It can be made excellent, and the formation efficiency of the alignment film can be made particularly excellent. In addition, it is possible to more effectively prevent color unevenness and density unevenness (particularly streak unevenness) in a display image.

In the alignment film forming composition of the present invention, the content of the fluorine-silicon copolymer in the alignment film forming composition is preferably 0.1 wt% or more and 5.0 wt% or less.
As a result, it is possible to more effectively prevent color unevenness and density unevenness (particularly streak unevenness) in the display image. Moreover, the ejection stability of the droplets of the composition for forming an alignment film can be made particularly excellent, and the formation efficiency of the alignment film can be made particularly excellent.

The alignment film of the present invention is formed using the alignment film forming composition of the present invention.
Thereby, it is possible to provide an alignment film that can effectively prevent the occurrence of color unevenness and density unevenness (particularly streak unevenness) in a display image.
The image display device of the present invention is characterized by including the alignment film of the present invention.
Accordingly, it is possible to provide an image display device that can effectively prevent the occurrence of color unevenness and density unevenness (particularly streak unevenness) in a display image displayed on the display unit.
An electronic apparatus according to the present invention includes the image display device according to the present invention.
Accordingly, it is possible to provide an electronic device that can effectively prevent the occurrence of color unevenness and density unevenness (particularly streak unevenness) in a display image displayed on the display unit.

1 is a schematic exploded perspective view showing an example of a liquid crystal display device (image display device) to which an alignment film of the present invention is applied. It is a flowchart which shows the manufacturing method of the liquid crystal display device (image display apparatus) to which the alignment film of this invention was applied. It is a schematic perspective view which shows the structure of a droplet discharge apparatus. It is a figure which shows the droplet discharge head in the droplet discharge apparatus shown in FIG. 3, (a) is a cross-sectional perspective view, (b) is a schematic plan view. It is a schematic plan view which shows a mother board | substrate. It is a schematic sectional drawing which shows the manufacturing method of a liquid crystal display device (image display apparatus). It is a schematic sectional drawing which shows the manufacturing method of a liquid crystal display device (image display apparatus). 1 is a perspective view illustrating a configuration of a mobile (or notebook) personal computer to which an electronic apparatus of the present invention is applied. It is a perspective view which shows the structure of the mobile telephone (PHS is also included) to which the electronic device of this invention is applied. It is a perspective view which shows the structure of the digital still camera to which the electronic device of this invention is applied.

DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments of the invention will be described with reference to the accompanying drawings. Note that the drawings referred to in this specification show part of the configuration in an emphasized manner, and do not accurately reflect actual dimensions and the like.
<< Alignment film forming composition >>
First, a preferred embodiment of the composition for forming an alignment film of the present invention will be described.

The composition for forming an alignment film (ink for forming an alignment film) of the present invention is a composition (ink) used for manufacturing an alignment film, and particularly used for manufacturing an alignment film by an inkjet method.
Moreover, the composition for forming an alignment film of the present invention (hereinafter also simply referred to as a composition or an ink) contains polyimide, γ-butyrolactone, and a fluorine-based leveling agent.

By the way, the method for manufacturing an alignment film using the ink jet method has an advantage that the waste (discard amount) of the material for forming the alignment film can be reduced, but in general, the alignment film to be formed has an uneven thickness unevenness. There is a problem that color unevenness, density unevenness (particularly, streak unevenness) and the like are easily generated in the display image.
Moreover, the droplet discharge device (industrial use) used for the production of the alignment film is completely different from that applied to the printer (consumer use). For example, a high-viscosity composition having a high solid content is used. In order to perform mass production or to eject liquid droplets onto a large workpiece (substrate), it is required to eject a large amount of liquid droplets over a long period of time while maintaining high accuracy. . Since it is used under such harsh conditions, it tends to cause fluctuations in the discharge amount of liquid droplets compared to those for consumer use. There are problems such as variations in characteristics among the alignment films, and variations in thickness at each portion of the alignment films become more prominent.
Therefore, as a result of intensive studies to solve the above-described problems, the present inventors have described above by including a fluorine-based leveling agent in the alignment film forming composition in addition to polyimide and γ-butyrolactone. It was found that such problems can be solved.

Hereinafter, each material which comprises the composition for alignment film formation is demonstrated in detail.
<Fluorine leveling agent>
The fluorine-based leveling agent contained in the composition for forming an alignment film of the present invention is not particularly limited, but as a monomer component, a fluorinated alkyl group-containing vinyl monomer f represented by the following formula (1) and the following formula (2) It is preferable that it is a fluorine-silicon-type copolymer comprised including the alkoxy silyl group containing vinyl monomer s shown to).

  When the composition for forming an alignment film contains a fluorine-silicon copolymer as a fluorine-based leveling agent, the composition for forming an alignment film is excellent in drainage from the nozzles during droplet discharge. Moreover, adhesion of solid content (polyimide etc.) in the composition to the nozzle is prevented. This is considered to be due to the fact that the fluorine-silicon copolymer in the vicinity of the nozzle reduces the affinity with the nozzle surface during droplet discharge. In particular, when the nozzle plate described in JP-A-2004-330604 is used as the nozzle plate for forming the nozzle, the liquid drainage of the alignment film forming composition from the nozzle is particularly excellent.

  In addition, since the fluorine-silicon copolymer has both fluorine and silicon-containing monomers, the fluorine-silicon copolymer becomes very bulky and easily takes in minute solids and the like. . For this reason, it is considered that even when solid content such as polyimide adheres to the nozzle surface, the fluorine-silicon copolymer can clean the nozzle by taking them in. In particular, such a cleaning effect is exerted on the nozzle surface of the inkjet head, the nozzle front portion of the nozzle plate, and the cavity portion that supplies ink to the nozzle portion.

As a result, the amount of droplets at the time of discharging the droplets becomes uniform, and the phenomenon that the droplets of the composition do not land at the target position due to solid content such as polyimide adhering to the vicinity of the nozzle (flight bending) Can be prevented. For this reason, the composition for forming an alignment film has excellent droplet ejection stability, and can impart a uniform amount of the composition to each cell.
Further, by including such a fluorine-silicon copolymer, the composition for forming an alignment film can be suitably spread on a substrate (particularly a glass substrate). This is considered because the affinity between the fluorine-silicon copolymer having silicon and the substrate is high. For this reason, generation | occurrence | production of the nonuniformity of unintentional thickness can be prevented more effectively.

As a result, it is possible to more effectively prevent the occurrence of color unevenness and density unevenness (particularly streak unevenness) in the display image. Moreover, the ejection stability of the droplets of the composition for forming an alignment film can be made particularly excellent, and the formation efficiency of the alignment film can be made particularly excellent.
Further, if the alignment film forming composition contains a fluorine-silicon copolymer as described above as a fluorine leveling agent, the arrangement of constituent molecules in the film itself formed by the ink jet method may be made regular. Therefore, the orientation of the finally obtained alignment film can be more reliably increased. In addition, in the alignment treatment (rubbing treatment) of the molecules constituting the film formed by the ink jet method, the alignment film forming composition contains the above-described fluorine-silicon copolymer as a fluorine leveling agent. The movement can be smooth, and the orientation of the finally obtained alignment film can be made higher.

[Fluorinated alkyl group-containing vinyl monomer f]
The fluorinated alkyl group-containing vinyl monomer f is a component represented by the above formula (1). By having such a fluorinated alkyl group-containing vinyl monomer f, the fluorine-silicon copolymer can be excellent in drainage from the nozzle of the composition for forming an alignment film.

Examples of the divalent linking group A in the formula (1) include — (CH ₂ ) _n —, —CH ₂ CH (OH) (CH ₂ ) _n —, and — (CH ₂ ) _n N (R ² ). ) SO ₂ —, — (CH ₂ ) _n N (R ² ) CO— (wherein n is an integer of 1 to 10 and R ² is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms). _{.), - CH (CH 3} ) -, - CH (CH 2 CH 3) -, - C (CH 3) 2 - linking group such as and the like.
In addition, R ^f in the formula (1) may be a fluorinated alkyl group as described above. For example, —C ₄ F ₉ , —C ₆ F ₁₃ , —C ₇ F ₁₅ , —C _{8 F 17, - (CF 2} ) 4 H, - (CF 2) 6 CF (CF 3) 2, - (OCF 2 CF 2) 4 OCF 2 CF 3, - (OCF 2 CF (CF 3)) 3 C Fluorinated alkyl groups such as ₃ F ₇ can be mentioned.

When R ¹ is a fluorinated alkyl group, R ¹ may have a branched chain or a straight chain. R ¹ may be a perfluoroalkyl group or a partially fluorinated alkyl group. When R ¹ is a partially fluorinated alkyl group, for example, a structure in which a branched or straight chain alkyl group as a divalent linking group and a perfluoroalkyl group are bonded, specifically, — (CH ₂ ) _N -C _j F _{2j + 1} (where n and j are integers of 0 or more and satisfy the relationship of 1 ≦ n + j ≦ 16).

The fluorinated alkyl group-containing vinyl monomer f is not particularly limited as long as it satisfies the formula (1). For example, CH ₂ = CHCOOCH ₂ CH ₂ C ₈ F ₁₇ , CH ₂ = C (CH _{3 ) COOCH 2 CH 2 C 8 F} 17, CH 2 = CHCOOCH 2 CH 2 C 12 F 25, CH 2 = C (CH 3) COOCH 2 CH 2 C 12 F 25, CH 2 = CHCOOCH 2 CH 2 C 10 F 21 _{, CH 2 = C (CH 3} ) COOCH 2 CH 2 C 10 F 21, CH 2 = CHCOOCH 2 CH 2 C 6 F 13, CH 2 = C (CH 3) COOCH 2 CH 2 C 6 F 13, CH 2 = _{CHCOOCH 2 CH 2 C 4 F 9} , CH 2 = CFCOOCH 2 CH 2 C 6 F 13, CH 2 = C (CH 3) COOCH 2 C _{2 C 20 F 41, CH 2} = C (Cl) COOCH 2 CH 2 C 4 F 9, CH 2 = C (CH 3) COO (CH 2) 6 C 10 F 21, CH 2 = C (CH 3) COOCH ₂ CF ₃ , CH ₂ = CHCOOCH ₂ CF ₃ , CH ₂ = CHCOOCH ₂ C ₈ F ₁₇ , CH ₂ = C (CH ₃ ) COOCH ₂ C ₈ F ₁₇ , CH ₂ = C (CH ₃ ) COOCH ₂ C ₂₀ F _{41, CH 2 = CHCOOCH 2 C} 20 F 41, CH 2 = C (CH 3) COOCH 2 CF (CF 3) 2, CH 2 = C (CH 3) COOCH 2 CFHCF 3, CH 2 = CFCOOCH 2 C 2 F ₅ , CH ₂ = CHCOO (CH ₂ ) ₇ CF (CF ₃ ) ₂ , CH ₂ = C (CH ₃ ) COOC (CH ₃ ) HCF ₂ CFHCF ₃ , CH ₂ ═C (CH ₃ ) COOC (C ₂ H ₅ ) HC ₁₀ F ₂₁ , CH ₂ ═CHCOOCH ₂ (CF) ₂ H, CH ₂ ═C (CH ₃ ) COOCH ₂ (CF) ₂ H, CH _{2 = CHCOOCH 2 (CF) 4} H, CH 2 = CHCOOCH 2 CF 3, CH 2 = C (CH 3) COOCH 2 (CF) 4 H, CH 2 = CHCOOCH 2 (CF 2) 6 H, CH 2 = C _{(CH 3) COOCH 2 (CF} 2) 6 H, CH 2 = CHCOOCH 2 (CF 2) 8 H, CH 2 = C (CH 3) COOCH 2 (CF 2) 8 H, CH 2 = CHCOOCH 2 (CF 2 ) ₁₀ H, CH ₂ = CHCOOCH ₂ (CF ₂ ) ₁₂ H, CH ₂ = CHCOOCH ₂ (CF ₂ ) ₁₄ H, CH ₂ = CHCOOCH ₂ (CF _{2) 18 H, CH 2 =} CHCOOC (CH 3) 2 (CF 2) 4 H, CH 2 = CHCOOCH 2 CH 2 (CF 2) 7 H, CH 2 = C (CH 3) COOCH 2 CH 2 (CF 2 ) ₇ H, CH ₂ = C (CH ₃ ) COOC (CH ₃ ) ₂ (CF ₂ ) ₆ H, CH ₂ = CHCOOC (CF ₃ ) HC ₈ F ₁₇ , CH ₂ = CHCOOCH ₂ C ₂ F ₅ , CH _{2 = CHCOOCH 2 C (OH) HCH} 2 C 8 F 17, CH 2 = C (CH 3) COOCH 2 C (OH) H (CH 2) 4 C 8 F 17, CH 2 = CHCOOCH 2 CH 2 N (C 3 _{H 7) SO 2 C 8 F} 17, CH 2 = C (CH 3) COOCH 2 CH 2 N (CH 3) SO 2 C 6 F 13, CH 2 = C (Cl) COO (CH 2) 6 _{(C 3 H 7) SO 2} C 12 F 25, CH 2 = CHCOOCH 2 CH 2 N (C 2 H 5) SO 2 C 7 F 15, CH 2 = CHCOO (CH 2) 8 N (CH 3) SO 2 _{C 12 F 25, CH 2 =} CHCOO (CH 2) 2 (CF 2) 8 CF (CF 3) 2, CH 2 = CHCOOCH 2 CH 2 N (C 2 H 5) SO 2 C 8 F 17, CH 2 = _{C (CH 3) COOCH 2 CH} 2 N (C 2 H 5) SO 2 C 6 F 13, CH 2 = CHCOOCH 2 CH 2 N (C 3 H 7) SO 2 C 8 F 17, CH 2 = C (CH _{2 CH 2 C 8 F 17)} COOCH like ₂ CH ₂ C ₈ F _17. among these may be used alone or in combination.

Further, among the above, the fluorinated alkyl group-containing vinyl monomers _{f, CH 2 = CHCOOCH 2 CH} 2 C 8 F 17 _{or, CH 2 = C (CH 2} CH 2 C 8 F 17) COOCH 2 CH 2 C _{When 8} F ₁₇ is used, the fluorine-silicon copolymer is sufficiently bulky, and the fluorinated alkyl group-containing vinyl monomer f and the alkoxysilyl group-containing vinyl monomer in the fluorine-silicon copolymer are used. Both the effects of the monomer s are exhibited as being particularly excellent.

[Alkoxysilyl group-containing vinyl monomer s]
The alkoxysilyl group-containing vinyl monomer s is a component represented by the above formula (2). The fluorine-silicon copolymer has such an alkoxysilyl group-containing vinyl monomer s, so that the wettability of the composition for forming an alignment film to a substrate (particularly a glass substrate) is excellent. Can do.

Examples of the divalent linking group B in the formula (2), for _{example, -CH 2 (OH) CH 2} OCO -, - (CH 2) p1 NHCH 2 CH (OH) CH 2 OCO -, - (CH 2 _{) p1 OCO -, - (CH} 2) q1 O (CH 2) q1 OCO -, - OCH in _{2 CH (OH) CH 2 OCO-} ( wherein, p1, q1 are each independently 2 to 6 integer And the like.

In the formula (2), the alkoxysilyl group may be a linear silicone chain, but preferably has a branched silicone chain. That is, in the formula (2), at least one of l and n is preferably 1 or more. As a result, the fluorine-silicon copolymer becomes sufficiently bulky.
In formula (2), as described above, l and n are each preferably 1 or more, more preferably 1 or more and 5 or less, and even more preferably 1 or 2. Thereby, the effect of the fluorinated alkyl group-containing vinyl monomer f and the alkoxysilyl group-containing vinyl monomer s in the fluorine-silicon copolymer is obtained while making the fluorine-silicon copolymer sufficiently bulky. Are both particularly excellent.

  In formula (2), m may be 1 or more, preferably 1 or more, 10 or less, more preferably 1 or more and 5 or less, and even more preferably 1 or 2. Thereby, the effect of the fluorinated alkyl group-containing vinyl monomer f and the alkoxysilyl group-containing vinyl monomer s in the fluorine-silicon copolymer is obtained while making the fluorine-silicon copolymer sufficiently bulky. Are both particularly excellent.

When R ² , R ^{2 ′} , R ^{2 ″} , R ³ , R ^{3 ′} , R ^{3 ″} , R ⁴ , R ^{4 ′} , R ^{4 ″} are alkyl groups, the carbon number of the alkyl group is Although it may be in the range as described above, it is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less. Thereby, the effect of the fluorinated alkyl group-containing vinyl monomer f and the alkoxysilyl group-containing vinyl monomer s in the fluorine-silicon copolymer is obtained while making the fluorine-silicon copolymer sufficiently bulky. Are both particularly excellent.
The alkoxysilyl group-containing vinyl monomer s may be any as long as it satisfies the formula (2). For example, the alkoxysilyl group represented by the following formulas (2-1) to (2-46) Examples thereof include vinyl monomers and the like, and one or two or more selected from these can be used in combination.

  Among the above-described compounds, it is preferable to use a compound represented by the formula (2-33) or the formula (2-40) as the alkoxysilyl group-containing vinyl monomer s. Thereby, the effect of the fluorinated alkyl group-containing vinyl monomer f and the alkoxysilyl group-containing vinyl monomer s in the fluorine-silicon copolymer is obtained while making the fluorine-silicon copolymer sufficiently bulky. Are both particularly excellent.

Use in particular, as a fluorinated alkyl group-containing vinyl monomers _{f, CH 2 = CHCOOCH 2 CH} 2 C 8 F 17, a combination of compounds represented by formula (2-40) as alkoxysilyl group-containing vinyl monomer s Or fluorinated alkyl group-containing vinyl monomer f, CH ₂ = C (CH ₂ CH ₂ C ₈ F ₁₇ ) COOCH ₂ CH ₂ C ₈ F ₁₇ , alkoxysilyl group-containing vinyl monomer s When the compounds represented by the formula (2-33) are used in combination, the effects as described above can be obtained more remarkably.

  The content of the alkoxysilyl group-containing vinyl monomer s in the fluorine-silicon copolymer (value obtained by conversion based on the weight of the monomer used for polymer synthesis) is 100 parts by weight of the fluorinated alkyl group. It is preferably 10 parts by weight or more and 1000 parts by weight or less, and more preferably 25 parts by weight or more and 400 parts by weight or less with respect to the vinyl monomer f contained. When the content of the alkoxysilyl group-containing vinyl monomer s in the fluorine-silicon copolymer is a value within the above range, the fluorine-silicon copolymer is sufficiently bulky while the fluorine-silicon copolymer is sufficiently bulky. Both the effects of the fluorinated alkyl group-containing vinyl monomer f and the alkoxysilyl group-containing vinyl monomer s in the copolymer are exhibited as being particularly excellent.

  In addition, the fluorine-silicon copolymer may have a vinyl monomer other than the fluorinated alkyl group-containing vinyl monomer f and the alkoxysilyl group-containing vinyl monomer s described above. Such a monomer is not particularly limited, but for example, fatty acid vinyl such as styrene, nucleus-substituted styrene, acrylonitrile, vinyl chloride, vinylidene chloride, vinylpyridine, N-vinylpyrrolidone, vinylsulfonic acid, vinyl acetate; Α, β-ethylenically unsaturated carboxylic acids such as mono- or divalent carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid; methyl, ethyl, propyl of (meth) acrylic acid; The alkyl group has 1 to 18 carbon atoms (methacrylic acid alkyl ester; 2-hydroxyethyl ester, hydroxypropyl ester, hydroxybutyl ester, such as butyl, octyl, 2-ethylhexyl, decyl, dodecyl, stearyl ester Like (meth) acrylic acid carbon atom A hydroxyalkyl ester having 1 to 18 carbon atoms; an aminoalkyl ester having 1 to 18 carbon atoms of (meth) acrylic acid such as dimethylaminoethyl ester, diethylaminoethyl ester, diethylaminopropyl ester; methoxyethyl ester, ethoxyethyl ester , A methoxypropyl ester, a methyl carbyl ester, an ethyl carbyl ester, a butyl carbyl ester, an ether oxygen-containing alkyl ester of (meth) acrylic acid having 3 to 18 carbon atoms; dicyclopentanyloxylethyl (meth) acrylate, Isobornyloxylethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, dicyclo Polyalkylene glycol such as tantanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, polyethylene glycol having a polymerization degree of 1 to 100, polypropylene glycol, and a copolymer of ethylene oxide and propylene oxide. Mono (meth) acrylic acid ester or di (meth) acrylic acid ester, or polyethylene glycol having a degree of polymerization of 1 to 100 and capped with an alkyl group having 1 to 6 carbon atoms, polypropylene glycol, and ethylene oxide and propylene Alkyl having 1 to 18 alkyl carbon atoms such as mono (meth) acrylic acid ester of polyalkylene glycol such as copolymer with oxide, methyl vinyl ether, propyl vinyl ether, dodecyl vinyl ether Glucidyl ester of (meth) acrylic acid such as glycidyl methacrylate, glycidyl acrylate; styrene macromonomer 4500 manufactured by Sartomer, macromonomer such as NK ester M-230G manufactured by Shin-Nakamura Chemical Co., Ltd .; 2 -(Meth) acryloyloxyethyl succinic acid, 2-acrylamido-2-methylpropane sulfonic acid, partially sulfonated styrene, mono (acryloyloxyethyl) acid phosphate, mono (methacryloxyethyl) acid phosphate, etc. Among these, one or a combination of two or more can be used.

  Among the above-mentioned, mono (meth) acrylic acid ester or di (meth) acrylic acid ester of polyalkylene glycol such as polyethylene glycol, polypropylene glycol, and a copolymer of ethylene oxide and propylene oxide in the side chain. Or polyalcohols such as polyethylene glycol, polypropylene glycol, and copolymers of ethylene oxide and propylene oxide having a degree of polymerization of 1 to 100 and capped with an alkyl group having 1 to 6 carbon atoms at the ends (Meth) acrylate monomer having a polyoxyalkylene group in the side chain like mono (meth) acrylate ester of xylene glycol; carbon atom like (meth) acrylate ester having an alkyl group having 6 or more carbon atoms Has an alkyl group of 6 or more in the side chain (Meth) acrylate monomers are preferred.

Further, the content of the other monomers as described above in the fluorine-silicon copolymer is the total content of the fluorinated alkyl group-containing vinyl monomer f and the alkoxysilyl group-containing vinyl monomer s. Is preferably 10 parts by weight or more and 10000 parts by weight or less, and more preferably 20 parts by weight or more and 8000 parts by weight or less. In addition, when there are multiple types of other monomers, it is preferable that the total content of these multiple types of monomers satisfies the above relationship.
Further, the fluorine-silicon copolymer may be a copolymer in which each monomer is randomly arranged, or a block copolymer constituted by blocks in which a plurality of identical monomers are polymerized. It may be.

  The weight average molecular weight of the fluorine-silicon copolymer is preferably 15000 or more and 500000 or less, and more preferably 20000 or more and 100000 or less. As a result, it is possible to more effectively prevent color unevenness and density unevenness (particularly streak unevenness) in the display image. Moreover, the ejection stability of the droplets of the composition for forming an alignment film can be made particularly excellent, and the formation efficiency of the alignment film can be made particularly excellent.

  The solubility parameter (SP value) of the fluorine-silicon copolymer is not particularly limited, but is preferably 5 or more and 8 or less. Thereby, the affinity with the other components in the composition for forming an alignment film of the fluorine-silicon copolymer can be made high, and the discharge stability of the droplet of the composition for forming an alignment film is particularly improved. It can be made excellent, and the formation efficiency of the alignment film can be made particularly excellent. In addition, it is possible to more effectively prevent color unevenness and density unevenness (particularly streak unevenness) in a display image.

The solubility parameter (SP value) δ [(cal / cm ³ ) ^1/2 ] is used as an index of compatibility and affinity of a plurality of substances, and is represented by the following formula (I). It is defined by an expression.
δ = (ΔE ^V / V ₀ ) ^1/2 ÷ 2.046 [(cal / cm ³ ) ^1/2 ] (I)
However, ΔE ^V [10 ⁶ N · m · mol ⁻¹ ] is the heat of evaporation, and V ₀ [m ³ · mol ⁻¹ ] is the volume per mol. The difference in solubility parameter between two substances is closely related to the energy required for the two substances to be compatible, and the smaller the difference in solubility parameter, the more necessary for the two substances to be compatible. Energy is small. That is, when two substances are present, in general, the smaller the difference in solubility parameter, the higher the affinity and the higher the compatibility.

  The solubility parameter can be determined experimentally or by calculation. Several methods for determining solubility parameters by calculation have been proposed. For example, for relatively high-volume materials, the Small method (PA Small: J. Appl. Chem, 3, 71 (1953)). ) Can be used. For relatively low molecular weight materials, the method of Hildebrand (JH Hildebrand and RL Scott: The Solubility of Non-Electrolytes, ACS Monograph Series, 1950) can be used.

  Further, the content of the fluorine-silicon copolymer in the composition for forming an alignment film is not particularly limited, but is preferably 0.1 wt% or more and 5.0 wt% or less, and is preferably 0.3 wt% or more and 3 or less. More preferably, it is 0.0 wt% or less. As a result, it is possible to more effectively prevent color unevenness and density unevenness (particularly streak unevenness) in the display image. Moreover, the ejection stability of the droplets of the composition for forming an alignment film can be made particularly excellent, and the formation efficiency of the alignment film can be made particularly excellent.

<Polyimide>
The polyimide is a main component of the alignment film formed using the alignment film forming composition.
The content of polyimide in the composition for forming an alignment film is not particularly limited, but is preferably 1 wt% or more and 15 wt% or less, and more preferably 2 wt% or more and 10 wt% or less.

<Γ-butyrolactone>
γ-Butyrolactone has a function of dissolving polyimide in the alignment film forming composition.
Although content of (gamma) -butyrolactone in the composition for alignment film formation is not specifically limited, It is preferable that they are 10 wt% or more and 95 wt% or less, and it is more preferable that they are 20 wt% or more and 80 wt% or less.

[Other ingredients]
Moreover, the composition for alignment film formation may contain components other than the above (other components).
Examples of such components include orientation materials such as polyamic acid, polyamic acid ester, polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, and poly (meth) acrylate. Ethylene carbonate, propylene carbonate, butylene carbonate, sulfolane, butyl cellosolve, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N′-dimethyl-2-imidazolidinone, diethylene glycol ethyl methyl ether, ethylene glycol monobutyl ether, diethylene glycol Solvents such as diethyl ether; 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyl Pyrtriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureido Propyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl- 3,6- Azanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxy Functional silane-containing compounds such as silane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane; ethylene glycol diglycidyl ether, polyethylene glycol di Glycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexane Diol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ′, N ′, -Epoxy such as tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N',-tetraglycidyl-4,4'-diaminodiphenylmethane Group-containing compounds; various antioxidants and the like.

  The viscosity at 25 ° C. of the composition for forming an alignment film (viscosity measured using a vibration viscometer) is not particularly limited, but is preferably 4 mPa · s or more and 12 mPa · s or less, preferably 5 mPa · s or more and 11 mPa · s. -More preferably, it is s or less. When the viscosity of the composition for forming an alignment film is a value within the above-mentioned range, the dispersion of the appropriate amount of the composition for forming an alignment film to be discharged is particularly small in droplet discharge by the inkjet method, and the formed alignment Unintentional variations in the thickness of the film can be effectively prevented. In addition, the measurement of the viscosity of the composition for alignment film formation can be performed, for example using a vibration type viscometer, and can be especially performed based on JISZ8809.

  In addition, the surface tension at 25 ° C. of the composition for forming an alignment film is preferably 25 dyn / cm or more and 38 dyn / cm or less, more preferably 25 dyn / cm or more and 35 dyn / cm or less, and more preferably 25 dyn / cm or more. More preferably, it is 32 dyn / cm or less. Thereby, the discharge property of the droplet can be made particularly stable. For this reason, the characteristic difference between individuals of the composition for forming an alignment film to be produced can be made particularly small. As the surface tension, a value measured according to JIS K 3362 can be adopted.

《Alignment film, image display device》
Next, an alignment film manufactured using the alignment film forming composition described above, and a liquid crystal display device as an image display device (electro-optical device) including the alignment film will be described.
FIG. 1 is a schematic exploded perspective view showing an example of a liquid crystal display device (image display device) to which the alignment film of the present invention is applied, and FIG. 2 is a liquid crystal display device (image display device) to which the alignment film of the present invention is applied. FIG. 3 is a schematic perspective view showing the configuration of the droplet discharge device, and FIG. 4 is a diagram showing a droplet discharge head in the droplet discharge device shown in FIG. Is a cross-sectional perspective view, and (b) is a schematic plan view. 5 is a schematic plan view showing a mother substrate, FIG. 6 is a schematic cross-sectional view showing a method for manufacturing a liquid crystal display device (image display device), and FIG. 7 is a method for manufacturing a liquid crystal display device (image display device). It is a schematic sectional drawing which shows.

  As shown in FIG. 1, the liquid crystal display device 200 includes a TFT (Thin Film Transistor) transmissive liquid crystal panel 220 and an illumination device 218 that illuminates the liquid crystal panel 220. The liquid crystal panel 220 includes a counter substrate 201 having a color filter 205, an element substrate 208 having a TFT element 211 in which one of three terminals is connected to the pixel electrode 210, and a liquid crystal sandwiched between the pair of substrates 201 and 208. (Not shown). Further, an upper polarizing plate 216 and a lower polarizing plate 217 for deflecting transmitted light are disposed on the surfaces of the pair of substrates 201 and 208 on the outer surface side of the liquid crystal panel 220.

  The counter substrate 201 is made of a material such as transparent glass, and has red (R), green (G), and blue (G) in a plurality of film formation regions 2 partitioned in a matrix by partition walls 204 on the surface side sandwiching the liquid crystal. B) Three color filters 205R, 205G, and 205B are formed. The partition wall portion 204 includes a lower layer bank 202 called a black matrix made of a light-shielding metal such as Cr or an oxide film thereof, and an upper layer bank 203 made of an organic compound formed on the lower layer bank 202 (downward in the drawing). It is comprised by. Further, a planarization layer 206 covering the partition wall portion 204 and the color filters 205R, 205G, and 205B, and a counter electrode 207 made of a transparent conductive film such as ITO (Indium Tin Oxide) formed so as to cover the planarization layer 206; It has. An alignment film 214 is formed so as to cover the counter electrode 207.

  The element substrate 208 is also made of a material such as transparent glass, and has a pixel electrode 210 formed in a matrix on the surface side with the liquid crystal sandwiched therebetween via an insulating film 209, and a plurality of pixel electrodes 210 formed corresponding to the pixel electrode 210. TFT element 211. Of the three terminals of the TFT element 211, the other two terminals not connected to the pixel electrode 210 are connected to the scanning line 212 and the data line 213 arranged in a grid so as to surround the pixel electrode 210 while being insulated from each other. It is connected. An alignment film 215 is formed so as to cover the pixel electrode 210, the TFT element 211, the scanning line 212, and the data line 213.

The alignment films 214 and 215 can horizontally align or vertically align liquid crystal molecules according to the display mode of the liquid crystal panel 220, and both use the alignment film forming composition as described above. It is formed by a droplet discharge method (inkjet method) as will be described later.
The lighting device 218 uses, for example, a white LED, EL, cold cathode tube, or the like as a light source, and has a configuration such as a light guide plate, a diffusion plate, and a reflection plate that can emit light from these light sources toward the liquid crystal panel 220. As long as it is provided with anything.
In the liquid crystal display device 200 of the present embodiment, since the alignment films 214 and 215 are formed using the alignment film forming composition described above, color unevenness and density unevenness (particularly streak unevenness) in a display image are caused. Occurrence is effectively prevented.

  Note that the image display device of the present invention is not limited to a TFT element as an active element, but may include a TFD (Thin Film Diode) element, and further, a passive element in which electrodes constituting a pixel intersect with each other. Type image display device (liquid crystal display device). Further, the upper and lower polarizing plates 216 and 217 may be combined with an optical functional film such as a retardation film used for the purpose of improving the viewing angle dependency. Further, the image display device (liquid crystal display device) of a reflection type or a transflective type is not limited to the transmission type.

<Method for Manufacturing Image Display Device>
Next, a method for manufacturing the liquid crystal display device (image display device) 200 will be described.
As shown in FIG. 2, the manufacturing method of the liquid crystal display device 200 of this embodiment includes a partition wall forming step (step S <b> 1) for forming the partition wall 204 on the surface of the counter substrate 201, and a film partitioned by the partition wall 204. A color filter (CF) formation step (step S2) for forming the three color filters 205R, 205G, and 205B in the formation region 2, and a flattening layer 206 that covers the partition wall portion 204 and the color filter 205. And a transparent conductive film forming step (step S4) for forming the counter electrode 207 so as to cover the planarizing layer 206. Also, a CF-side alignment film forming step (step S5) for forming the alignment film 214 so as to cover the counter electrode 207, and an element-side alignment film formation for forming the alignment film 215 so as to cover the pixel electrode 210, the TFT element 211, and the like. And a process (step S6). Furthermore, a liquid crystal filling / assembling step (step S7) is performed in which the counter substrate 201 and the element substrate 208 are opposed to each other, the liquid crystal is filled in the gap, and both the substrates 201 and 208 are joined at a predetermined position.
In the method for manufacturing the liquid crystal display device 200 of the present embodiment, in the CF forming step (step S2), the CF side alignment film forming step (step S5), and the element side alignment film forming step (step S6), a droplet discharge method (inkjet) Method) is used to form a desired thin film.

Hereinafter, the droplet discharge apparatus 100 used for the droplet discharge method will be described in detail.
As shown in FIG. 3, the droplet discharge device 100 discharges a liquid (a composition for forming a color filter 205 or a composition for forming an alignment film) as droplets onto a work W as a discharge target. Thus, a coating film made of a liquid material is formed. A stage 104 on which the workpiece W is placed, and a head unit 101 on which a plurality of droplet ejection heads 20 (see FIG. 4) for ejecting a liquid material as droplets on the placed workpiece W are mounted. .

  An X-direction guide shaft 102 for driving the head unit 101 in the sub-scanning direction (X direction) and an X-direction drive motor 103 for rotating the X-direction guide shaft 102 are provided. Also, a Y-direction guide shaft 105 for guiding the stage 104 in the main scanning direction (Y direction) orthogonal to the sub-scanning direction, and a Y-direction drive motor 106 that engages and rotates with the Y-direction guide shaft 105 It has. The X-direction guide shaft 102 and the Y-direction guide shaft 105 have a base 107 disposed in the upper part, and a control device 108 is provided in the lower part of the base 107.

Further, in order to clean (recovery) the plurality of droplet discharge heads 20 of the head unit 101, the cleaning mechanism 109 that moves along the Y-direction guide shaft 105 and the discharged liquid material are heated to evaporate / solve the solvent. And a heater 111 for drying. The cleaning mechanism 109 has a Y-direction drive motor 110 that rotates by engaging with the Y-direction guide shaft 105.
The head unit 101 includes a plurality of liquid droplet ejection heads 20 (see FIG. 4) for applying a liquid material to the workpiece W. The plurality of liquid droplet ejection heads 20 can individually eject liquid materials in accordance with ejection control signals supplied from the control device 108.

The X-direction drive motor 103 is not limited to this, but is a stepping motor, for example. When a drive pulse signal is supplied from the control device 108, the X-direction guide shaft 102 is rotated and the X-direction guide shaft 102 is rotated. The head unit 101 engaged with is moved in the X direction.
Similarly, the Y-direction drive motors 106 and 110 are, for example, stepping motors, but are not limited thereto. When a drive pulse signal is supplied from the control device 108, the Y-direction drive motors 106 and 110 are engaged with the Y-direction guide shaft 105. It rotates and moves the stage 104 and the cleaning mechanism 109 provided with the Y direction drive motors 106 and 110 in the Y direction.

When cleaning the droplet discharge head 20, the cleaning mechanism 109 moves to a position facing the head unit 101, and closes the nozzle surface of the droplet discharge head 20 so as to suck an unnecessary liquid material. Wiping for wiping off the nozzle surface to which the liquid has adhered, preliminary discharge for discharging the liquid material from all nozzles of the droplet discharge head 20, or processing for receiving and discharging the liquid material that is no longer needed.
The heater 111 is means for heat-treating the workpiece W by lamp annealing, for example, and heats the liquid discharged on the workpiece W to evaporate the solvent and convert it into a film. The controller 108 also controls the heater 111 to be turned on and off.

  In the coating operation of the droplet discharge device 100, a predetermined drive pulse signal is sent from the control device 108 to the X direction drive motor 103 and the Y direction drive motor 106, the head unit 101 is moved in the sub-scanning direction (X direction), and the stage 104 is moved. Relative movement in the main scanning direction (Y direction). During this relative movement, a control signal for ejection is supplied from the control device 108, and the liquid material is ejected as droplets from each droplet ejection head 20 to a predetermined region of the workpiece W to perform coating.

As shown in FIG. 4A, the liquid droplet ejection head 20 is formed with a liquid material flow path including a nozzle plate 21 having a plurality of nozzles 22 and a partition portion 24 for partitioning the nozzle plate 21 corresponding to each nozzle 22. This is a so-called piezo-type inkjet head having a three-layer structure including the reservoir plate 23 and a diaphragm 28 having a piezoelectric element (piezo) 29 as energy generating means. A plurality of pressure generating chambers 25 are configured by the partition portion 24 and the diaphragm 28 of the nozzle plate 21 and the reservoir plate 23. Each nozzle 22 communicates with each pressure generation chamber 25. A plurality of piezoelectric elements 29 are arranged on the diaphragm 28 so as to correspond to the respective pressure generation chambers 25.
The reservoir plate 23 is provided with a common flow path 27 in which a liquid material supplied from a tank (not shown) through a supply hole 28a formed in the vibration plate 28 is temporarily stored. The liquid filled in the common flow path 27 is supplied to each pressure generating chamber 25 through the supply port 26.

As shown in FIG. 4 (b), the droplet discharge head 20 has two nozzle rows 22a, has a 22b, a plurality (180) of a diameter of approximately 28μm sequence nozzles 22 at a pitch _{P 1} of is doing. Then, the two nozzle rows 22a, 22b are arranged in the nozzle plate 21 with a shift nozzle pitch _{P 2} of the half of the pitch _{P 1} together. In this case, the pitch _{P 1} is approximately 140 .mu.m. Therefore, the nozzle rows 22a, 360 nozzles 22 when viewed from a direction perpendicular is in the state of being arranged at a nozzle pitch _{P 2} of about 70μm to 22b. Therefore, the total length of the effective nozzles of the droplet discharge head 20 having the two nozzle rows 22a and 22b is the nozzle pitch P ₂ × 359 (approximately 25 mm). The interval between the nozzle rows 22a and 22b is approximately 2.54 mm.

When a drive waveform as an electrical signal is applied to the piezoelectric element 29, the droplet discharge head 20 deforms the diaphragm 28 by distorting the piezoelectric element 29 itself. As a result, the volume of the pressure generating chamber 25 changes, and the liquid material filled in the pressure generating chamber 25 is pressurized by the pumping action, and the liquid material can be discharged as droplets D from the nozzle 22.
In the present embodiment, the droplet discharge head 20 includes so-called double nozzle rows 22a and 22b, but is not limited thereto, and may be a single nozzle. Furthermore, the driving means for discharging the liquid material from the nozzle 22 as the droplet D is not limited to the piezoelectric element 29, and may be a heater as an electrothermal conversion element, an electrostatic actuator as an electromechanical conversion element, or the like.

  In the droplet discharge device 100 having such a droplet discharge head 20, discharge data for applying a liquid material to a desired region on the work W is input to the control device 108 from an external information processing device such as a host computer. Then, the liquid material is discharged as the droplet D from the nozzle 22 based on the discharge data. The ejection data includes position data on the desired area on the workpiece W, control data for defining ejection timing, and selection (ON) / non-selection of a plurality of nozzles 22 in the main scanning of the droplet ejection head 20 and the workpiece W. (OFF) data and nozzle data such as the number of ejections of the droplet D are included.

Hereinafter, a method for manufacturing the liquid crystal display device 200 will be described in detail.
As shown in FIG. 5, in manufacturing the liquid crystal display device 200, actually, a mother substrate M1 having a plurality of counter substrates 201 and a mother substrate M2 having a plurality of element substrates 208 are used. In each of the mother substrates M1 and M2, a component formation region corresponding to the size of the liquid crystal panel 220 is determined in design. In FIG. 5, the film formation region 3 represented by a hatched portion indicates a formation region of the alignment film 214 (alignment film 215). That is, the counter substrate 201 corresponding to four liquid crystal panels 220 is obtained from one mother substrate M1. Similarly, element substrates 208 corresponding to four liquid crystal panels 220 are obtained from one mother substrate M2. The liquid crystal panel 220 is taken out by bonding the mother substrate M1 and the mother substrate M2, each of which has a pixel component, and cutting the bonded body.

  Step S1 in FIG. 2 is a partition wall forming process. In step S1, as shown in FIG. 6A, first, the lower layer bank 202 is formed on the surface of the counter substrate 201 so as to partition the film formation region 2. As a forming method, a metal film such as Cr or Al or a film of a metal compound is formed on the surface of the counter substrate 201 so as to have a light-shielding property by a vacuum evaporation method or a sputtering method. Then, a photosensitive resin (photoresist) is applied by photolithography, and exposure, development, and etching are performed so that the film formation region 2 is opened. Subsequently, a photosensitive partition wall forming material is applied in a thickness of about 2 μm by photolithography, and is exposed and developed to form the upper layer bank 203 on the lower layer bank 202. The partition wall portion 204 has a so-called two-layer bank structure including a lower layer bank 202 and an upper layer bank 203. Note that the partition wall 204 is not limited to this, and may have a single-layer structure including only the upper bank 203 formed using a photosensitive partition wall forming material having a light shielding property.

  Step S2 in FIG. 2 is a CF forming process. In step S2, as shown in FIG. 6B, the mother substrate M1 (counter substrate 201) is placed on the stage 104 of the droplet discharge device 100. Then, in synchronism with the relative movement of the stage 104 on which the mother substrate M1 (counter substrate 201) is placed and the droplet discharge head 20 in the main scanning direction, a composition for forming a color filter as a liquid containing a coloring material. The droplets D are ejected from the plurality of nozzles 22 of the droplet ejection head 20 filled with the object 30R to the film forming region 2. The total discharge amount of the color filter forming composition 30R discharged to the film forming region 2 is based on discharge data in which the number of discharges is set in advance so that a predetermined film thickness can be obtained in the subsequent drying step. An appropriate control signal is sent from the control device 108 to the droplet discharge head 20 to be controlled. The color filter forming composition 30 </ b> R contains a red (R) coloring material and is discharged to a desired film formation region 2. Then, as shown in FIG. 6C, the mother substrate M1 (counter substrate 201) is heated by the heater 111 provided in the droplet discharge device 100, and the solvent component is discharged from the discharged color filter forming composition 30R. Is evaporated and solidified to form a red color filter 205R.

  Subsequently, a color filter forming composition containing different coloring materials in the order of green (G) and blue (B) is sequentially discharged and dried, so that the three color filters 205R, as shown in FIG. 205G and 205B are formed. However, the present invention is not limited to this method. For example, three color filter forming compositions containing different coloring materials are filled in different liquid droplet ejection heads 20, and each liquid droplet ejection head 20 is equipped in the head unit 101. Then, after discharging the color filter forming composition from each droplet discharge head 20 to the desired film forming region 2, the solvent components may be removed from these three color filter forming compositions all at once. .

  The mother substrate M1 has a lyophilic property in the film formation region 2 and at least the upper bank 203 of the partition wall portion 204 has a liquid repellency before discharging the color filter forming composition as a liquid. It is desirable to perform surface treatment so that it has. According to this, the landed droplets D spread out evenly in the film formation region 2. Further, the droplet D that has landed on the upper layer bank 203 can be easily accommodated in the film formation region 2.

  Step S3 in FIG. 2 is a planarization layer forming step. In step S <b> 3, as shown in FIG. 6E, the planarization layer 206 is formed so as to cover the color filter 205 and the upper layer bank 203. Examples of the forming method include a method in which an acrylic resin is coated and dried by a spin coating method, a roll coating method, or the like. Further, a method in which a photosensitive acrylic resin is coated and then cured by irradiation with ultraviolet light can be employed. The film thickness is approximately 100 nm. Note that the planarization layer forming step may be omitted if the surface of the counter substrate 201 on which the color filter 205 is formed is relatively flat.

  Step S4 in FIG. 2 is a transparent conductive film forming step. In step S4, as shown in FIG. 6F, a counter electrode 207 made of a conductive material such as ITO (Indium Tin Oxide) is formed on the planarizing layer 206. Examples of the film forming method include a method of vapor deposition or sputtering in vacuum using a conductive material such as ITO as a target. The film thickness is approximately 10 nm. The formed counter electrode 207 is appropriately processed into a necessary shape (pattern).

Step S5 in FIG. 2 is a CF-side alignment film forming step. In step S5, as shown in FIG. 7G, the alignment film forming composition 50 as described above is applied as a liquid so as to cover the counter electrode 207. As a coating method, the droplet discharge device 100 is used, the alignment film forming composition 50 is filled in the droplet discharge head 20, and the droplets D are discharged into the film formation region 3 shown in FIG. Also in this case, it is desirable to perform surface treatment on the mother substrate M1 (counter substrate 201) in advance so that the discharged droplets D are uniformly spread on the surface of the counter electrode 207. Examples of the surface treatment method include plasma treatment using a treatment gas as O ₂ .

  In discharging the alignment film forming composition 50 using the droplet discharge apparatus 100 as described above, the alignment film forming composition 50 as a liquid is excellent in discharge stability and suitable for the ink jet method. Since it has surface tension and viscosity, the liquid droplet D can be discharged from the nozzle 22 with a stable discharge amount without applying a high drive voltage to the piezoelectric element 29. In other words, the droplet discharge head 20 can be driven at a low voltage. Furthermore, the drawing speed can be increased by enabling high-frequency driving.

  Subsequently, the applied alignment film forming composition 50 is dried to form a film (pre-baking). In this embodiment, the mother substrate M1 is placed on a heated hot plate (HP) with a gap so that the drying progresses uniformly on the application surface, and is dried. As drying conditions, for example, the heating temperature of HP can be set to 70 ° C. or higher and 100 ° C. or lower, preferably 75 ° C. or higher and 90 ° C. or lower, and the gap can be set to 4 mm or larger and 6 mm or smaller.

By performing drying under the above-described conditions, it is possible to more effectively prevent undesired thickness unevenness in the alignment film 214 to be finally formed, and color unevenness / density unevenness in the display image. Generation of (particularly streak irregularity) can be more effectively prevented.
Further, post-baking is performed to obtain the alignment film 214 in a solidified (cured) state. As the post-baking conditions, it is desirable to heat dry at 180 ° C. or higher and 250 ° C. or lower for 10 minutes or longer and 1 hour or shorter. Thereafter, if necessary, an alignment process such as a rubbing process is performed to complete the formation of the alignment film 214 as shown in FIG.

  Step S6 in FIG. 2 is an element-side alignment film forming step. In step S6, as shown in FIG. 7I, the alignment film forming composition 50 is applied so as to cover the pixel electrodes 210 of the mother substrate M2 (element substrate 208). The coating method and the pre-bake and post-bake methods are the same as in step S5. Thereby, as shown in FIG. 7J, the alignment film 215 can be stacked on the element substrate 208. A known method may be used for forming the pixel electrode 210, the TFT element 211, the scanning line 212, and the data line 213 on the mother substrate M2, and the description thereof is omitted here.

Step S7 in FIG. 2 is a liquid crystal filling / assembling process. In step S7, as shown in FIG. 7 (k), the counter substrate 201 on which the alignment film 214 is formed and the element substrate 208 on which the alignment film 215 is formed are opposed to each other at a predetermined position. Join. A liquid crystal is filled in a gap between the counter substrate 201 and the element substrate 208 to form a liquid crystal layer 219. As a method of filling the liquid crystal, a sealing material is formed in a frame shape on one of a pair of substrates by a printing method or a discharge method. There is a method in which a required amount of liquid crystal is dropped in a vacuum after seeing it on a saucer and then bonded to the other substrate. As the sealing material, for example, a thermosetting epoxy adhesive is preferably used. The sealing material contains a gap material so that the gap (gap) between the counter substrate 201 and the element substrate 208, that is, the thickness of the liquid crystal layer 219 is constant. Examples of the gap material include glass fibers and hard resin particles having a predetermined diameter.
By attaching the upper and lower polarizing plates 216 and 217 to the front and back surfaces of the cell thus formed, the liquid crystal display device 200 is completed. The liquid crystal display device 200 is used with a lighting device 218 for illuminating the liquid crystal display device 200 provided on the back side of the element substrate 208 (see FIG. 1).

"Electronics"
An image display device (electro-optical device) 1000 such as a liquid crystal display device having the alignment films 214 and 215 as described above can be used for display portions of various electronic devices.
FIG. 8 is a perspective view showing the configuration of a mobile (or notebook) personal computer to which the electronic apparatus of the present invention is applied.
In this figure, a personal computer 1100 includes a main body 1104 having a keyboard 1102 and a display unit 1106. The display unit 1106 is supported by the main body 1104 via a hinge structure so as to be rotatable. Yes.
In the personal computer 1100, the display unit 1106 includes an image display device 1000.
FIG. 9 is a perspective view showing a configuration of a mobile phone (including PHS) to which the electronic apparatus of the present invention is applied.
In this figure, a cellular phone 1200 is provided with an image display device 1000 in a display unit, together with a plurality of operation buttons 1202, an earpiece 1204, and a mouthpiece 1206.

FIG. 10 is a perspective view showing the configuration of a digital still camera to which the electronic apparatus of the present invention is applied. In this figure, connection with an external device is also simply shown.
Here, an ordinary camera sensitizes a silver halide photographic film with a light image of a subject, whereas a digital still camera 1300 photoelectrically converts a light image of a subject with an imaging device such as a CCD (Charge Coupled Device). An imaging signal (image signal) is generated.

On the back of the case (body) 1302 in the digital still camera 1300, an image display device 1000 is provided in the display unit, and is configured to display based on an imaging signal from the CCD, and a finder that displays a subject as an electronic image. Function as.
A circuit board 1308 is installed inside the case. The circuit board 1308 is provided with a memory that can store (store) an imaging signal.

A light receiving unit 1304 including an optical lens (imaging optical system), a CCD, and the like is provided on the front side of the case 1302 (on the back side in the illustrated configuration).
When the photographer confirms the subject image displayed on the display unit and presses the shutter button 1306, the CCD image pickup signal at that time is transferred and stored in the memory of the circuit board 1308.

  In the digital still camera 1300, a video signal output terminal 1312 and an input / output terminal 1314 for data communication are provided on the side surface of the case 1302. As shown in the figure, a television monitor 1430 is connected to the video signal output terminal 1312 and a personal computer 1440 is connected to the input / output terminal 1314 for data communication as necessary. Further, the imaging signal stored in the memory of the circuit board 1308 is output to the television monitor 1430 or the personal computer 1440 by a predetermined operation.

The electronic apparatus of the present invention includes, for example, a television (for example, a liquid crystal television), a video camera, a viewfinder type, a monitor in addition to the above-described personal computer (mobile personal computer), mobile phone, and digital still camera. Direct-view video tape recorder, laptop personal computer, car navigation system, pager, electronic notebook (including communication function), electronic dictionary, calculator, electronic game device, word processor, workstation, videophone, security TV monitor , Electronic binoculars, POS terminals, devices equipped with touch panels (for example, cash dispensers of financial institutions, automatic ticket vending machines), medical devices (for example, electronic thermometers, blood pressure monitors, blood glucose meters, electrocardiographic display devices, ultrasonic diagnostic devices, endoscopy) Mirror display device), Group detector, various measuring instruments, gages (e.g., gages for vehicles, aircraft, and ships), a flight simulator, various monitors such, can be applied to the projection type display device such as a projector.
Since the electronic device of the present invention includes the alignment film as described above, it is possible to effectively prevent color unevenness and density unevenness (particularly, streak unevenness) in the display image displayed on the display unit.

As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to these.
For example, each unit included in the alignment film, the image display device, and the electronic device can be replaced with any one that exhibits the same function, or another configuration can be added.
In the above-described embodiment, the liquid crystal display device has been described as including three color filters of red (R), green (G), and blue (B). Good. Moreover, you may provide a color filter of four or more colors.
In the above-described embodiment, the case where the present invention is applied to a plurality of alignment films included in the image display device has been described. However, the present invention is applied to at least one alignment film included in the image display device. May be.

Next, specific examples of the present invention will be described.
[1] Synthesis of fluorine-silicon copolymer (Synthesis Example 1)
A stirrer, a _{condenser, CH 2 = CHCOOCH 2 CH 2} C 8 F 17 in the compounds represented by the glass flask equipped with a thermometer as a fluorinated alkyl group-containing vinyl monomer f: 18 and parts, alkoxysilyl group-containing Compound represented by formula (2-40) as vinyl monomer s: 12 parts by weight and monoacrylate compound having a side chain of a copolymer of ethylene oxide and propylene oxide having a weight average molecular weight of 400: 58 parts by weight Then, 4 parts by weight of a compound in which both ends of tetraethylene glycol were ester-bonded to methacrylic acid, 8 parts by weight of methyl methacrylate, and 350 parts by weight of isopropyl alcohol were charged. Then, under reflux in a nitrogen gas stream, 1.0 part by weight of azobisisobutyronitrile (hereinafter referred to as AIBN) as a polymerization initiator and 10 parts by weight of lauryl mercaptan as a continuous transfer agent are added. After that, the temperature in the glass flask was set to 85 ° C. and refluxed for 12 hours.
Thereafter, the reaction product was purified to obtain a fluorine-silicon copolymer FS1. The weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) of the fluorine-silicon copolymer FS1 was 18,000.
(Synthesis Examples 2 to 6)
The same operation as in Synthesis Example 1 was performed except that the type and amount of monomer components used for polymer synthesis (preparation of polymer solution) were changed as shown in Table 1. As a result, five types of fluorine-silicon copolymers FS2 to FS6 were obtained.

Table 1 shows the types and amounts of monomers used in the synthesis of the fluorine-silicon copolymers in Synthesis Examples 1 to 6 (compositions of the fluorine-silicon copolymers synthesized in Synthesis Examples 1 to 6). Are shown together. In the table, “f1” represents a compound represented by the structural formula CH ₂ ═CHCOOCH ₂ CH ₂ C ₈ F ₁₇ , and “f2” represents the structural formula CH ₂ ═C (CH ₂ CH ₂ C ₈ F ₁₇ ) COOCH ₂ CH ₂ C ₈ F ₁₇ represents a compound, “f3” represents a compound represented by the structural formula CH ₂ ═C (CH ₃ ) COOCH ₂ C ₂₀ F ₄₁ , and “s1” represents the above formula (2-40) represents a compound, “s2” represents a compound represented by the formula (2-33), “s3” represents a compound represented by the formula (2-1), and “PEA” "Represents a monoacrylate compound having a copolymer of ethylene oxide and propylene oxide having a weight average molecular weight of 400 in the side chain, and" TGMA "represents both ends of tetraethylene glycol with methacrylic acid and ethylene. Indicates ether bound compound, "MMA" represents methyl methacrylate. The table also shows the weight average molecular weight Mw of the synthesized fluorine-silicon copolymer. In the table, the SP value of the fluorine-silicon copolymer was determined by the method of Small.

[2] Preparation of composition for forming alignment film (Example 1)
A composition for forming an alignment film was obtained by mixing a polyimide solution (AL-16470, manufactured by JSR), γ-butyrolactone, and fluorine-silicon copolymer FS1.
(Examples 2 to 11)
An alignment film forming composition was prepared in the same manner as in Example 1 except that the types and contents of the components of the alignment film forming composition were changed as shown in Table 2.
(Comparative Example 1)
An alignment film forming composition was prepared in the same manner as in Example 1 except that the types and amounts of components used for the preparation of the alignment film forming composition were changed as shown in Table 2.

  The compositions of the alignment film forming compositions of the above Examples and Comparative Examples are shown together in Table 2. In the table, the polyimide constituting AL-16470 (manufactured by JSR) is indicated by “ALI”, the polyimide constituting AL-60601 (manufactured by JSR) is indicated by “ALV”, and disparon as a fluorine-based leveling agent UVX-270 (manufactured by Enomoto Kasei Co., Ltd.) was indicated by “UVX-270”, γ-butyrolactone was indicated by “γ-BL”, N-methylpyrrolidone was indicated by “NMP”, and butyl cellosolve was indicated by “BC”. In addition, the viscosity at 25 ° C. of the composition for forming an alignment film of each of the above examples measured according to JIS Z8809 using a vibration viscometer is in the range of 5 mPa · s to 11 mPa · s. The value was within.

[3] Evaluation of ejection stability of alignment film-forming composition With respect to the alignment film-forming compositions of the examples and comparative examples, the ejection stability of droplets was evaluated by the following tests.
First, a droplet discharge device as shown in FIGS. 3 and 4 was prepared.
Next, in the state in which the driving waveform of the piezo element was optimized, 5000000 (5000000 drops) of droplets were continuously discharged from each nozzle of the droplet discharge head for each alignment film forming composition. For the two specified nozzles on the left and right ends of the droplet discharge head, the total weight of the discharged droplets is obtained, and the absolute value ΔW [ng] of the difference between the average discharge amounts of the droplets discharged from the two nozzles is calculated. Asked. A ratio (ΔW / W _T ) of ΔW with respect to the target discharge amount W _T [ng] of the droplet was obtained and evaluated according to the following five-stage criteria. As the value of [Delta] W / W _T is small, it can be said that the greater the stability of the droplet discharge amount.

A: The value of ΔW / _{W T} is less than 0.015.
B: The value of ΔW / _{W T} is less than 0.015 than 0.080.
C: The value of ΔW / _{W T} is less than 0.080 than 0.150.
D: The value of ΔW / _{W T} is less than 0.150 than 0.250.
E: The value of ΔW / _{W T} is 0.250 or more.

[4] Manufacture of Liquid Crystal Display Device A liquid crystal display device was manufactured using the method described in the above embodiment. In each example and comparative example, a liquid crystal display device was manufactured using the same conditions except that the alignment film forming composition used for forming the alignment film was changed.

[5] Evaluation of the occurrence of color unevenness In the darkroom, the liquid crystal display device for each of the examples and comparative examples manufactured in [4] above was displayed in a single color display of red, a single display of green, a single display of blue, Visual observation was performed in a state where monochromatic display was performed, and the occurrence of color unevenness at each part was evaluated according to the following five-stage criteria.

A: Color unevenness is not recognized at all.
B: Color unevenness is hardly recognized.
C: Color unevenness is slightly observed.
D: Uneven color is clearly recognized.
E: Color unevenness is noticeable.
The results of the above evaluation are shown in Table 3.

As is clear from Table 3, the present invention gave excellent results, whereas the comparative example did not give satisfactory results. Moreover, in this invention, the rubbing process (orientation process) at the time of manufacture of an alignment film (at the time of manufacture of a liquid crystal display device) was able to be performed suitably.
Further, when a commercially available liquid crystal television was disassembled and the liquid crystal display device part was replaced with one manufactured as described above, and the same evaluation as described above was performed, the same result as above was obtained.

DESCRIPTION OF SYMBOLS 200 ... Liquid crystal display device 201 ... Counter substrate 202 ... Lower layer bank 203 ... Upper layer bank 204 ... Partition part 205, 205R, 205G, 205B ... Color filter 206 ... Planarization layer 207 ... Counter electrode 208 ... Element substrate 209 ... Insulating film 210 ... Pixel electrode 211 ... TFT element 212 ... Scanning line 213 ... Data line 214 ... Alignment film 215 ... Alignment film 216 ... Upper polarization plate 217 ... Lower polarization plate 218 ... Lighting device 219 ... Liquid crystal layer 220 ... Liquid crystal panel S1, S2, S3, S4, S5, S6, S7 ... Step 100 ... Droplet discharge device 101 ... Head unit 102 ... X direction guide shaft 103 ... X direction drive motor 104 ... Stage 105 ... Y direction guide shaft 106 ... Y direction drive motor 107 ... Base DESCRIPTION OF SYMBOLS 108 ... Control apparatus 109 ... Cleaning mechanism 110 ... Y direction Dynamic motor 111 ... heater 20 ... droplet discharge head 21 ... nozzle plate 22 ... nozzle 22a ... nozzle row 22b ... nozzle row 23 ... reservoir plate 24 ... partition 25 ... pressure generating chamber 26 ... supply port 27 ... common flow path 28a ... supply holes 28 ... diaphragm 29 ... piezoelectric elements P 1 _... pitch P 2 _... nozzle pitch M1 ... mother substrate M2 ... mother board 2 ... film forming region 3 ... film forming region D ... droplets 30R ... color filter forming composition 50 ... Composition for forming alignment film 1000 ... Image display device 1100 ... Personal computer 1102 ... Keyboard 1104 ... Main body 1106 ... Display unit 1200 ... Mobile phone 1202 ... Operation buttons 1204 ... Earpiece 1206 ... Mouthpiece 1300 ... Digital still camera 1302 ... Case (body) 1304 Light receiving unit 1306 ... Shutter button 1308 ... Circuit board 1312 ... Video signal output terminal 1314 ... Input / output terminal for data communication 1430 ... Television monitor 1440 ... Personal computer

Claims (8)

An alignment film forming composition used for manufacturing an alignment film by an inkjet method,
A composition for forming an alignment film, comprising polyimide, γ-butyrolactone, and a fluorine-based leveling agent. The fluorine-based leveling agent includes a fluorinated alkyl group-containing vinyl monomer f represented by the following formula (1) and an alkoxysilyl group-containing vinyl monomer s represented by the following formula (2) as monomer components. The composition for forming an alignment film according to claim 1, comprising the prepared fluorine-silicon copolymer.

  The composition for forming an alignment film according to claim 2, wherein the fluorine-silicon copolymer has a weight average molecular weight of 15,000 or more and 500,000 or less.   The alignment film forming composition according to claim 2 or 3, wherein the fluorine-silicone copolymer has a solubility parameter of 5 or more and 8 or less.   5. The composition for forming an alignment film according to claim 2, wherein the content of the fluorine-silicon copolymer in the composition for forming an alignment film is 0.1 wt% or more and 5.0 wt% or less. .   An alignment film formed using the alignment film-forming composition according to claim 1.   An image display device comprising the alignment film according to claim 6.   An electronic apparatus comprising the image display device according to claim 7.

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