JP2006195096A - Method for forming spacer, exposure mask used therefor, and color filter substrate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming spacers by which spacers of 12 μmΦ level are formed uniformly on the entire surface of a color filter substrate by using a proximity exposure technique. <P>SOLUTION: In the proximity exposure technique, a first exposure to expose respective spacer forming regions via first mask openings with a predetermined aperture width arranged on an exposure mask, and a second exposure to expose regions inside the regions subjected to the first exposure via second mask openings with an aperture width less than the predetermined aperture width arranged on the exposure mask or on another exposure mask, are successively conducted. The first exposure determines a width (a base portion width) of the spacers to be formed, and the second exposure has no influence on the width of the spacers to be formed. The height (thickness) of the spacer to be formed is determined with the exposure by setting the exposure to the region where the first exposure and the second exposure overlap with each other to be the exposure sufficient for hardening the negative type photosensitive material layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  According to the present invention, a spacer for controlling a gap between a color filter substrate and its counter substrate when used in a display device is applied to the color filter substrate from a negative photosensitive material layer by a photolithography method using a proximity exposure method. The present invention relates to a spacer forming method to be formed, an exposure mask used therefor, and a color filter substrate provided with spacers formed by the spacer forming method.

In recent years, color liquid crystal displays have attracted attention as flat displays. As an example of a color liquid crystal display, a black matrix, a colored layer composed of a plurality of colors (usually three primary colors of red (R), green (G), and blue (B)), a transparent conductive layer (common electrode), and an alignment layer The color filter provided and a counter electrode substrate provided with a thin film transistor (TFT element), a pixel electrode and an alignment layer face each other with a predetermined gap, and a liquid crystal material is injected into the gap to form a liquid crystal layer. is there.
In such a color liquid crystal display, the gap is the thickness of the liquid crystal layer itself, and in order to enable good display performance required for the color liquid crystal display, such as high-speed response, high contrast ratio, wide viewing angle, etc. The thickness of the liquid crystal layer, that is, the gap distance between the color filter and the counter electrode substrate must be kept strictly constant.

Conventionally, as a method for determining the thickness of a liquid crystal layer in a color liquid crystal display, a liquid crystal in which a large number of particles or rods called spacers made of glass, alumina, plastic, or the like are mixed is injected into a gap between a color filter and a counter electrode substrate. There is a way.
The size of the gap between the two substrates, that is, the thickness of the liquid crystal layer is determined by the size of the spacer.
However, the method for forming the gap between the color filter and the counter electrode substrate as described above has the following problems in the operation of the color liquid crystal display.
That is, if the density of the spacers scattered on the substrate surface is appropriate and the spacers are not uniformly dispersed on the substrate surface, a gap having a uniform size over the entire surface of the color liquid crystal display is not formed.
In general, when the scattering amount (density) of spacers is increased, the variation deviation in the thickness of the gap portion is reduced, but when the scattering amount (density) is increased, the number of spacers present on the display pixel portion is also increased, and the display pixel portion is increased. Then, this spacer becomes a foreign material of the liquid crystal material.
The presence of the spacer causes disturbances in the alignment of the liquid crystal molecules regulated by the alignment film, and only the liquid crystal around the spacer has problems such as the inability to control the alignment by turning the voltage on and off, and the contrast ratio. There has been a problem that display performance is reduced.

In order to solve such a problem, a color filter (hereinafter also referred to as a color filter substrate) provided with columnar convex portions as an interval holding member for determining a gap (the thickness of the liquid crystal layer) is disclosed in, for example, Japanese Patent Laid-Open No. 4-318816. No. 1 (Patent Document 1) and the like.
In this color filter, after forming a colored layer and forming a protective layer so as to cover the colored layer, a columnar convex portion is formed on the black matrix by a photolithography process using a photosensitive resin. It is formed at a predetermined location.

This columnar protrusion (hereinafter also referred to as a spacer) has been conventionally formed by a photolithography method using a proximity exposure method from the viewpoint of productivity and quality.
However, there has been a strong demand for display refinement in recent years, particularly in liquid crystal displays for PDAs, mobile phones, and the like. In these color filter substrates for liquid crystal displays, the size of columnar protrusions (spacers) is also required to be miniaturized. In recent years, a spacer having a width (bottom) of 12 μmΦ or less has been required.
In the conventional proximity exposure method, a negative photosensitive material layer is used, and exposure is performed to form one spacer by one exposure through one opening of an exposure mask. If the width of the space (bottom part) is reduced to about 12 μmΦ, the spacer width becomes too large when the exposure amount is increased, and when the exposure is performed with the exposure amount reduced, the target height of the spacer ( Thickness), it has become difficult to form the color filter substrate on the entire surface with good uniformity.

As described above, there has been a strong demand for display refinement in recent years. Particularly, in color filter substrates for liquid crystal displays such as PDAs and mobile phones, spacers for controlling the gap between the color filter substrate and the counter substrate are fine. In recent years, a space width (bottom) of 12 μmΦ or less has been demanded.
Along with this, to form a spacer of 12 μmΦ level, the conventional proximity exposure method is used to form one spacer by one exposure through one opening of the exposure mask, and the spacer is formed. In the spacer formation method using the photolithographic method, it has become difficult to form the spacer with a desired height (thickness) on the entire surface of the color filter substrate with good uniformity.
The present invention corresponds to this, and an object of the present invention is to provide a spacer forming method capable of forming a 12 μmφ level spacer on the entire surface of the color filter substrate with good uniformity using a proximity exposure method.

In the spacer forming method of the present invention, a spacer for controlling the gap between the color filter substrate and the counter substrate in the display device is applied to the color filter forming substrate from a negative photosensitive material layer by a photolithography method using a proximity exposure method. A method of forming a spacer, wherein the proximity exposure method includes: a first exposure that exposes each spacer formation region through a first mask opening having a predetermined opening width provided in an exposure mask; A second mask opening provided in another exposure mask having an opening width smaller than the predetermined opening width exposes an inner area of the exposure area by the first exposure, and the second exposure is performed before and after. The second exposure is performed by exposing a region inside the exposure region by the first exposure, and the first exposure is performed by the width of the spacer to be formed ( Side width) and the second exposure does not affect the width of the spacer to be formed (bottom side width), and the first exposure and the second exposure The height (thickness) of the spacer formed by the exposure amount is determined by setting the exposure amount in the region where the layers overlap as an exposure amount sufficient to cure the negative photosensitive material layer. It is.
In the spacer formation method, the first exposure and the second exposure are performed with the same exposure amount.
And in the spacer forming method according to any one of the above, the first mask opening and the second mask opening are provided in the same one exposure mask,
The exposure mask is characterized in that the first exposure and the second exposure are performed at predetermined positions by changing the relative positions of the exposure mask and the color filter substrate, respectively. Is characterized in that the first mask openings and the second mask openings are alternately and repeatedly arranged at a predetermined pitch in the X direction and / or the Y direction.
The spacer forming method according to any one of the above, wherein the spacer has a fine width of 12 μm or less.
The spacer forming method according to any one of the above, wherein the color filter forming substrate is for a liquid crystal display device.
Here, the order of performing the first exposure and the second exposure does not matter.
Here, a substrate in which a color filter layer is formed before the formation of a spacer is referred to as a color filter formation substrate, and a substrate in which a spacer is formed on such a color filter formation substrate is referred to as a color filter substrate.

  The color filter substrate of the present invention is characterized in that a spacer formed by the spacer forming method according to any one of claims 1 to 6 is disposed.

  The exposure mask of the present invention includes a spacer for controlling a gap between a color filter substrate and its counter substrate when used in a display device from a negative photosensitive material layer by a photolithography method using a proximity exposure method. A spacer forming method for forming on a color filter substrate, wherein the proximity exposure method exposes each spacer forming region through a first mask opening having a predetermined opening width provided in an exposure mask. And a second exposure that exposes an area inside the exposure area by the first exposure using a second mask opening having an opening width smaller than the predetermined opening width provided in the or another exposure mask. Is an exposure mask used in a spacer forming method that is performed in a row, and the first mask opening and the second mask are formed at a predetermined pitch in the X direction and / or the Y direction. It is characterized in that the disk and the opening are alternately repeatedly arranged.

(Function)
The spacer forming method of the present invention can provide a spacer forming method that can form a 12 μmφ level spacer on the entire surface of the color filter substrate with good uniformity by using the proximity exposure method. .
Specifically, in the proximity exposure method, each spacer formation region is exposed to the first exposure with a first mask opening having a predetermined opening width provided in the exposure mask, and to the above or another exposure mask. A second mask opening having an opening width smaller than the predetermined opening width provided is used to expose a region inside the exposure region by the first exposure, and the second exposure is performed before and after. The first exposure determines the width (bottom side width) of the spacer to be formed, and the second exposure does not affect the width (bottom side width) of the spacer to be formed. Further, the exposure amount in the region where the first exposure and the second exposure overlap is set as an exposure amount sufficient to cure the negative photosensitive material layer, and the height (thickness) of the spacer formed by the exposure amount Have achieved this by determining .
That is, the second exposure is performed by the second mask opening formed smaller than the first mask opening so as not to affect the width (base width) of the spacer to be formed. It is assumed that the inner area of the exposure area is exposed and does not affect the width (bottom width) of the spacer to be formed. As a result, the width of the spacer (bottom width) formed only by the first exposure. ) Can be determined.
Then, the exposure area exposed by overlapping the first exposure and the second exposure is irradiated with an exposure amount sufficient to cure the negative photosensitive material, and the negative photosensitive material in the exposure area is sufficiently cured. Thus, the first exposure is not necessarily sufficient to cure the negative photosensitive material, but the exposure amount of the area where the first exposure and the second exposure overlap is cured with the negative photosensitive material. It is assumed that the exposure amount is sufficient to achieve this, and the height (thickness) of the formed spacer can be stably obtained.
Further, by adjusting the first exposure and the second exposure with the same exposure amount, it is not necessary to adjust the exposure amount.
Further, the first mask opening and the second mask opening are provided in the same exposure mask, and the first exposure and the second exposure are performed with the exposure mask. By doing so, it is possible to use only one exposure mask for spacer formation, and it is possible to perform the exposure work efficiently.
As such an exposure mask, for example, a mask in which the first mask openings and the second mask openings are alternately and repeatedly arranged at a predetermined pitch in the X direction and / or the Y direction. It is done.
This is particularly effective when the spacer width (base width) is a fine width of 12 μm or less.
As described above, in the conventional proximity exposure method, a negative photosensitive material layer is used to perform exposure for forming one spacer by one exposure through one opening of an exposure mask. Therefore, as the miniaturization progresses recently and the width of the space (bottom) becomes as small as about 12 μmΦ, the spacer width becomes too large when the exposure amount is increased, and when the exposure is performed with the exposure amount reduced, the spacer However, it is difficult to form the color filter substrate on the entire surface with a uniform height (thickness), but the spacer can be used even when the spacer width (bottom width) is 12 μm or less. Can be formed with good uniformity over the entire surface of the color filter substrate.
In particular, it is effective for forming a spacer on a color filter substrate for a liquid crystal display device that requires uniformity in the height (thickness) of the spacer.

  By adopting such a configuration, the color filter substrate of the present invention can provide a color filter substrate capable of forming a spacer having a spacer width of 12 μmφ level on the entire surface with good uniformity.

  The exposure mask according to the present invention can practically implement the spacer formation method of claim 3 by adopting such a configuration.

As described above, the present invention makes it possible to provide a spacer forming method capable of forming a 12 μmφ level spacer on the entire surface of the color filter substrate with good uniformity using the proximity exposure method.
As a result, it is possible to provide a color filter substrate in which spacers of 12 μmΦ level are arranged on the entire surface with good uniformity.

Embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a process cross-sectional view of an example of an embodiment of a spacer forming method of the present invention, and FIG. 2A is an embodiment of a color filter substrate of the present invention in which spacers are formed by the spacer forming method shown in FIG. FIG. 2B is a cross-sectional view at the position B1-B2 in FIG. 1A, and FIG. 3A is a spacer formed by the spacer forming method of the embodiment shown in FIG. FIG. 3B is a diagram illustrating the degree of variation in the height (thickness) of an example spacer in which a spacer is formed. FIG. 3B is a diagram illustrating another example in which a spacer is formed by the spacer forming method of the embodiment shown in FIG. FIG. 4 is a diagram schematically showing a measurement position of the spacer height (thickness), and FIG. 5 is a diagram illustrating a spacer forming method according to a conventional exposure method. Illustrates the degree of variation in spacer height (thickness) In FIG, 6 is a cross-sectional view of one example of a liquid crystal display device using a color filter substrate of the present invention.
Note that FIG. 2A is a view as seen from the transparent overcoat layer side, and the dotted line indicates the filter opening.
1, 2, 4, and 6, 110 is a color filter forming substrate, 110 A is a color filter substrate (with spacers formed), 111 is a transparent substrate, 112 is a black matrix, 115 is a pixel portion, and 115 a is a first pixel. 1 color portion (red portion) region, 115b a second color portion (green portion) region, 115c a third color portion (blue portion) region, 116 an overcoat layer, 120 a photosensitive material layer, and 121 a An exposure area by the first exposure, 122 an exposure area by the second exposure, 123 an exposure area by the first exposure and the second exposure, 125 a spacer, 130 an exposure mask, 131 a light shielding portion, 132 1st mask opening, 133 is 2nd mask opening, 140 is exposure light, 150 is a gap, 1-26 is a spacer position number, 50 is a color filter substrate, 51 is a transparent substrate, 52 is a bra Cstripes, 53a, 53b, 53 are colored layers, 54 are overcoat layers, 55 are transparent electrodes, 58 are columnar spacers, 59 are control protrusions, 61 are liquid crystals, 62a and 62b are alignment materials, 70 is a counter substrate, 71 is a transparent substrate, 72 is a transparent electrode, 80 is a diffusion plate, and 81 is a backlight.

First, an example of an embodiment of the spacer forming method of the present invention will be described with reference to FIG. The spacer forming method of this example is a method for forming a color filter substrate for a liquid crystal display device in which the gap between the color filter substrate and the counter substrate is controlled by a spacer formed as a part of the color filter substrate. In this method, the spacer 125 is formed on the color filter forming substrate 110 from the negative photosensitive material layer 120 by the photolithography method using the proximity exposure method.
In the proximity exposure method in this example, the first exposure for exposing each spacer formation region through a first mask opening 132 having a predetermined opening width W1 provided in one exposure mask 130, and the exposure mask 130 described above. The second exposure, in which the second mask opening 133 having an opening width W2 smaller than the predetermined opening width W1 is exposed to the inner area of the exposure area by the first exposure. In brief, using a single exposure mask 130, the relative positions of the exposure mask 130 and the color filter forming substrate 110 provided with the photosensitive material layer are shifted and aligned, The exposure is performed once at each position.
The first exposure determines the width (bottom side width) W0 of the spacer to be formed, and the second exposure does not affect the width (bottom side width) W0 of the spacer to be formed. is there.
In this example, as shown in FIG. 2A, in the exposure mask 130, the first mask opening 132 and the second mask opening have a predetermined pitch P0 in one direction (X direction or Y direction). Thus, the first mask openings 132 and the second mask openings 133 are alternately and repeatedly arranged.
Then, assuming that the exposure amount in the region where the first exposure and the second exposure overlap is an exposure amount sufficient to cure the negative photosensitive material layer 120, the height (thickness) of the spacer formed by the exposure amount. ) H0 is determined.
In this example, the first exposure and the second exposure are performed with the same exposure amount, whereby the exposure amount is set separately for the first exposure and the second exposure. There is no need to do.

A color filter forming substrate 110 on which a color filter layer is formed and a spacer is not formed is prepared in advance, and a negative photosensitive material layer for forming a spacer is formed on the color filter layer side.
First, with a predetermined proximity exposure apparatus, the exposure mask 130 and the color filter forming substrate 110 provided with the negative photosensitive material layer 120 are aligned with a gap of 75 μm to 150 μm, The photosensitive material layer 120 is exposed (also referred to as first exposure) through the exposure mask 130 for the time T0. (Fig. 1 (a))
The first exposure that is exposed through the first mask opening 132 having the predetermined opening width W1 and the second exposure that is exposed through the second mask opening 133 having the opening width W2 are performed corresponding to the respective openings.
By this first exposure, the exposure area 121 is exposed by the second mask opening 133 having the opening width W2 corresponding to the first exposure that is exposed by the first mask opening 132 having the predetermined opening width W1. Corresponding to the exposure of 2, an exposure area 122 is obtained as an area exposed by each exposure.
Next, the exposure mask 130 and the color filter forming substrate 110 provided with the negative photosensitive material layer 120 are moved relative to each other in a predetermined direction by one pitch (P0), and adjusted to the same gap as the previous exposure. Then, alignment is performed, and exposure of the photosensitive material layer 120 (also referred to as second exposure) is performed through the exposure mask 130 for a predetermined time T0 as in the previous exposure. (FIG. 1B) Also in the second exposure, the first exposure that is exposed through the first mask opening 132 having the predetermined opening width W1 and the second exposure that is exposed through the second mask opening 133 having the opening width W2. However, since the exposure mask 130 and the color filter forming substrate 110 are relatively shifted by one pitch (P0) as compared with the case of the first exposure, By the second exposure, the exposure by the first exposure and the exposure by the second exposure overlap in each exposure unit.
As a result of the second exposure, an exposure area 121 for only the first exposure and an exposure area 123 in which the first exposure and the second exposure overlap are obtained as the exposed areas.
Subsequently, after this, development processing is performed to obtain the color filter substrate 110A on which the spacer 125 is formed.
In this way, the exposure region 123 where the first exposure and the second exposure overlap can be sufficiently cured with a sufficient exposure amount to obtain a uniform height (thickness) H0, and only the first exposure. In the exposure region 121, the exposure amount is not so large and can be prevented from becoming thicker than the width W1 of the first mask opening 132 of the exposure mask 130. As a result, the spacer width (bottom width) W0 is set to the mask opening size W1. Can be obtained with a width close to.

There are various arrangement forms of the spacer, and there is no particular limitation.
For example, as shown in FIG. 2, a color filter 110 </ b> A substrate having an arrangement form in which spacers 125 are arranged every other interval between openings of the second color portion (green portion) region 115 b can be cited. This is not limited.

Next, the material of the negative photosensitive material layer 120 for forming the spacer 125 will be described below.
The photosensitive material layer 120 can be formed using a photosensitive resin composition containing a monomer, a polymer, a photopolymerization initiator, and the like.
The photosensitive material layer 120 is composed of a photosensitive resin composition in which the type and content of the contained monomer and the type and content of the contained polymer are adjusted, such as a direct gravure coating method, a gravure reverse coating method, a reverse roll coating method, a slide die. It can be formed by applying and drying by a known application means such as a coating method, a slit die coating method or a comma coating method.
The photosensitive material layer 120 is subjected to the first exposure shown in FIG. 1A and the second exposure shown in FIG. 1B, and after development, as shown in FIG. 1C. A spacer composed of columnar protrusions can be formed.

  Specifically, as monomers, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2 -Hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, 1, 4-butanediol Acrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,3-propanediol acrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate , Tripropylene glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyoxyethylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyltrimethylolpropane tri Acrylate, butylene glycol diacrylate, 1,2,4-butanetriol triacryl 2,2,4-trimethyl-1,3-pentanediol diacrylate, diallyl fumarate, 1,10-decanediol dimethyl acrylate, pentaerythritol hexaacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, And those obtained by changing the above acrylates to methacrylates, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, etc., and the above monomers as one kind or a mixture of two or more kinds, or others It can be used as a mixture with the compound.

  Examples of the polymer used in the photosensitive resin composition include ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethylene vinyl copolymer, polystyrene, acrylonitrile-styrene copolymer, ABS resin, polymethacrylate. Acid resin, ethylene methacrylate resin, polyvinyl chloride resin, chlorinated vinyl chloride, polyvinyl alcohol, cellulose acetate propionate, cellulose acetate butyrate, nylon 6, nylon 66, nylon 12, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, Polyvinyl acetal, polyether ether ketone, polyether sulfone, polyphenylene sulfide, polyarylate, polyvinyl butyral, epoxy resin, phenoxy resin, polyimide Fatty acid, polyamideimide resin, polyamic acid resin, polyetherimide resin, phenol resin, urea resin, etc., and polymerizable monomers such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl Methacrylate, isopropyl acrylate, isopropyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-hexyl acrylate, n -Hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, n-octyl acrylate , N-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, styrene, α-methyl styrene, N-vinyl-2-pyrrolidone, glycidyl (meth) acrylate, tricyclodecanyl (meth) acrylate, methyl adamantyl One or more of (meth) acrylates and dimers of acrylic acid, methacrylic acid and acrylic acid (for example, M-5600 manufactured by Toa Gosei Chemical Co., Ltd.), itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl Examples thereof include polymers or copolymers composed of one or more of acetic acid and acid anhydrides thereof. Moreover, the polymer etc. which added the ethylenically unsaturated compound which has a glycidyl group or a hydroxyl group to said copolymer are mentioned, However It is not limited to these.

  Photopolymerization initiators used in the photosensitive resin composition include benzophenone, methyl o-benzoylbenzoate, 4,4-bis (dimethylamine) benzophenone, 4,4-bis (diethylamine) benzophenone, α-amino. Acetophenone, 4,4-dichlorobenzophenone, 4-benzoyl-4-methyldiphenyl ketone, dibenzyl ketone, fluorenone, 2,2-diethoxyacetophonone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy- 2-methylpropiophenone, p-tert-butyldichloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyldimethyl ketal, benzylmethoxyethyla Tar, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, dibenzsuberon, methyleneanthrone, 4-azidobenzylacetophenone, 2,6-bis ( p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1-phenyl-propanedione 2- (o-ethoxycarbonyl) oxime, 1,3-diphenyl-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-ben) Yl) oxime, Michler's ketone, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone , Naphthalenesulfonyl chloride, quinolinesulfonyl chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzthiazole disulfide, triphenylphosphine, camphorquinone, N1717 manufactured by ADEKA Corporation, tetrabromine Examples thereof include a combination of a photoreducing dye such as carbonized carbon, tribromophenyl sulfone, benzoin peroxide, eosin, and methylene blue and a reducing agent such as ascorbic acid and triethanolamine.

  Furthermore, an epoxy resin can be contained in the photosensitive resin composition. As the epoxy resin to be used, the Epicote series manufactured by Mitsubishi Yuka Shell Co., Ltd., the Celoxide series manufactured by Daicel Co., Ltd., the Epolide series, or the bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol- S type epoxy resin, novolak type epoxy resin, polycarboxylic acid glycidyl ester, polyol glycidyl ester, aliphatic or cycloaliphatic epoxy resin, amine epoxy resin, triphenolmethane type epoxy resin, dihydroxybenzene type epoxy resin, glycidyl (meth) Examples thereof include a copolymerized epoxy compound of an acrylate and a monomer capable of radical polymerization. In this invention, said epoxy resin can be used individually or as a 2 or more types of mixture.

  Examples of the solvent used in the photosensitive resin composition include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, terpenes such as α- or β-terpineol, acetone, and methyl ethyl ketone. , Ketones such as cyclohexanone and N-methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, cellosolve, methylcellosolve, ethylcellosolve, carbitol, methylcarbitol, ethylcarbitol, butyl Carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol Glycol ethers such as coal monomethyl ether and triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether Examples include acetates such as acetate and propylene glycol monoethyl ether acetate.

The material of each part of the color filter 110A substrate will be briefly described below.
As the transparent substrate 111, non-alkali glass has been used in recent years in addition to a plastic substrate and 100% silicon dioxide quartz glass.
As the colored layer including the black matrix 112, all the colored pattern layers formed using the pigment dispersion method have been used in recent years, but are not limited thereto.
In addition to those formed by the pigment dispersion method, those in which each colored pattern layer is formed by a conventionally known dyeing method, electrodeposition method, printing method, ink jet method or the like may be used.
As the photosensitive material for forming each colored pattern layer, the same composition as that for the photosensitive material for forming the spacer described above is used, and the pigments for forming the respective colors are mixed therein. . For the black matrix 112, a light shielding layer mainly composed of chromium formed by sputtering or the like may be used in addition to the one formed by the above forming method.
The overcoat layer 116 is also called a protective film, and a general cross-linked polymer material such as acrylic, styrene, polyether, or polyimide is usually used.
The film is applied on the colored pattern layer of the color filter forming substrate by a spin coating method, a roll coating method, a bar coating method, a casting method, or the like.

Further, as a liquid crystal display device using a color filter substrate provided with spacers by the spacer forming method of the present invention, for example, a multi-alignment division type (MVA mode) liquid crystal display device as shown in FIG. Although not limited to this.
The liquid crystal display device shown in FIG. 6 has a structure in which a color filter substrate 50 and a TFT side substrate (also referred to as a counter substrate) 70 including a large number of pixel electrodes 72 are opposed to each other, and a liquid crystal 74 is sealed therebetween.
The color filter substrate 50 shown here is different from that shown in FIG. 2 in that a control projection 59 for controlling the orientation is provided in addition to the columnar spacer 58 which is a gap control spacer.

<Example>
A negative photosensitive material layer for forming the spacer 125 is coated with a photosensitive material having the following composition, dried, exposed and developed under the following conditions by the spacer forming method shown in FIG. The variation in the height (thickness) of the spacer 125 formed on the filter forming substrate 110 was examined. When a spacer having a spacer width (bottom width) of 12 μm or less is formed, a conventional exposure method is used. As compared with the case where the spacers according to (Comparative Example 1 and Comparative Example 2) were formed, it was found that the spacers were superior in terms of variation in the height (thickness).
(Photosensitive material)
10 parts by weight of polymer (tricyclodecanyl methacrylate-methacrylic acid-styrene copolymer), 80 parts by weight of monomer (dipentaerythritol pentaacrylate), 10 parts by weight of photopolymerization initiator (Irgacure 907 manufactured by Ciba Specialty Chemicals) exposure)
Gap 100μm, 60mJ (High pressure mercury lamp, 365nm wavelength)
(developing)
Developer (potassium hydroxide solution), development time 50 seconds (PB (post-bake)) 230 ° C
The height was measured with a stylus-type measuring device (manufactured by KLA-Tencor Co., Ltd., model number P15).
In the measurement, a spacer is formed between each numbered pixel (115) shown in FIG. 3 and the adjacent pixel, and the position is indicated by the number.

The opening widths of the exposure masks used in the examples and the opening widths of the exposure masks used in the comparative examples are shown in Tables 1 and 2, respectively.

<Comparative example>
An exposure method is a method in which a spacer is formed by exposing and developing only once under the same exposure conditions as in the embodiment using an exposure mask having one opening width W for forming a spacer. The spacer is formed by the exposure method.
The procedure was the same as in the example except for the exposure conditions.
For reference, Reference Example 1 and Reference Example 2 are given.
Reference Example 1 and Reference Example 2 are the formation of spacers by the same conventional exposure method as Comparative Example 1 and Comparative Example 2, and the processing conditions are the same, but the opening width W is the same as Comparative Example 1 and Comparative Example 2. It was different.

Comparing FIG. 3A for Example 1 and FIG. 5A for Comparative Example 1, in the spacer formation method of the present invention, the spacer width is not changed, but the height (thickness) varies. It is clear that is improved.
Similarly, comparing FIG. 3B for Example 2 and FIG. 5B for Comparative Example 1, the spacer formation method of the present invention does not change the spacer width, but the height. It can be clearly seen that the variation in (thickness) is improved.
Further, when FIG. 5C for the reference example 1 and FIG. 5D for the reference example 2 are seen, the variation in the height (thickness) of the spacer is similar to the example, as in the comparative example 1. Compared with Comparative Example 2, it is superior to that of Example 1 and Example 2.
This is because, since the opening W at the time of exposure is larger than those of Comparative Examples 1 and 2, the exposure amount in the exposed area is substantially larger than that of Comparative Examples 1 and 2, and the photosensitive region is exposed to light. This is because the material layer is sufficiently cured.
However, in order to obtain such curing, in Comparative Example 1 and Comparative Example 2, when only the exposure amount is increased, the width (bottom width) of the spacer to be formed increases rapidly, and the target spacer The width cannot be obtained.
As described above, the conventional exposure method cannot substantially reduce the width (bottom width) of the formed spacer to a level of 12 μm or less, but also from the results of Examples 1 and 2. As can be seen, in the spacer forming method of the present invention, the width (bottom width) of the formed spacer can be made 12 μm or less.

It is process sectional drawing of one example of embodiment of the spacer formation method of this invention. FIG. 2A is a plan view of an example of an embodiment of the color filter substrate of the present invention in which spacers are formed by the spacer forming method shown in FIG. 1, and FIG. 2B is B1 in FIG. It is sectional drawing in position -B2. FIG. 3A is a diagram illustrating the variation degree of the height (thickness) of an example spacer in which the spacer is formed by the spacer forming method of the embodiment shown in FIG. 1, and FIG. It is the figure which illustrated the dispersion | variation degree of the height (thickness) of the spacer of another example which formed the spacer by the spacer formation method of embodiment shown in FIG. It is the figure which showed roughly the measurement position of the height (thickness) of a spacer. It is the figure which illustrated the variation degree of the height (thickness) of the spacer in the spacer formation method by the conventional exposure method. It is sectional drawing of one example of the liquid crystal display element using the color filter substrate of this invention.

Explanation of symbols

110 color filter forming substrate 110A color filter substrate 111 (with spacers formed) transparent substrate 112 black matrix 115 pixel portion 115a first color portion (red portion) region 115b second color portion (green portion) region 115c third Color part (blue part) region 116 Overcoat layer 120 Photosensitive material layer 121 Exposure region 122 by first exposure 122 Exposure region 123 by second exposure 125 Exposure region 125 by first exposure and second exposure 125 Spacer 130 Exposure mask 131 Light-shielding part 132 1st mask opening 133 2nd mask opening 140 Exposure light 150 Gap 1-26 Spacer position number 50 Color filter substrate 51 Transparent substrate 52 Black stripe 53a, 53b, 53c Colored layer 54 Overcoat layer 55 Transparent Electrode 58 Columnar spacer 59 For control It caused 61 LCD 62a, 62b alignment material 70 counter substrate 71 transparent substrate 72 transparent electrode 80 diffusion plate 81 backlight

Claims (8)

  A spacer forming method in which a spacer for controlling a gap between a color filter substrate and a counter substrate in a display device is formed on a color filter forming substrate from a negative photosensitive material layer by a photolithography method using a proximity exposure method. In the proximity exposure method, each spacer formation region is provided with a first exposure that is exposed through a first mask opening having a predetermined opening width provided in the exposure mask, and the or another exposure mask. In addition, a second mask opening having an opening width smaller than the predetermined opening width exposes an area inside the exposure area by the first exposure, and the second exposure is performed before and after, The exposure of 1 determines the width (bottom side width) of the spacer to be formed, and the second exposure does not affect the width of the spacer to be formed (bottom side width). In addition, the exposure amount in a region where the first exposure and the second exposure overlap is set as an exposure amount sufficient to cure the negative photosensitive material layer, and the height (thickness) of the spacer formed by the exposure amount. A method for forming a spacer, wherein:   The spacer forming method according to claim 1, wherein the first exposure and the second exposure are performed with the same exposure amount.   3. The spacer forming method according to claim 1, wherein the first mask opening and the second mask opening are provided in the same exposure mask, and the exposure mask is provided. The spacer formation method is characterized in that the first exposure and the second exposure are performed at predetermined positions by changing the relative positions of the exposure mask and the color filter substrate.   4. The spacer forming method according to claim 3, wherein the first mask opening and the second mask opening are alternately repeated on the exposure mask at a predetermined pitch in the X direction and / or the Y direction. A spacer forming method, wherein the spacers are arranged.   5. The spacer forming method according to claim 1, wherein the spacer has a fine width of 12 μm or less (base width).   The spacer forming method according to claim 1, wherein the color filter forming substrate is for a liquid crystal display device. A color filter substrate comprising a spacer formed by the spacer forming method according to claim 1. A spacer for controlling a gap between a color filter substrate and a counter substrate when used in a display device from a negative photosensitive material layer by a photolithography method using a proximity exposure method on the color filter substrate. In the forming method, the proximity exposure method includes a first exposure for exposing each spacer formation region by a first mask opening having a predetermined opening width provided in the exposure mask, and the above or another exposure method. A second mask opening provided in a mask with a second mask opening having an opening width smaller than the predetermined opening width exposes an area inside the exposure area by the first exposure, and is performed before and after the second exposure. An exposure mask used in the spacer forming method, wherein the first mask opening and the second mask opening are staggered at a predetermined pitch in the X direction and / or the Y direction. Exposure mask, wherein the return are arranged Ri.

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