JP2007156011A - Photosensitive resin composition for photo spacer, substrate with spacer, method for producing the same and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition for photo spacers capable of enhancing resist hardness after exposure, excellent in developer resistance, and capable of forming high-quality photo spacers free of defects such as a dot chip, and to provide a substrate with spacers using the composition, a method for producing the substrate and a liquid crystal display device. <P>SOLUTION: The photosensitive resin composition for photo spacers comprises at least an ethylenically unsaturated compound, a photopolymerization initiator and a binder and is used in an exposure system by which a two-dimensional image is formed by relatively scanning while modulating monochromatic light or a bright line within a range of 350-420 nm based on image data with two-dimensionally arranged spatial light modulation devices. The OD of the photosensitive resin composition at the wavelength of the monochromatic light or bright line is in a range of 0.05-1.2 and the binder contains a crosslinking group. There are also provided the substrate with spacers using the composition, the method for producing the substrate and the liquid crystal display device. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition for photospacers, a substrate with spacers, a method for producing the same, and a liquid crystal display device.

In recent years, liquid crystal displays (hereinafter referred to as LCDs as appropriate) used in various display devices are very compact and have significantly improved performance, and are replacing conventional CRT displays.
A color image in a liquid crystal display is formed by the light passing through the color filter being colored in the hue of each pixel of the color filter and combining the light of those colors.
In recent years, the development of technology for increasing the screen size and resolution of liquid crystal displays (LCDs) has progressed, and their applications are used not only for personal computer displays but also for television monitors. ing.
Improvements in display characteristics include higher pixel definition, improved display uniformity on the screen by correcting mask errors, higher contrast for faster display of the difference between bright and dark images, and faster response. In particular, reduction of the ITO resistance value is being studied.

In general, a liquid crystal display device is provided with a liquid crystal layer capable of displaying an image with a predetermined orientation between a pair of substrates, and maintaining the spacing between the substrates, that is, the thickness of the liquid crystal layer, determines the image quality. For this purpose, a spacer for keeping the thickness of the liquid crystal layer constant is provided. However, in order to improve the positional accuracy, the positional accuracy is improved by photolithography using a photosensitive resin composition. High spacers are being formed. A spacer formed using such a photosensitive resin composition is called a photo spacer.
The photosensitive resin composition used here is useful not only for the formation of spacers, but also partition walls for partitioning pixels of a liquid crystal cell, a black matrix, and further the pixels themselves.
As a method for producing a color filter using such a photosensitive resin composition, a fine pattern is generally formed by exposing the photosensitive resin composition to cure an exposed region and removing an unexposed portion by development. A photolithography method is known.

  Conventionally, a method of performing exposure through a mask pattern has been common, but in recent years, with the development of a laser irradiation apparatus, a laser beam such as a semiconductor laser or a gas laser is used as a pixel pattern, without using a photomask. A laser direct imaging system (hereinafter sometimes referred to as “LDI”) that performs patterning by scanning exposure on the surface of a photosensitive resin composition layer based on digital data such as a spacer pattern has attracted attention. Application to plate making is underway.

As an exposure apparatus using the LDI, light from the light irradiation means is received in accordance with a control signal by a light modulation means having n picture elements for receiving and emitting light from light irradiation means using laser light as a light source. A spatial light modulation element that modulates, an enlargement imaging optical system for enlarging an image of light modulated by the spatial light modulation element, and a spatial light modulation element disposed on an imaging surface of the enlargement imaging optical system An exposure apparatus comprising a microlens array having a microlens array corresponding to each pixel part, and an imaging optical system that forms an image of light that has passed through the microlens array on a pattern forming material or a screen Is known (see, for example, Non-Patent Document 1 and Patent Document 1).
LDI has the advantage that an expensive photomask is not required. However, as mentioned above, LCDs are required to improve significantly in terms of performance, and at the same time, productivity (tact, etc.) is also strictly demanded. To achieve these demands with LDI, (1) exposure It is necessary to take measures such as performing multiple exposures to eliminate unevenness due to (2) increasing the laser scanning speed to increase productivity.
When these countermeasures are performed on a conventionally known photosensitive resin composition, various problems such as rough pixel surfaces, pixel defects, and color unevenness occur due to insufficient sensitivity.

  Taking a photo spacer as an example, for a photo spacer prepared by patterning a conventionally known photosensitive resin composition by LDI, alkali development, and baking, the compressive strength of the spacer dot is weak. There is a tendency for plastic deformation to increase during formation. For high-quality image display, it is required that there is no problem that uniformity cannot be maintained or image unevenness is caused because the thickness of the liquid crystal layer becomes smaller than the design value. Moreover, it is also important that the alkali development residue of the photosensitive resin composition does not occur in terms of increasing the accuracy of the liquid crystal display device.

In recent years, a VA mode with a wide viewing angle has been proposed as a display mode of a liquid crystal display device (see, for example, Non-Patent Document 2). In the VA mode, a protrusion having a low dielectric constant called a rib is formed on one or both of a pair of upper and lower transparent electrodes, or both of the pair of upper and lower transparent electrodes are used by patterning (for example, see Non-Patent Document 3). A partial tilt is imparted to the electric field generated between the electrodes, whereby the orientation of the liquid crystal is made multi-domain, and a display device that can be observed with the same brightness from any angle is realized. Those using ribs are called MVA, ASV, CPA, etc., and those using both the upper and lower transparent electrodes by patterning are called PVA.
This VA mode is one of the display modes in which the variation in the cell thickness of the liquid crystal cell is likely to cause color unevenness, and there are some display modes that exhibit the same tendency in other display modes such as the IPS mode and the OCB mode.
In relation to the above, as a spacer forming technique for keeping the thickness (cell thickness) of the liquid crystal layer constant, it is disclosed to use a resin having an allyl group for forming the spacer (for example, Patent Document 1). The present situation is that there is still room for improvement in the ease of manufacturing such as uniformity and molding accuracy.
Japanese Patent Laid-Open No. 2004-1244 Akihito Ishikawa “Development shortening and mass production application by maskless exposure”, “Electrotronics Packaging Technology”, Technical Research Committee, Vol.18, No.6, 2002, p.74-79 "Nikkei Microdevices separate volume flat panel display 2003" business edition, pages 82-85, Nikkei BP "Nikkei Microdevices separate volume flat panel display 2003" business edition, page 103, Nikkei BP

In order to increase the sensitivity of the photosensitive resin composition for photospacers used in conventional LDI exposure, the OD at the exposure wavelength must be increased. When such a resin composition is subjected to LDI exposure, defects called dot defects frequently occur, making it difficult to produce a high-quality photospacer.
The present invention has been made in view of the above-mentioned conventional problems, can increase the resist hardness after exposure, has excellent developer resistance, and can form a high-quality photospacer free from defects such as missing dots. An object is to provide a photosensitive resin composition for a photospacer, a substrate with a spacer using the same, a method for producing the same, and a liquid crystal display device.

That is, the present invention
<1> Monochromatic light or bright line in the range of 350 nm to 420 nm based on image data using a spatial light modulation device that includes at least an ethylenically unsaturated compound, a photopolymerization initiator, and a binder and is arranged in two dimensions. Is a photosensitive resin composition for a photospacer used in an exposure method for forming a two-dimensional image by relative scanning while modulating the OD, and the OD at the wavelength of the monochromatic light or bright line is 0.05 to 1. A photosensitive resin composition for a photospacer, wherein the binder contains a crosslinkable group.

  <2> A step of forming a photosensitive layer containing the photosensitive resin composition for a photospacer according to <1> on a substrate, and a spatial light modulation device arranged in a two-dimensional manner, based on image data, from 350 nm to And a step of curing the photosensitive layer by performing relative scanning while modulating monochromatic light or bright lines within a range of 420 nm.

  <3> A substrate with spacers manufactured by the method for manufacturing a substrate with spacers according to <2>.

  <4> A liquid crystal display device comprising the substrate with a spacer according to <3>.

  According to the present invention, a photosensitive resin composition for a photospacer that can increase the resist hardness after exposure, has an excellent developer resistance, and can form a high-quality photospacer free from defects such as missing dots and the like. It is possible to provide a substrate with a spacer, a manufacturing method thereof, and a liquid crystal display device.

  Hereinafter, the photosensitive resin composition for photospacers of the present invention will be described in detail. In addition, a substrate with spacers using the photosensitive resin composition for photospacers and a method for producing the same will be described in detail, and details of the liquid crystal display device of the present invention will also be described.

  The photosensitive resin composition for photospacers of the present invention (hereinafter sometimes referred to as “the photosensitive resin composition of the present invention”) contains at least an ethylenically unsaturated compound, a photopolymerization initiator, and a binder, Used in an exposure system that forms a two-dimensional image by performing relative scanning while modulating monochromatic light or bright lines in the range of 350 nm to 420 nm based on image data using spatial light modulation devices arranged in two dimensions. A photosensitive resin composition for a photospacer, wherein an OD at a wavelength of the monochromatic light or bright line is in a range of 0.05 to 1.2, and the binder contains a crosslinkable group. .

  In the photosensitive resin composition of the present invention, the photopolymerization initiator is decomposed by exposure to generate an initiating species, and the polymerization of the coexisting ethylenically unsaturated compound proceeds and the exposed region is cured. By using this characteristic, it is possible to form a high-definition pattern according to the exposure conditions. Furthermore, since the binder which concerns on the photosensitive resin composition of this invention contains a crosslinkable group, the crosslinking rate of the photosensitive resin composition (hardened | cured material) after exposure can be raised. As a result, it is possible to form a high-quality photospacer free from dot defects after development even in a high-sensitivity resist having a high OD at the exposure wavelength.

  Since the photosensitive resin composition of the present invention is cured by exposing monochromatic light or bright lines in the range of 350 nm to 420 nm, it preferably contains a hexaarylbiimidazole compound as a photopolymerization initiator. In addition, when this photopolymerization initiator is allowed to coexist with a spectral sensitizer as necessary, it is possible to efficiently decompose the photopolymerization initiator and generate active species such as radicals. Furthermore, if a photo-initiator is allowed to coexist with a hydrogen donor as necessary, radicals generated by the function of the hydrogen donor can be efficiently converted into a curing reaction, thus achieving further higher sensitivity. can do.

  The OD of the photosensitive resin composition of the present invention at the wavelength of the monochromatic light or bright line is 0.05 to 1.2. If the OD is less than 0.05, the sensitivity is lowered and cannot be sufficiently hardened by exposure. If the OD is greater than 1.2, the OD is too high so that the light at the time of exposure is below the photospacer (away from the light source). May not reach the substrate side) and curing may be insufficient, and the photo spacer shape may not be an ideal shape. The OD at the wavelength of the monochromatic light or bright line is preferably 0.07 to 1.1, and most preferably 0.1 to 1.0. Note that when a light source having two or more bright lines at 350 nm to 420 nm is used, it is sufficient that the OD satisfies the above range at at least one wavelength of the bright lines.

In this invention, OD means OD measured in the thickness when the photosensitive layer containing the photosensitive resin composition of this invention is formed as a photospacer. The transmission optical density (OD) in the present invention is determined by measuring a substrate concentration D ⁰ using a spectrophotometer, and then forming a photosensitive layer containing the photosensitive resin composition of the present invention on the substrate. of the total concentration D ¹ of the concentration and the concentration of the substrate was measured, it can be determined from the difference of the obtained concentration (D 1 ^{-D 0).}
In order to set the transmission optical density (OD) at the light source wavelength within the above range, (1) adjusting the concentration of the photopolymerization initiator, (2) selecting the type of the photopolymerization initiator as desired, etc. It is effective.

(Photopolymerization initiator)
The photosensitive resin composition of the present invention preferably contains a hexaarylbiimidazole compound as a photopolymerization initiator, and examples of such a compound include compounds represented by the following formula (I). it can.

(In the general formula (I), R ^{1 to} R ¹⁵ each independently represents a hydrogen atom or a monovalent substituent)

More specific examples of R ^{1 to} R ¹⁵ in the general formula (I) include a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a phenyl group, a phenoxy group, a benzyl group, a hydroxyl group, an amino group, and a carboxyl group. Among them, a hydroxyl group, a halogen atom, an alkyl group, and an alkoxy group are preferable.

  Specific examples of the compound represented by the general formula (I) include, for example, a triarylimidazole dimer described in US Pat. No. 3,549,367, 2,2′-bis (o-chlorophenyl)- 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (p-carboethoxyphenyl) biimidazole, 2, 2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (p-bromophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5 '-Tetra (o, p-dichlorophenyl) biimidazole can be mentioned, among which 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole is preferred. Messenger It is.

  The photosensitive resin composition of the present invention can be used in combination with a photopolymerization initiator having sensitivity to exposure at the above wavelength other than the hexaarylbiimidazole compound within a range not impairing the effect. Examples of photopolymerization initiators that can be used in combination include aromatic ketones, vicinal polyketaldonyl compounds disclosed in US Pat. No. 2,367,660, and acyloin ether compounds described in US Pat. No. 2,448,828. An aromatic acyloin compound substituted with an α-hydrocarbon described in US Pat. No. 2,722,512, a polynuclear quinone compound described in US Pat. Nos. 3,046,127 and 2,951,758, Japanese Patent Publication No. 51-48516 Benzothiazole compounds and trihalomethyl-s-triazine compounds described in US Pat. No. 4,239,850, trihalomethyl-s-triazine compounds described in US Pat. No. 4,239,850, and trihalo described in US Pat. No. 4,221,976 And methyl oxadiazole compounds.

  Preferred examples of the aromatic ketone include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone and 2-carboxy. Benzophenone, 2-ethoxycarbonylbenzolphenone, benzophenone tetracarboxylic acid or tetramethyl ester thereof, 4-methoxy-4′-dimethylaminobenzophenone, 4,4′-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone , Anthraquinone, 2-tert-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chlorothioxa , 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, fluorene, acridone and benzoin, benzoin ethers (eg, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyldimethyl) Ketal), 4,4′-bis (dialkylamino) benzophenones (eg, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) Benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone). A particularly preferred example is benzophenone.

The content of the photopolymerization initiator in the photosensitive resin composition (when containing a plurality of types, the total amount) is generally 0.1 to 10% by mass in terms of solid content, and 0.5 to 5% by mass. % Is preferred.
In addition, about the ratio of content of a hexaarylbiimidazole-type compound and other photoinitiators, a hexaarylbiimidazole-type compound shall make 20-80 mass% with respect to content of all the photoinitiators. It is preferable that it is 30-70 mass% especially.

[Spectral sensitizer]
The photosensitive resin composition of the present invention may contain a spectral sensitizer suitable for light in the range of 350 nm to 420 nm for the purpose of improving the sensitivity of the photopolymerization initiator.
The spectral sensitizer is not particularly limited as long as it has sensitivity in the above-mentioned wavelength range, but is preferably one or more selected from compounds represented by the following general formula (II).

(In general formula (II), A represents an oxygen atom, a sulfur atom or NR ¹⁰ , and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^10. Each independently represents a hydrogen atom or a monovalent substituent.)
Of these, compounds represented by the following formula (III) are preferred.

(In General Formula (III), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent a hydrogen atom or a monovalent substituent. .)

In the general formulas (II) and (III), the monovalent substituent represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ is an alkyl group (for example, Methyl group, ethyl group, propyl group, butyl group, hydroxyethyl group, trifluoromethyl group, benzyl group, sulfopropyl group, diethylaminoethyl group, cyanopropyl group, adamantyl group, p-chlorophenethyl group, ethoxyethyl group, Ethylthioethyl group, phenoxyethyl group, carbamoylethyl group, carboxyethyl group, ethoxycarbonylmethyl group, acetylaminoethyl group, etc.), alkenyl group (eg, allyl group, styryl group, etc.), aryl group (eg, phenyl group, Naphthyl group, p-carboxyphenyl group, 3,5-dicarboxyphenyl group, m-sulfophenyl Group, p-acetamidophenyl group, 3-caprylamidophenyl group, p-sulfamoylphenyl group, m-hydroxyphenyl group, p-nitrophenyl group, 3,5-dichlorophenyl group, p-anisyl group, o-anisyl Group, p-cyanophenyl group, p-N-methylureidophenyl group, m-fluorophenyl group, p-tolyl group, m-tolyl group, etc.), heterocyclic group (for example, pyridyl group, 5-methyl-2- Pyridyl group, thienyl group, etc.), halogen atom (eg, chlorine atom, bromine atom, fluorine atom, etc.), mercapto group, cyano group, carboxyl group, sulfo group, hydroxy group, carbamoyl group, sulfamoyl group, nitro group, alkoxy group (For example, methoxy group, ethoxy group, 2-methoxyethoxy group, 2-phenylethoxy group, etc.), aryloxy (Eg, phenoxy group, p-methylphenoxy group, p-chlorophenoxy group, α-naphthoxy group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), acylamino group (eg, acetylamino group, caproylamino) Group), sulfonyl group (eg, methanesulfonyl group, benzenesulfonyl group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), amino group (eg, diethylamino group, hydroxyamino group, etc.) , Alkylthio group or arylthio group (for example, methylthio group, carboxyethylthio group, sulfobutylthio group, phenylthio group, etc.), alkoxycarbonyl group (for example, methoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group, etc.) Etc. It is.

These may further have a substituent. Examples of the substituent that can be introduced into the monovalent substituent represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ include an alkyl group (for example, a methyl group) , Ethyl group, propyl group, butyl group, hydroxyethyl group, trifluoromethyl group, benzyl group, sulfopropyl group, diethylaminoethyl group, cyanopropyl group, adamantyl group, p-chlorophenethyl group, ethoxyethyl group, ethylthioethyl Group, phenoxyethyl group, carbamoylethyl group, carboxyethyl group, ethoxycarbonylmethyl group, acetylaminoethyl group, etc.), alkenyl group (for example, allyl group, styryl group, etc.), aryl group (for example, phenyl group, naphthyl group, p-carboxyphenyl group, 3,5-dicarboxyphenyl group, m-sulfophenyl group, p-aceto Midphenyl group, 3-caprylamidophenyl group, p-sulfamoylphenyl group, m-hydroxyphenyl group, p-nitrophenyl group, 3,5-dichlorophenyl group, p-anisyl group, o-anisyl group, p-cyano Phenyl group, pN-methylureidophenyl group, m-fluorophenyl group, p-tolyl group, m-tolyl group, etc.), heterocyclic group (for example, pyridyl group, 5-methyl-2-pyridyl group, thienyl group) Etc.), halogen atoms (eg chlorine atom, bromine atom, fluorine atom etc.), mercapto group, cyano group, carboxyl group, sulfo group, hydroxy group, carbamoyl group, sulfamoyl group, nitro group, alkoxy group (eg methoxy group) Ethoxy group, 2-methoxyethoxy group, 2-phenylethoxy group, etc.), aryloxy group (for example, phenoxy group) Xyl group, p-methylphenoxy group, p-chlorophenoxy group, α-naphthoxy group, etc.), acyl group (eg, acetyl group, benzoyl group, etc.), acylamino group (eg, acetylamino group, caproylamino group, etc.) Sulfonyl group (eg methanesulfonyl group, benzenesulfonyl group etc.), sulfonylamino group (eg methanesulfonylamino group, benzenesulfonylamino group etc.), amino group (eg diethylamino group, hydroxyamino group etc.), alkylthio group Or an arylthio group (for example, methylthio group, carboxyethylthio group, sulfobutylthio group, phenylthio group, etc.), an alkoxycarbonyl group (for example, methoxycarbonyl group), an aryloxycarbonyl group (for example, phenoxycarbonyl group, etc.), etc. It is done.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are connected to each other by a saturated straight chain, a saturated branched chain, an unsaturated straight chain, an unsaturated branched chain, or the like. May form a ring structure, and they may further have the above substituents.

As the monovalent substituent represented by R ⁹ , an alkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group, an acyl group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, and an aryloxycarbonyl group are preferable. Particularly preferred are groups, aryl groups, alkenyl groups, and acyl groups. Among these, an alkyl group is preferable, and the number of carbon atoms of the alkyl group is preferably 1 to 12, and more preferably 1 to 6.
These may further have a substituent, and examples of the substituent that can be introduced into the monovalent substituent represented by R ⁹ include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group). , Hydroxyethyl group, trifluoromethyl group, benzyl group, sulfopropyl group, diethylaminoethyl group, cyanopropyl group, adamantyl group, p-chlorophenethyl group, ethoxyethyl group, ethylthioethyl group, phenoxyethyl group, carbamoylethyl group Carboxyethyl group, ethoxycarbonylmethyl group, acetylaminoethyl group, etc.), alkenyl group (eg, allyl group, styryl group, etc.), aryl group (eg, phenyl group, naphthyl group, p-carboxyphenyl group, 3, 5 -Dicarboxyphenyl group, m-sulfophenyl group, p-acetamidophenyl group 3-caprylamidophenyl group, p-sulfamoylphenyl group, m-hydroxyphenyl group, p-nitrophenyl group, 3,5-dichlorophenyl group, p-anisyl group, o-anisyl group, p-cyanophenyl group P-N-methylureidophenyl group, m-fluorophenyl group, p-tolyl group, m-tolyl group, etc.), heterocyclic group (for example, pyridyl group, 5-methyl-2-pyridyl group, thienyl group, etc.) , Halogen atoms (eg, chlorine atoms, bromine atoms, fluorine atoms), mercapto groups, cyano groups, carboxyl groups, sulfo groups, hydroxy groups, carbamoyl groups, sulfamoyl groups, nitro groups, alkoxy groups (eg, methoxy groups, ethoxy groups) Group, 2-methoxyethoxy group, 2-phenylethoxy group, etc.), aryloxy group (for example, phenoxy group, p-methyl group). Ruphenoxy group, p-chlorophenoxy group, α-naphthoxy group etc.), acyl group (eg acetyl group, benzoyl group etc.), acylamino group (eg acetylamino group, caproylamino group etc.), sulfonyl group (eg Methanesulfonyl group, benzenesulfonyl group, etc.), sulfonylamino group (eg, methanesulfonylamino group, benzenesulfonylamino group, etc.), amino group (eg, diethylamino group, hydroxyamino group, etc.), alkylthio group or arylthio group (eg, Methylthio group, carboxyethylthio group, sulfobutylthio group, phenylthio group and the like), alkoxycarbonyl group (for example, methoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group and the like), and the like. R ⁹ is R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ together with saturated straight chain, saturated branched chain, unsaturated straight chain, unsaturated branched chain, etc. They may be linked to form a ring structure, and they may further have the above substituents.

The monovalent substituent represented by R ¹⁰ is preferably an alkyl group, aryl group, alkenyl group, alkoxy group, aryloxy group, acyl group, alkylthio group, arylthio group, alkoxycarbonyl group, or aryloxycarbonyl group. Group, alkoxy group, aryloxy group, acyl group, alkylthio group and alkoxycarbonyl group are particularly preferred.
These may further have a substituent, and examples of the substituent that can be introduced into the monovalent substituent represented by R ¹⁰ include an alkyl group (for example, a methyl group, an ethyl group, a propyl group, a butyl group). , Hydroxyethyl group, trifluoromethyl group, benzyl group, sulfopropyl group, diethylaminoethyl group, cyanopropyl group, adamantyl group, p-chlorophenethyl group, ethoxyethyl group, ethylthioethyl group, phenoxyethyl group, carbamoylethyl group Carboxyethyl group, ethoxycarbonylmethyl group, acetylaminoethyl group, etc.), alkenyl group (eg, allyl group, styryl group, etc.), aryl group (eg, phenyl group, naphthyl group, p-carboxyphenyl group, 3, 5 -Dicarboxyphenyl group, m-sulfophenyl group, p-acetamidophenyl Group, 3-caprylamidophenyl group, p-sulfamoylphenyl group, m-hydroxyphenyl group, p-nitrophenyl group, 3,5-dichlorophenyl group, p-anisyl group, o-anisyl group, p-cyanophenyl Group, p-N-methylureidophenyl group, m-fluorophenyl group, p-tolyl group, m-tolyl group, etc.), heterocyclic group (for example, pyridyl group, 5-methyl-2-pyridyl group, thienyl group, etc.) ),

Halogen atom (for example, chlorine atom, bromine atom, fluorine atom, etc.), mercapto group, cyano group, carboxyl group, sulfo group, hydroxy group, carbamoyl group, sulfamoyl group, nitro group, alkoxy group (for example, methoxy group, ethoxy group) , 2-methoxyethoxy group, 2-phenylethoxy group, etc.), aryloxy group (for example, phenoxy group, p-methylphenoxy group, p-chlorophenoxy group, α-naphthoxy group, etc.), acyl group (for example, acetyl group, Benzoyl group etc.), acylamino group (eg acetylamino group, caproylamino group etc.), sulfonyl group (eg methanesulfonyl group, benzenesulfonyl group etc.), sulfonylamino group (eg methanesulfonylamino group, benzenesulfonylamino) Group), amino group (for example, diethyl) Mino group, hydroxyamino group etc.), alkylthio group or arylthio group (eg methylthio group, carboxyethylthio group, sulfobutylthio group, phenylthio group etc.), alkoxycarbonyl group (eg methoxycarbonyl group), aryloxycarbonyl group (For example, a phenoxycarbonyl group etc.) etc. are mentioned. R ¹⁰ is R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , and R ⁹ and saturated linear, saturated branched, unsaturated linear, unsaturated branched They may be linked by a chain or the like to form a ring structure, and they may further have the above substituents.

  Specific examples of the spectral sensitizers represented by the general formulas (II) and (III) preferably used in the present invention are shown below, but the present invention is not limited thereto.

  Specific examples of preferable spectral sensitizers other than the compounds represented by the general formulas (II) and (III) include the following compounds.

  The content of the spectral sensitizer in the photosensitive resin composition is preferably 0.5 to 3.0% by mass and more preferably 1.0 to 2.0% by mass in terms of solid content. preferable.

[Hydrogen donor]
The hydrogen donor used in the present invention is not particularly limited as long as it is a compound that can donate a hydrogen atom to a radical generated by the decomposition of the photopolymerization initiator, and a compound having an acidic proton is generally used. . Such a compound has a function as a chain transfer agent and is known to be useful for promoting radical polymerization. A known compound having this function can be used as a hydrogen donor in the present invention. Examples thereof include amine compounds and mercapto compounds, and among these, compounds having a mercapto group are preferably used.

As a compound having a mercapto group, in addition to a compound having 1 functional group having one mercapto group in the molecule, a compound having 2 to 4 mercapto groups in the molecule can also be used.
(Mercapto compound with 1 functional group)
Examples of the mercapto compound having 1 functional group include compounds represented by the following general formula (IV-1).

In the general formula (IV-1), R ²⁵ represents an alkyl group or an aryl group, and R ²⁶ represents a hydrogen atom or an alkyl group.
The alkyl groups which may R ^{25, R 26} represents an alkyl group, preferably from 1 to 4 carbon atoms. In addition, when R ²⁵ represents an aryl group, the aryl group preferably has 6 to 10 carbon atoms such as a phenyl group or a naphthyl group, and the substituted aryl group includes an aryl group as described above and a chlorine atom. And those substituted with an alkoxy group such as a halogen atom, an alkyl group such as a methyl group, a methoxy group, or an ethoxy group. R ²⁵ and R ²⁶ may be bonded to each other to form an atomic group necessary for completing a heterocyclic ring which may have a condensed ring together with a carbon atom and a nitrogen atom. In this case, examples of the condensed ring include a benzene ring.

Specific examples of the mercapto compound represented by the general formula (IV-1) include the following [(e-1) to (e-73)].
e-1. Thioformamide,
e-2. Thioacetamide,
e-3. N-methylthioformamide,
e-4. N-methylthioacetamide,
e-5. N-phenylthiopropionic acid amide,
e-6. N-phenylthiocaproic acid amide,
e-7. N-o-chloro-phenylthioacetamide,
e-8. N-o-chlorophenylthiocaproic acid amide,
e-9. Np-tolylthiocaproic acid amide,
e-10. Nm-methoxyphenylthioacetamide,
e-11. Nm-methoxyphenyl thiopropionic acid amide,
e-12. Np-ethoxyphenylthioacetamide,
e-13. Np-ethoxyphenylthiopropionic acid amide,
e-14. N-o-methoxyphenylthiocaproic acid amide,
e-15.2-mercapto-4,5-dihydro-2-thiazole,
e-16.2-Mercapto-4-methyl-4,5-dihydro-2-thiazole,
e-17.2-mercapto-5-methyl-4,5-dihydro-2-thiazole,
e-18.2-mercapto-4,4-dimethyl-4,5-dihydro-2-thiazole,
e-19.2-mercapto-5,5-dimethyl-4,5-dihydro-2-thiazole,
e-20.2-mercapto-4,5-dihydro-2-oxazole,
e-21.2-mercapto-4-methyl-4,5-dihydro-2-oxazole,
e-22.2-mercapto-4,4-dimethyl-4,5-dihydro-2-oxazole,
e-23.1-methyl-2-mercapto-1,3-imidazole,
e-24.2 2-mercapto-4,5-dihydro-1,3-thiazine,
e-25.2-mercapto-6-methyl-4,5-dihydro-1,3-thiazine,

e-26.2-mercapto-4,5-dihydro-1,3-oxazine,
e-27.2-mercapto-tetrahydro-1-pyridine,
e-28.1- [p- (n-hexylaminocarbonyl) phenyl} -2-mercaptoimidazole,
e-29.1- (p-tolyl) -2-mercapto-4,5,6,7-tetrahydro-1,3-benzimidazole,
e-30.2-mercapto-5-methylthio-1,3,4-oxadiazole,
e-31.2-mercapto-3,4,5,6-tetrahydro-1-azepine,
e-32.2-mercapto-1,3-benzoxazole,
e-33.3-mercapto-5-chloro-1,2-benzisoxazole,
e-34.2, 2-mercapto-1,3-benzimidazole,
e-35.2-mercapto-6-methoxy-1,3-benzimidazole,
e-36.1-Methyl-2-mercapto-1,3-benzimidazole,
e-37.2-Mercapto-6-methyl-1,3-benzimidazole,
e-38.2-mercapto-5,6-dimethyl-1,3-benzimidazole,
e-39.2-mercapto-6-methoxy-1,3-benzimidazole,
e-40.2-mercapto-5-caproylamino-1,3-benzimidazole,
e-41.1- (n-propyl) -2-mercapto-1,3-benzimidazole,
e-42.1-Isopropyl-2-mercapto-1,3-benzimidazole,
e-43.2-mercapto-6-chloro-1,3-benzimidazole,
e-44.1- (n-heptyl) -2-mercapto-1,3-benzimidazole,
e-45.1- (n-hexyl) -2-mercapto-5-chloro-1,3-benzimidazole,
e-46.2-mercapto-6-chloro-1,3-benzimidazole,
e-47.1- (n-octyl) -2-mercapto-5-methoxy-1,3-benzimidazole,
e-48.1- (n-hexyl) -2-mercapto-5-ethoxycarbonyl-1,3-benzimidazole,
e-49.1- (2-methoxyethyl) -2-mercapto-1,3-benzimidazole,
e-50.3-mercapto-6-methyl-1,2-benzothiazole,

e-51.1-phenyl-2-mercapto-1,3-benzimidazole,
e-52.1-phenyl-2-mercapto-5-methylsulfonyl-1,3-benzimidazole,
e-53.1- (p-sulfonatomethylphenyl) -2-mercapto-1,3-benzimidazole sodium salt,
e-54.3-mercapto-1,2-benzothiazole,
e-55.3-mercapto-6-caproylamino-1,2-benzothiazole,
e-56.3-mercapto-6-chloro-1,2-benzothiazole,
e-57.3-mercapto-6-methyl-1,2-benzothiazole,
e-58.2-mercapto-naphtho [2,1] -1,3-imidazole,
e-59.1- (n-butyl) -2-mercapto-naphtho [2,1] -1,3-imidazole,
e-60.1- (n-octyl) -2-mercapto-imidazo [4,5-b] pyridine,
e-61.1- (n-octyl) -2-mercapto-imidazo [4,5-b] pyrazine,
e-62.1- (n-butyl) -2-mercapto-1,3-imidazo [4,5-b] quinoxaline,
e-63.1- (n-hexyl) -2-mercapto-6-chloro-1,3-imidazo [4,5-b] quinoxaline,
e-64.1,5-diethyl-3-mercapto-1,2,4-triazole,
e-65.4- (n-hexyl) -3-mercapto-1,2,4-triazole,
e-66.4-phenyl-3-mercapto-1,2,4-triazole,
e-67.4-Phenyl-3-mercapto-5-methylthio-1,2,4-triazole,
e-68.1- (n-hexyl) -5-mercaptotetrazole,
e-69.1- (n-octyl) -5-mercaptotetrazole,
e-70.1-phenyl-5-mercaptotetrazole,
e-71.2- (n-hexyl) -3-mercapto-1,2,4-oxadiazine,
e-72.2-phenyl-3-mercapto-5-methyl-1,2,4-thiadiazine,
e-73.3-Phenyl-4-mercapto-6-phenyl-1,2,3,6-tetrahydro-1,3,5-thiadiazine.
Among these, e-51.1-phenyl-2-mercapto-1,3-benzimidazole can be preferably used.

(Mercapto compound with 2 functional groups)
Examples of the hydrogen donor having two mercapto groups in one molecule include 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5- Pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 2,3-dimercapto-1-propanol, dithioerythritol, 2,3-dimercaptosuccinic acid, 1,2- Benzenedithiol, 1,2-benzenedimethanethiol, 1,3-benzenedithiol, 1,3-benzenedimethanethiol, 1,4-benzenedimethanethiol, 3,4-dimercaptotoluene, 4-chloro-1 , 3-benzenedithiol, 2,4,6-trimethyl-1,3-benzenedimethanethiol, 4,4 ′ -Thiodiphenol, 2-hexylamino-4,6-dimercapto-1,3,5-triazine, 2-diethylamino-4,6-dimercapto-1,3,5-triazine, 2-cyclohexylamino-4,6 Dimercapto-1,3,5-triazine, 2-di-n-butylamino-4,6-dimercapto-1,3,5-triazine, ethylene glycol bis (3-mercaptopropionate), butanediol bismercapto Acetate, ethylene glycol bismercaptoacetate, 2,5-dimercapto-1,3,4-thiadiazole, 2,2 '-(ethylenedithio) diethanethiol, 2,2-bis (2-hydroxy-3-mercaptopropoxyphenyl) Propane), 1,4-butanediol bis (3-mercaptobutyrate), and Includes compounds represented by the following structural formulas (a) to (d).

(Mercapto compound with 3 functional groups)
Examples of the hydrogen donor having three mercapto groups in one molecule include 1,2,6-hexanetriol trithioglycolate, 1,3,5-trithiocyanuric acid, 2,4,6-trimercapto-1 , 3,5-triazine, trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane trismercaptoacetate, and the like.

(Mercapto compounds with 4 or more functional groups)
Examples of the compound having four or more mercapto groups in one molecule include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakismercaptoacetate, dipentaerythritol hexakis (3-mercaptopropionate), And dipentaerythritol hexakis mercaptoacetate.

These hydrogen donors may be used alone or in combination of two or more.
The content of the hydrogen donor in the photosensitive resin composition is preferably 0.05 to 5.0% by mass, more preferably 0.1 to 2.0% by mass in terms of solid content. .

〔binder〕
The binder contained in the photosensitive resin composition functions as a film-forming substance when a photosensitive layer containing the photosensitive resin composition is formed on the substrate surface, and a resin capable of alkali development can be used. From the viewpoint of curing sensitivity, it is essential that the polymer compound used as the binder has a crosslinkable group (also referred to as a polymerizable group).

-Definition of crosslinkable group-
The term “containing a crosslinkable group” in the present invention means that the side chain of the binder polymer has a group capable of forming a bond with a surrounding binder or an ethylenically unsaturated compound by some chemical reaction. There is no particular limitation as long as it has a function.

  As described above, the polymer compound constituting the binder itself has a crosslinkable group. The polymer compound may be any one of a monomer homopolymer and a copolymer composed of a plurality of monomers appropriately selected according to the purpose, etc., and a structural unit having a carboxyl group, A copolymer having at least a structural unit represented by the general formula (1) and a structural unit composed of (meth) acrylate having at least one aromatic ring and / or aliphatic ring is preferable.

  This copolymer includes, for example, a polymerizable monomer having a carboxyl group, a monomer represented by the following formula (2), a (meth) acrylate having one or more aromatic rings and / or aliphatic rings, and as necessary. It can be obtained by copolymerizing other monomers copolymerizable with these by a known method.

In the general formulas (1) and (2), R ¹ represents a hydrogen atom or a methyl group, and R ^{2 to} R ⁶ each independently represent a hydrogen atom or an alkyl group which may have a substituent, An aryl group, a halogen atom, or a cyano group is represented.

  Examples of the polymerizable monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. An addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride or phthalic anhydride can also be used. An anhydride monomer such as maleic anhydride or itaconic anhydride can also be used as a precursor of carboxylic acid. Among these, (meth) acrylic acid is particularly preferable from the viewpoint of polymerizability and raw material price.

  Examples of the monomer represented by the formula (2) include allyl (meth) acrylate, 3-chloro-2-propenyl (meth) acrylate, 3-phenyl-2-propenyl (meth) acrylate, and 3- (hydroxyphenyl). ) -2-propenyl (meth) acrylate, 3- (2-hydroxyphenyl) -2-propenyl (meth) acrylate, 3- (3,4-dihydroxyphenyl) -2-propenyl (meth) acrylate, 3- (2 , 4-Dihydroxyphenyl) -2-propenyl (meth) acrylate, 3- (3,4,5-trihydroxyphenyl) -2-propenyl (meth) acrylate, 3- (3-methoxy-4-hydroxyphenyl)- 2-propenyl (meth) acrylate, 3- (3,4-dihydroxy-5-methoxyphenyl) 2-propenyl (meth) acrylate, 3- (3,5-dimethoxy-4-hydroxyphenyl) -2-propenyl (meth) acrylate, 3- (2-hydroxy-4-methylphenyl) -2-propenyl (meth) Acrylate, 3- (4-methoxyphenyl) -2-propenyl (meth) acrylate, 3- (4-ethoxyphenyl) -2-propenyl (meth) acrylate, 3- (2-methoxyphenyl) -2-propenyl (meth) ) Acrylate, 3- (3,4-dimethoxyphenyl) -2-propenyl (meth) acrylate, 3- (3-methoxy-4-propoxyphenyl) -2-propenyl (meth) acrylate, 3- (2,4, 6-trimethoxyphenyl) -2-propenyl (meth) acrylate, 3- (3-methoxy-4-benzi Oxyphenyl) -2-propenyl (meth) acrylate, 3- (3- (3′-methoxyphenyl) -4-benzyloxyphenyl) -2-propenyl (meth) acrylate, 3- (3,4,5-tri Methoxyphenyl) -2-propenyl (meth) acrylate, 3- (4-methylphenyl) -2-propenyl (meth) acrylate;

3-phenyl-3- (2,4,6-trimethylphenyl) -2-propenyl (meth) acrylate, 3,3- [di- (2,4,6-trimethylphenyl)]-2-propenyl (meth) Acrylate, 3-phenyl-3- (4-methylphenyl) -2-propenyl (meth) acrylate, 3,3-diphenyl-2-propenyl (meth) acrylate, 3- (2-chlorophenyl) -2-propenyl ( (Meth) acrylate, 3- (3-chlorophenyl) -2-propenyl (meth) acrylate, 3- (4-chlorophenyl) -2-propenyl (meth) acrylate, 3- (2,4-dichlorophenyl)- 2-propenyl (meth) acrylate, 3- (2-bromophenyl) -2-propenyl (meth) acrylate, 3-bromo-3-phenyl-2 Propenyl (meth) acrylate, 3-chloro-3-phenyl-2-propenyl (meth) acrylate, 3- (4-nitrophenyl) -2-propenyl (meth) acrylate, 3- (2-nitrophenyl) -2- Propenyl (meth) acrylate, 3- (3-nitrophenyl) -2-propenyl (meth) acrylate, 2-methyl-3-phenyl-2-propenyl (meth) acrylate, 2-methyl-3- (4-chlorophenyl) ) -2-propenyl (meth) acrylate,

2-methyl-3- (4-nitrophenyl) -2-propenyl (meth) acrylate, 2-methyl-3- (4-aminophenyl) -2-propenyl (meth) acrylate, 2-methyl-3,3- Diphenyl-2-propenyl (meth) acrylate, 2-ethyl-1,3-diphenyl-2-propenyl (meth) acrylate, 2-ethoxymethylene-3-phenyl-2-propenyl (meth) acrylate, 2-methyl-3 -(4-methoxyphenyl) -2-propenyl (meth) acrylate, 2,3-diphenyl-2-propenyl (meth) acrylate, 1,2,3-triphenyl-2-propenyl (meth) acrylate, 2,3 , 3-Triphenyl-2-propenyl (meth) acrylate, 1,3-diphenyl-2-propenyl (meth) acrylate 1- (4-methylphenyl) -3-phenyl-2-propenyl (meth) acrylate, 1-phenyl-3- (4-methylphenyl) -2-propenyl (meth) acrylate, 1-phenyl-3 -(4-methoxyphenyl) -2-propenyl (meth) acrylate, 1- (4-methoxyphenyl) -3-phenyl-2-propenyl (meth) acrylate, 1,3-di (4-chlorophenyl) -2 -Propenyl (meth) acrylate, 1- (4-bromophenyl) -3-phenyl-2-propenyl (meth) acrylate;

1-phenyl-3- (4-nitrophenyl) -2-propenyl (meth) acrylate, 1,3-di (2-nitrophenyl) -2-propenyl (meth) acrylate, 1- (4-dimethylaminophenyl) -3-phenyl-2-propenyl (meth) acrylate, 1-phenyl-3- (4-dimethylaminophenyl) -2-propenyl (meth) acrylate, 1,1-di (4-dimethylaminophenyl) -3- Phenyl-2-propenyl (meth) acrylate, 1,1,3-triphenyl-2-propenyl (meth) acrylate, 1,1,3,3-tetraphenyl-2-propenyl (meth) acrylate, 1- (4 -Methylphenyl) -3-phenyl-2-propenyl (meth) acrylate, 1-phenyl-2-propenyl (meth) acrylate 1,2-diphenyl-2-propenyl (meth) acrylate, 1-phenyl-2-methyl-2-propenyl (meth) acrylate, 1-cyclohexyl-2-propenyl (meth) acrylate, 2-benzyl-2-propenyl (Meth) acrylate, 1,1-di (4-chlorophenyl) -2-propenyl (meth) acrylate, 1-cyano-2-propenyl (meth) acrylate, 3-anilino-2-propenyl (meth) acrylate, 3 -(2-methylphenyl) -2-propenyl (meth) acrylate, 3- (2,4-dimethylphenyl) -2-propenyl (meth) acrylate, 1- (2-carbethoxyisopropyl) -3-methyl-2 -Propenyl (meth) acrylate, 1- (1-carbethoxyisopropyl) -2-propenyl (Meth) acrylate, 1- (1-carbethoxyethyl) -3-methyl-2-propenyl (meth) acrylate, 1-carbethoxy-3-chloro-3-methyl-2-propenyl (meth) acrylate, 1-carb Toximethylene-3-methyl-2-propenyl (meth) acrylate, 1-cyano-3-methyl-2-propenyl (meth) acrylate, 1-cyclohexyl-3- (2-hydroxycyclohexyl) -2-propenyl ( (Meth) acrylate, 3-cyclopentyl-2-propenyl (meth) acrylate;

3-furyl-2-propenyl (meth) acrylate, 3-chloro-2-propenyl (meth) acrylate, 3-bromo-2-propenyl (meth) acrylate, 2-methyl-3-chloro-2-propenyl (meth) Acrylate, 2-methyl-3-bromo-2-propenyl (meth) acrylate, 2-chloro-3-phenyl-2-propenyl (meth) acrylate, 2-bromo-3-phenyl-2-propenyl (meth) acrylate, 2-bromo-3- (4-nitrophenyl) -2-propenyl (meth) acrylate, 2-fluoro-3-phenyl-2-propenyl (meth) acrylate, 2-fluoro-3- (4-methoxyphenyl)- 2-propenyl (meth) acrylate, 2-cyano-3-phenyl-2-propenyl (meth) acrylate 2-chloro-2-propenyl (meth) acrylate, 2-bromo-2-propenyl (meth) acrylate, 2-chloro-3,3-difluoro-2-propenyl (meth) acrylate, 2-fluoro-3-chloro 2-propenyl (meth) acrylate, 2,3-dibromo-2-propenyl (meth) acrylate, 2-chloro-3-methyl-2-propenyl (meth) acrylate, 1,1-dimethyl-2-propenyl (meta ) Acrylate, 2-pentenyl (meth) acrylate, 2-hexenyl (meth) acrylate, 2-heptenyl (meth) acrylate, and the like.
Among these, allyl (meth) acrylate is particularly preferable in terms of curability and raw material price.

Examples of the “(meth) acrylate having at least one aromatic ring and / or aliphatic ring” include, for example, (meth) acrylic acid cycloalkyl ester [eg, (meth) acrylic acid cyclohexyl, (meth) acrylic acid norbornyl, ( Meth) acrylic acid adamantyl, etc.], (meth) acrylic acid aryl ester [eg, (meth) acrylic acid phenyl, (meth) acrylic acid chlorophenyl, (meth) acrylic acid methoxyphenyl, etc.), aralkyl And esters [for example, benzyl (meth) acrylate, phenethyl (meth) acrylate, etc.], and the like.
Among these, benzyl (meth) acrylate and cyclohexyl (meth) acrylate are preferable in terms of raw material price, solubility, pigment dispersibility, and the like.

Examples of the “other monomers” copolymerizable with these structural units include (meth) acrylic acid alkyl esters [for example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid. Propyl, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, (meth ) (Meth) acrylic acid (C ¹ -C ¹⁸ ) alkyl esters such as 2-ethylhexyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate];

(Meth) acrylic acid aralkyl esters [for example, benzyl (meth) acrylate], substituted (meth) acrylic acid alkyl esters [for example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) Acrylate, diethylaminopropyl (meth) acrylate, etc.], (meth) acrylamides [for example, (meth) acrylamide, dimethyl (meth) acrylamide, isopropyl (meth) acrylamide, t-butyl (meth) acrylamide, etc.), substituted (meth) Acrylamides [eg (meth) acryloylmorpholine, dimethylaminopropyl (meth) acrylamide etc.], aromatic vinyls [eg styrene, vinyltoluene, α-methylstyrene etc.] Heterocyclic vinyls [eg, vinyl imidazole, vinyl pyridine, etc.], vinyl esters [eg, vinyl acetate, vinyl propionate, vinyl versatate], N-vinylamides [eg, N-vinylpyrrolidone, N-vinylformamide N-vinylacetamide, etc.], allyl esters [eg, allyl acetate, etc.], halogen-containing monomers [eg, vinylidene chloride, vinyl chloride, etc.], vinyl cyanides [eg, (meth) acrylonitrile, etc.], olefins [eg, , Ethylene, propylene, etc.].

Among these, (meth) acrylic acid alkyl ester [for example, methyl (meth) acrylate, (meth), from the viewpoint of the copolymerizability, the solvent solubility of the polymer to be formed, the film forming property of the resulting film, and the like. Ethyl acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, Particularly preferred are octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.
These other copolymerizable components may be used singly or in combination of two or more.

  In addition to allyl groups and (meth) acryloyl groups, ethylenically unsaturated groups such as styryl groups, cyclic ether-containing groups such as epoxy groups, glycidyl groups and oxetanyl groups, cyclic heteroether-containing groups such as thiirane and aziridine, isocyanate , May have a cumulene functional group such as thioisocyanate, and among them, a binder having an ethylenically unsaturated group and a cyclic ether group in the side chain is preferable from the viewpoint of availability, reactivity, and handleability. Among them, a binder having an allyl group, a (meth) acryloyl group, or a glycidyl group in the side chain is particularly preferably used.

Regarding the copolymer composition ratio of each component, the “structural unit having a carboxyl group” is preferably 10 to 40 mol%, more preferably 15 to 35 mol%, particularly preferably 20 to 35 mol%. When the structural unit having a carboxyl group is within the above range, good developability is obtained and the developer resistance of the image area is also good. Moreover, 20-80 mol% is preferable, as for "the structural unit represented by General formula (1)", 20-75 mol% is further more preferable, and 25-75 mol% is especially preferable. When the structural unit represented by the general formula (1) is within the above range, good curability and developability can be obtained.
The crosslinkable group content in the binder polymer is preferably 10% to 90%, more preferably 15% to 85%, and most preferably 20% to 80%. If the crosslinkable group content is 10% or less, the effect of the present invention may not be obtained.

  The weight average molecular weight of the copolymer suitable as a binder is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, and particularly preferably 12,000 to 80,000. When the weight average molecular weight is within the above range, it is desirable from the viewpoint of production suitability and developability of the copolymer.

  Hereinafter, as specific examples of the copolymer suitable as a binder, JP-A Nos. 2003-131379 and 2003-207787 can be referred to.

  The said copolymer suitable as a binder can be obtained by copolymerizing a monomer corresponding to each by a well-known method according to a conventional method. For example, it can be obtained by dissolving these monomers in a suitable solvent, adding a radical polymerization initiator thereto and polymerizing them in a solution.

  Examples of a suitable solvent for copolymerization can be arbitrarily selected according to the solubility of the monomer and the copolymer to be produced. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, Examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, chloroform, toluene, and a mixture thereof. Further, a polymerization initiator can be used. Examples of the polymerization initiator include 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis- (2,4′-dimethyl). An azo compound such as valeronitrile), a peroxide compound such as benzoyl peroxide, a persulfate, or the like can be used.

In addition, a known chain transfer agent can be appropriately used for the purpose of adjusting the molecular weight. Furthermore, it may be necessary to appropriately adjust the polymerization concentration, the initiator amount, the chain transfer agent, the polymerization temperature, and the like. For example, the polymerization concentration is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass.
As content of the binder in the photosensitive resin composition, 30-70 mass% is preferable in conversion of solid content, and 40-50 mass% is preferable.

[Ethylenically unsaturated compound]
As the ethylenically unsaturated compound, those having a crosslinking group are preferable, and those having at least one addition-polymerizable ethylenically unsaturated group are not particularly limited and can be appropriately selected according to the purpose. Examples include ester compounds, amide compounds, and other compounds.

  Examples of the ester compound include monofunctional (meth) acrylic acid ester, polyfunctional (meth) acrylic acid ester, itaconic acid ester, crotonic acid ester, isocrotonic acid ester, maleic acid ester, and other ester compounds. It is done. These may be used individually by 1 type and may use 2 or more types together. Of these, monofunctional (meth) acrylic acid esters and polyfunctional (meth) acrylic acid esters are preferable.

  Examples of the monofunctional (meth) acrylic acid ester include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl mono (meth) acrylate.

  Examples of the polyfunctional (meth) acrylic acid ester include polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and 1,3-butanediol di (meth). Acrylate, tetramethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) ) Acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol poly (meth) acrylate, sorbitol Tri (meth) acrylate, sorbitol tetra (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate. Of these, dipentaerythritol poly (meth) acrylate is particularly preferable.

  As another example of the polyfunctional (meth) acrylic acid ester, a polyfunctional alcohol such as glycerin or trimethylolethane is added with ethylene oxide or propylene oxide and then (meth) acrylated, Japanese Patent Publication No. 48-41708 No. 50-6034, urethane acrylates described in JP-A 51-37193, JP-A 48-64183, JP-B 49-43191, and JP-B 52-30490 Polyester acrylates described in the above, epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, (meth) acrylic acid esters and urethane (meth) acrylates described in JP-A-60-258539, And vinyl esters.

  Examples of the “other compounds” include trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, Japan Adhesion Association Vol. 20, no. 7, photocurable monomers and oligomers described on pages 300 to 308, and the like.

Examples of the amide compound include amides (monomers) of unsaturated carboxylic acids and aliphatic polyvalent amine compounds. Specific examples include methylene bis- (meth) acrylamide, 1,6-hexamethylene. Examples thereof include bis- (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, xylylene bis (meth) acrylamide, and (meth) acrylic acid amide described in JP-A-60-258539.
Examples of the “other compounds” include allyl compounds described in JP-A-60-258539.

An ethylenically unsaturated compound may be used in combination of two or more, in addition to being used alone.
As content of the ethylenically unsaturated compound in the photosensitive resin composition, 10-60 mass% is preferable with respect to the total solid of this composition or this layer, and 20-50 mass% is more preferable.

  In the present invention, the ratio (M / B) of the content B (mass%) of the binder and the content M (mass%) of the ethylenically unsaturated compound in the photosensitive resin composition is 0. 6-1.5 is preferable. Moreover, the range of more preferable ratio M / B is 0.7-1.0.

[Other ingredients]
In the photosensitive resin composition in the present invention, in addition to the essential components of the ethylenically unsaturated compound, the photopolymerization initiator and the binder, if necessary, a colorant, a surfactant, a solvent, a thermal polymerization inhibitor, Known additives such as ultraviolet absorbers can be used.

-Colorant-
Examples of the colorant include dyes and pigments. This is used as needed for the color filter member formed by the photosensitive resin composition.
Taking the case of the purpose of forming the spacer as an example, the preferred pigment type, size and the like can be appropriately selected from the description of JP-A-11-149008, for example. Further, when a colorant such as a pigment is contained, a colored pixel can be formed. Examples of usable pigments include extender pigments and colored pigments. There is no restriction | limiting in particular as an extender, According to the objective, it can select suitably, For example, the extender described in paragraph number [0035]-[0041] of Unexamined-Japanese-Patent No. 2003-302039 is mentioned suitably. Preferable examples of the color pigment include pigments described in paragraph [0043] of JP-A No. 2003-302039.

-Surfactant-
As the surfactant, any surfactant can be used as long as it is mixed with the constituent components of the photosensitive resin composition (or photosensitive layer). As preferable surfactants, paragraph numbers [0015] to [0024] of JP-A No. 2003-337424, paragraph numbers [0012] to [0017] of JP-A No. 2003-177522, and JP-A No. 2003-177523 are disclosed. Paragraph Nos. [0012] to [0015], Paragraph Nos. [0010] to [0013] of JP-A No. 2003-177521, Paragraph Nos. [0010] to [0013] of JP-A No. 2003-177519, JP-A 2003-2003 Preferred examples include surfactants described in paragraph numbers [0012] to [0015] of JP-A No. 177520, paragraph numbers [0034] to [0035] of JP-A No. 11-133600, and JP-A No. 6-16684. .
From the viewpoint of obtaining a higher effect, a fluorosurfactant and / or a silicon surfactant (a fluorosurfactant or a silicon surfactant, a surfactant containing both a fluorine atom and a silicon atom) It is preferable to select any one of them, or two or more thereof, and a fluorosurfactant is most preferable.

  When using a fluorosurfactant, the number of fluorine atoms in the fluorine-containing substituent in the surfactant molecule is preferably 1 to 38, more preferably 5 to 25, and most preferably 7 to 20. It is desirable for the number of fluorine atoms to be in the above-mentioned range since the solubility is good and the effect of improving unevenness is obtained.

  As a particularly preferred surfactant, a monomer A represented by the following general formula (a) and a monomer B represented by the following general formula (b) are included as copolymerization components, and the monomer A and the monomer B Examples thereof include a copolymer having a copolymerization ratio (A / B [mass ratio]) of 20/80 to 60/40 (hereinafter also referred to as “surfactant suitable for the present invention”).

In the general formulas (a) and (b), R ¹ , R ² , and R ³ each independently represents a hydrogen atom or a methyl group, preferably R ¹ , R ² are hydrogen atoms, and R ³ is It is a methyl group.
R ⁴ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Examples of the alkyl group represented by R ⁴ include a methyl group, an ethyl group, a propyl group, and a butyl group. Among them, an alkyl group having 1 to 2 carbon atoms is preferable. R ⁴ is particularly preferably a hydrogen atom.

In said general formula (a), n represents the integer of 1-18, Preferably it is an integer of 2-10. m represents an integer of 2 to 14, preferably an integer of 4 to 12. C _m F _{2m + 1} in the general formula (a) may be linear or branched, and the ratio of C _m F _{2m + 1 to} the monomer A is preferably 20 to 70% by mass, particularly preferably 40 to 60% by mass. .

In the general formula (b), p and q each independently represent an integer of 0 to 18, preferably 2 to 8. p and q do not represent 0 at the same time.
In the surfactant suitable for the present invention, the plurality of monomers A contained in one molecule may have the same structure or different structures, and the same applies to the monomer B.

  The surfactant (copolymer) suitable for the present invention is such that the monomer A is 20 to 60% by mass, the monomer B is 80 to 40% by mass, and the monomer A is based on the total mass of the copolymer. And other optional monomers other than B are preferably copolymerized at a copolymerization ratio of the remaining mass%, and further, monomer A is 25 to 60 mass%, monomer B is 60 to 40 mass%, In addition, it is preferably copolymerized at a copolymerization ratio in which any other monomer other than the monomers A and B is the remaining mass%, the monomer A being 25 to 60 mass%, and the monomer B being 75 to 40 mass% It is more preferable that the copolymerization is carried out at a copolymerization ratio in which any other monomer other than the monomers A and B is the remaining mass%.

Among the surfactants suitable for the present invention (a copolymer obtained by copolymerizing at least monomer A and monomer B), a preferred embodiment is that R ¹ in the general formula (a) is a hydrogen atom, and n = 2 and m = 6, R ² in the general formula (b) is a hydrogen atom, R ³ is a methyl group, R ⁴ is a hydrogen atom, and p = 7 , Q = 0, or monomer B wherein R ² , R ³ , and R ^{4 in the} general formula (b) are hydrogen atoms, and p = 0 and q = 7, It is a copolymer formed by copolymerization at a copolymerization ratio (A / B) of 80 to 60/40. Particularly preferred is the case of a copolymerization ratio of 25/60 to 60/40.
Specific examples of the copolymer containing the monomer A represented by the general formula (a) and the monomer B represented by the general formula (b) as copolymerization components are described in paragraph No. 2003-337424. [0068] in Table 1.

-Solvent-
In the preparation of the photosensitive resin composition, an organic solvent can be used in addition to the above components. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam and the like.

-Thermal polymerization inhibitor-
The photosensitive resin composition can further contain a thermal polymerization inhibitor. Examples of thermal polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl- 6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like.

-UV absorber-
The photosensitive resin composition can contain an ultraviolet absorber as necessary. Examples of the ultraviolet absorber include compounds described in JP-A-5-72724, salicylate series, benzophenone series, benzotriazole series, cyanoacrylate series, nickel chelate series, hindered amine series, and the like.

  Specifically, phenyl salicylate, 4-t-butylphenyl salicylate, 2,4-di-t-butylphenyl-3 ′, 5′-di-t-4′-hydroxybenzoate, 4-t-butylphenyl salicylate 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2 '-Hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, ethyl-2-cyano-3,3-diphenyl acrylate, 2,2'-hydroxy-4-methoxybenzophenone, nickel Dibutyldithiocarbamate, bis (2,2,6,6-tetramethyl-4-pyridine Sebacate, 4-tert-butylphenyl salicylate, phenyl salicylate, 4-hydroxy-2,2,6,6-tetramethylpiperidine condensate, succinic acid-bis (2,2,6,6-tetramethyl-4 -Piperenyl) -ester, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 7-{[4-chloro-6- (diethylamino) -5 And triazin-2-yl] amino} -3-phenylcoumarin.

  Moreover, the photosensitive resin composition can also contain the "adhesion adjuvant", other additives, etc. of Unexamined-Japanese-Patent No. 11-133600 other than the said additive.

<Manufacturing method of substrate with spacer>
Hereinafter, the manufacturing method of the board | substrate with a spacer using the photosensitive resin composition of the said this invention is demonstrated in detail with the exposure system peculiar to this invention. The method for producing a substrate with a spacer according to the present invention comprises a step of forming a photosensitive layer containing the photosensitive resin composition for a photospacer according to the present invention on a substrate, and a spatial light modulation device arranged two-dimensionally. And a step of curing the photosensitive layer by performing relative scanning while modulating monochromatic light or bright lines in the range of 350 nm to 420 nm.
More specifically, in the first aspect of the method for manufacturing a substrate with a spacer, photosensitive layer formation is performed by coating the photosensitive resin composition of the present invention on the substrate surface and drying to form a photosensitive resin composition layer. It has a process, the exposure process which exposes this photosensitive resin composition layer in pattern shape, and the image development process which removes the uncured area | region of the photosensitive layer after exposure. Hereinafter, the first aspect of this production method will be referred to as a coating method (liquid registration method) as appropriate.
The second aspect is a method of using a transfer material using the photosensitive resin composition. On the temporary support, 1) a thermoplastic resin layer, and 2) the photosensitive resin composition of the present invention. A photosensitive layer formed by laminating a photosensitive layer made of a material in this order, and contacting the surface on the opposite side of the temporary support with the substrate, laminating the workable material on the substrate, After the photosensitive layer is peeled off and the photosensitive layer is transferred to the substrate surface, the photosensitive layer is exposed in a pattern, and the uncured region of the exposed photosensitive layer is removed. Hereinafter, the second aspect of this production method will be referred to as a transfer method as appropriate. In the second aspect, the exposure process and the development process performed after forming the photosensitive layer are the same processes as in the first aspect.

First, the photosensitive layer forming process using the coating method according to the first aspect will be described. In this step, the photosensitive resin composition of the present invention is dissolved or dispersed in an appropriate liquid to prepare a coating solution, which is applied to the substrate surface and dried to form a photosensitive layer.
The solvent or dispersant can be appropriately selected from known liquids such as water or organic solvents, depending on the composition of the photosensitive resin composition.

There is no particular limitation on the method for applying the coating liquid to the substrate surface, and known coating methods such as spin coating method, curtain coating method, slit coating method, dip coating method, air knife coating method, roller coating method, wire bar, etc. A coating method, a gravure coating method, or an extrusion coating method using a popper described in US Pat. No. 2,681,294 may be selected and applied according to the purpose. Among them, a method using a slit coater provided with a slit nozzle having a slit-like hole in a portion where liquid is discharged is preferable.
As a slit coater provided with the slit-shaped nozzle, JP 2004-89851 A, JP 2004-17043 A, JP 2003-170098 A, JP 2003-164787 A, JP 2003-10767 A, and the like. The slit-shaped nozzle and slit coater described in JP-A-2002-79163 and JP-A-2001-310147 are preferably used.

  As a method of drying the coating film containing the photosensitive resin composition applied on the substrate, a known method can be appropriately used. The drying conditions vary depending on the formulation of the photosensitive resin composition used, the type of solvent, and the like, but in general, a temperature range of 70 to 150 ° C. is preferable.

When the photosensitive layer is formed by a coating method, the layer thickness is preferably in the range of 0.5 to 10.0 μm, and more preferably in the range of 1 to 6 μm. When the layer thickness is within the above range, the occurrence of pinholes during coating formation during production is prevented, and the development and removal of the unexposed area does not affect the exposed and hardened area within an appropriate time. Can be done.
In the manufacturing method in this aspect, the photosensitive resin composition is applied to the substrate surface to form a photosensitive layer, but other layers may be provided depending on the purpose. Other optional layers include an oxygen-blocking protective layer for suppressing inhibition of polymerization by oxygen in the photosensitive layer curing reaction, an adhesive layer for improving adhesion between layers, and light transmission to a desired region. And a light blocking layer that suppresses the property. In these layers, the photosensitive layer can be similarly provided by a coating method, or a layer previously formed into a sheet shape can be laminated by a laminating method.

Next, the photosensitive layer forming process using the transfer method according to the second aspect will be described. In this step, a photosensitive material produced using the photosensitive resin composition of the present invention is used. Here, the photosensitive material will be described.
The photosensitive material of the present invention functions as a photosensitive transfer material, and the configuration thereof uses an integral transfer film such as a resin transfer material described in JP-A-5-72724. Examples of the structure of the integral transfer photosensitive material that can be suitably formed include: 1) a thermoplastic resin layer, then an intermediate layer, if desired, and 2) the present invention on a temporary support. A configuration having a laminated structure in which a photosensitive layer made of a photosensitive resin composition and further a protective layer is provided as desired is suitable.

<Photosensitive material>
Next, the layer structure of the photosensitive material of the present invention for producing a photospacer will be described.

-Photosensitive layer-
The photosensitive layer in this embodiment is a layer composed of the photosensitive resin composition of the present invention, and a photosensitive coating solution obtained by dissolving or dispersing it in an appropriate solvent is applied and dried by a known coating method. It can form more suitably.

As described in the application method, the photosensitive resin composition can be applied by using a known application method as appropriate. However, in this aspect as well, a slit-like shape having a slit-like hole in the portion from which the liquid is discharged. Application by a nozzle is preferred. Details of the slit nozzle and the slit coater are as described above.
The layer thickness of the photosensitive layer in the photosensitive material is preferably 0.5 to 10 μm and more preferably 1 to 6 μm for the same reason as described in the coating method.

-Thermoplastic resin layer-
The photosensitive material of the present invention (hereinafter also referred to as “photosensitive transfer material”) has at least one thermoplastic resin layer between the photosensitive layer and the temporary support.
This thermoplastic resin layer functions as a cushion material that effectively prevents transfer defects caused by irregularities present on the transfer material (substrate) when the photosensitive layer is transferred to the transfer material. And can be deformed corresponding to the unevenness on the transfer material when the photosensitive transfer material is heat-pressed on the transfer material, and the adhesion between the photosensitive layer and the transfer material can be improved.
Further, after the transfer, it is removed together with an unnecessary (uncured) photosensitive layer by development, so it is preferable to use a thermoplastic resin capable of alkali development. In addition, it is necessary to use an alkali-soluble resin from the viewpoint of suppressing the contamination of the transferred material by the thermoplastic resin layer itself protruding during transfer.

The layer thickness of the thermoplastic resin layer is preferably 0.1 to 20 μm. When the layer thickness is within the above range, it is excellent in releasability from the temporary support during transfer, and is effective in absorbing irregularities on the transfer material, and reticulation occurs in the photosensitive layer. There is no transfer failure. The layer thickness is more preferably 1.5 to 16 μm, and most preferably 5 to 15.0 μm.
Reticulation means that when the intermediate layer is stretched due to moisture absorption, etc., the flexible cushion layer buckles and fine “wrinkles” occur on the surface of the photosensitive layer. Cause.

  The thermoplastic resin layer can be configured using at least a thermoplastic resin, and other components can be appropriately used as necessary. The thermoplastic resin is not particularly limited as long as it has alkali solubility, and can be appropriately selected. However, those having a substantial softening point of 80 ° C. or less are preferable.

  Examples of the thermoplastic resin having a substantial softening point of 80 ° C. or lower include saponified products of ethylene and acrylate copolymers, saponified products of styrene and (meth) acrylate copolymers, and vinyl toluene. And saponified products of (meth) acrylic acid ester copolymers, poly (meth) acrylic acid esters, and (meth) acrylic acid ester copolymers of butyl (meth) acrylate and vinyl acetate, The softening point described in “Plastic Performance Handbook” (edited by the Japan Plastic Industry Federation, edited by the All Japan Plastics Molding Industry Association, published by the Industrial Research Council, issued on October 25, 1968) is about 80 ° C. Among the following organic polymers, alkali-soluble ones are also included. These may be used individually by 1 type and may use 2 or more types together.

  Further, various plasticizers having compatibility with the organic polymer substance, even if the organic polymer substance itself has a softening point of 80 ° C. or more, assuming that the substantial softening point is 80 ° C. or less. And those having a substantial softening point of 80 ° C. or less by adding. The plasticizer is not particularly limited and may be appropriately selected depending on the intended purpose.For example, polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate , Biphenyl diphenyl phosphate, and the like.

  In addition to the thermoplastic resin, the alkali-soluble thermoplastic resin layer has various components within the range where the softening point does not substantially exceed 80 ° C. for the purpose of adjusting the adhesive force with the temporary support as other components. A polymer, a supercooling substance, an adhesion improving agent, a surfactant, a release agent, and the like can be added.

-Intermediate layer-
The photosensitive transfer material is preferably provided with an intermediate layer for the purpose of preventing mixing of components during the application of a plurality of layers and during storage after the application. In particular, it is preferably provided between the thermoplastic resin layer provided on the temporary support and the photosensitive layer. An organic solvent is used to form the thermoplastic resin layer and the photosensitive layer. However, by providing an intermediate layer, mixing due to the compatibility of adjacent layers can be prevented when the photosensitive layer is applied.

As a component used for an intermediate | middle layer, what is disperse | distributed thru | or melt | dissolved in water or aqueous alkali solution is preferable. A known material can be used for the constituent material of the intermediate layer. For example, the polyvinyl ether / maleic anhydride polymer described in JP-A No. 46-2121 and JP-B No. 56-40824, water-soluble carboxyalkyl cellulose. Salts, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamides, water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, various starches and the like Water-soluble salts of the group consisting of products, styrene / maleic acid copolymers, maleate resins, and the like.
These may be used in combination of two or more, in addition to being used alone.

Among these, it is preferable to use a water-soluble resin, that is, a water-soluble polymer material. Among these, it is more preferable to use at least polyvinyl alcohol, and the combined use of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable.
There is no restriction | limiting in particular as said polyvinyl alcohol, According to the objective, it can select suitably, The thing whose saponification degree is 80 mol% or more is preferable.

  When polyvinylpyrrolidone is used, the content thereof is preferably 1 to 75% by volume, more preferably 1 to 60% by volume, and particularly preferably 10 to 50% by volume based on the solid content of the intermediate layer. When the content is within the above range, sufficient adhesion with the thermoplastic resin layer is obtained, and the oxygen blocking ability is also good.

  The intermediate layer preferably has a low oxygen permeability. That is, it is preferably composed of an oxygen-blocking film having an oxygen-blocking function, and the sensitivity at the time of exposure can be increased, the time load of the exposure apparatus can be reduced, the productivity can be improved, and the resolution can be improved.

  The thickness of the intermediate layer is preferably about 0.1 to 5 μm, and more preferably 0.5 to 2 μm. When the thickness of the intermediate layer is within the above range, the oxygen barrier property is not deteriorated, and it is possible to prevent the intermediate layer removal time during development from increasing.

-Temporary support-
As the temporary support, those having a peelability from the thermoplastic resin layer to the extent that does not hinder the transfer are preferable, and those having chemical and thermal stability and flexibility are preferable.

  The material for the temporary support is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polytetrafluoroethylene, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, and polypropylene.

There is no restriction | limiting in particular as a structure of a temporary support body, According to the objective, it can select suitably, Either a single layer structure or a laminated structure may be sufficient. In addition, the temporary support is preferably not subjected to surface treatment such as glow discharge from the viewpoint of ensuring good releasability with the thermoplastic resin layer, and no undercoat layer such as gelatin is provided. preferable.
The thickness of the temporary support is preferably about 5 to 300 μm, and preferably 20 to 150 μm.

The temporary support preferably has a conductive layer on at least one surface thereof, or the temporary support itself has conductivity. When the temporary support is configured as described above, the temporary support or The transferred object is not charged and attracts surrounding dust, and as a result, even after the temporary support is peeled off, the dust does not adhere to the thermoplastic resin layer, and it is not necessary in the subsequent exposure process. It is possible to effectively prevent the formation of pinholes due to the formation of unexposed portions. The surface electrical resistance on the surface of the conductive layer on the temporary support or the temporary support having conductivity is preferably 10 ¹³ Ω or less.

The temporary support having conductivity can be obtained by containing a conductive substance in the temporary support. There is no restriction | limiting in particular as an electroconductive substance, Although it can select suitably according to the objective, For example, a metal oxide, an antistatic agent, etc. are mentioned.
Examples of the metal oxide include zinc oxide, titanium oxide, tin oxide, aluminum oxide, indium oxide, silicon oxide, magnesium oxide, barium oxide, and molybdenum oxide. These may be used alone or in combination of two or more. In addition, examples of the form of the metal oxide include crystal fine particles and composite fine particles.

  Examples of the antistatic agent include Electro Stripper A (manufactured by Kao Corporation), Elenon No. 19 (Daiichi Kogyo Seiyaku Co., Ltd.) alkyl phosphate anionic surfactants, Amogen K (Daiichi Kogyo Seiyaku Co., Ltd.) betaine amphoteric surfactants, Nissan Nonion L (Nippon Yushi Polyoxyethylene fatty acid ester nonionic surfactants such as Emulgen 106, 120, 147, 420, 220, 905, 910 (made by Kao Corporation) and Nissan Nonion E (made by Kao Corporation) Polyoxyethylene alkyl ether type nonionic surfactants such as Nippon Oil & Fats Co., Ltd., polyoxyethylene alkylphenol ether type, polyhydric alcohol fatty acid ester type, polyoxyethylene sorbitan fatty acid ester type, polyoxyethylene alkylamine type, etc. Other nonionic surfactants. These may be used individually by 1 type and may use 2 or more types together.

The conductive layer can be formed by appropriately selecting from a configuration using a known conductive substance, and the conductive substance can obtain a stable conductive effect without being affected by the humidity environment. For example, ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO _{3 and the} like are preferable. These may be used in combination of two or more, in addition to being used alone.

The volume resistance value of the metal oxide or the conductive substance is preferably 10 ⁷ Ω · cm or less, and more preferably 10 ⁵ Ω · cm or less. Moreover, as a particle diameter of the said metal oxide or the said electroconductive substance, 0.01-0.7 micrometer is preferable and 0.02-0.5 micrometer is more preferable.

  In the conductive layer, as a binder, for example, cellulose esters such as gelatin, cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate, vinylidene chloride, vinyl chloride, styrene, acrylonitrile, Homopolymers or copolymers containing vinyl acetate, alkyl acrylates having 1 to 4 carbon atoms, vinyl pyrrolidone, etc., soluble polyesters, polycarbonates, soluble polyamides, etc. can be used.

In addition to the above, the photosensitive transfer material can be further provided with a protective film as another layer.
The protective film has a function of protecting the photosensitive layer from dirt and damage during storage and the like, and can be made of the same or similar material as the temporary support. The protective film is not particularly limited as long as it can be easily peeled off from the photosensitive layer, and examples thereof include silicon paper, polyolefin sheet, and polytetrafluoroethylene sheet. Among these, a polyethylene sheet or film and a polypropylene sheet or film are preferable. As thickness of a protective film, about 5-100 micrometers is preferable and 10-30 micrometers is more preferable.

  The photosensitive transfer material is a thermoplastic resin in which a thermoplastic organic polymer (thermoplastic resin) and a solution in which an additive is dissolved are coated on a temporary support and dried. After the layer is provided, a prepared solution (intermediate layer coating solution) prepared by adding a resin or an additive to a solvent that does not dissolve the thermoplastic resin layer is applied onto the thermoplastic resin layer, and dried to dry the intermediate layer. It is preferably prepared by laminating and applying the photosensitive resin composition prepared as described above on the intermediate layer using a solvent that does not dissolve the intermediate layer, and drying and laminating the photosensitive layer. be able to.

  In addition to the above, a first sheet in which a thermoplastic resin layer and an intermediate layer are provided in order from the temporary support side on the temporary support side, and a second sheet in which a photosensitive layer is provided on a protective film are prepared. It can also be produced by bonding so that the surface of the intermediate layer of the sheet is in contact with the surface of the photosensitive layer of the second sheet. Furthermore, a first sheet provided with a thermoplastic resin layer on a temporary support and a second sheet provided with a photosensitive layer and an intermediate layer in this order from the protective film side on a protective film are prepared. It can also be produced by bonding the intermediate layer surface and the surface of the thermoplastic resin layer of the first sheet so as to contact each other.

Next, a method for forming a photosensitive layer on the substrate surface using such a photosensitive transfer material will be described.
In the photosensitive layer forming process by the transfer method, the photosensitive transfer material is laminated on the substrate by contacting the surface opposite to the temporary support and the substrate, and the temporary support is peeled off to form the photosensitive layer on the substrate surface. This is a transfer process.
When the photosensitive layer formed in a film form on the temporary support has a protective film on the surface, it is peeled off, and the exposed surface of the photosensitive layer is brought into contact with the substrate surface as a transfer material, and then Then, after bonding by heating or pressing with a heated and / or pressurized roller or flat plate, the photosensitive layer is transferred onto the substrate by peeling the temporary support. Bonding can be suitably performed using a known laminator (such as a vacuum laminator), and an auto-cut laminator is preferable from the viewpoint of increasing productivity.
Specifically, the laminator and laminating method described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794 can be applied. From the viewpoint of preventing contamination, it is preferable to use the method described in JP-A-7-110575.

  The layer thickness when the photosensitive layer is formed by the transfer method is the same as that by the coating method. Since this film thickness is determined when preparing a photosensitive material for transfer, it may be formed to have a desired film thickness when forming a photosensitive layer made of 2) a photosensitive resin composition.

Examples of the substrate on which the photosensitive layer is formed include a transparent substrate (for example, a glass substrate or a plastics substrate), a substrate with a transparent conductive film (for example, an ITO film), a substrate with a color filter (also referred to as a color filter substrate), and driving. Examples include a drive substrate with an element (for example, a thin film transistor [TFT]). The thickness of the substrate is appropriately selected according to the purpose of use of the color filter, but generally it is preferably in the range of 700 to 1200 μm.
Moreover, the substrate can be made to have good adhesion with the photosensitive resin composition or the photosensitive layer of the photosensitive material by performing a coupling treatment in advance. As the coupling treatment, a method described in JP 2000-39033 A is preferably used.

  After the formation of the photosensitive layer, an oxygen-blocking protective layer can be further provided on the photosensitive layer for the purpose of improving the curing sensitivity by exposure. The oxygen blocking film may have the same structure as that described in the section of the intermediate layer of the photosensitive material for transfer. The thickness of the oxygen blocking film is preferably 0.5 to 3.0 μm.

[Exposure process]
By performing pattern exposure on the photosensitive layer formed in the photosensitive layer forming step, the exposed region is cured, and a pattern is formed by this step and the subsequent developing step, and spacers can be formed as desired. In the exposure process according to the present invention, a two-dimensional image of a two-dimensional image is obtained by performing relative scanning while modulating monochromatic light or bright lines within a range of 350 nm to 420 nm based on image data using two-dimensional spatial light modulation devices. The exposure is performed by the exposure method.
Hereinafter, an exposure method that can be suitably used in the exposure process according to the present invention and an exposure apparatus used therefor will be described.

  The exposure of the present invention is sometimes called maskless exposure because it performs scanning exposure as represented by a laser direct imaging system without using a mask pattern. More specifically, the maskless exposure applied to the present invention can be referred to as exposure for forming a two-dimensional image by performing relative scanning while modulating light based on image data.

(Description of light source)
In the exposure method of the present invention, an ultrahigh pressure mercury lamp or a laser is used as a light source.
An ultra-high pressure mercury lamp is a discharge lamp in which mercury is enclosed in a quartz glass tube, etc., and is set to a high vapor pressure by increasing the vapor pressure of mercury (the vapor pressure of mercury during lighting is about 5 MPa) There are also W. Ellenbaas: Light Sources, Philips Technical Library 148-150). Of the bright line spectrum, i-line (365 nm) and h-line (405 nm) are used, and i-line with a wavelength of 365 nm is mainly used.

  Laser is an acronym for Light Amplification by Stimulated Emission of Radiation in English. Oscillators and amplifiers that produce monochromatic light with stronger coherence and directivity by amplifying and oscillating light waves, utilizing the phenomenon of stimulated emission that occurs in materials with an inverted distribution. Excitation media include crystals, glass, liquids, dyes, gases, etc. From these media, solid lasers (YAG lasers), liquid lasers, gas lasers (argon lasers, He-Ne lasers, carbon dioxide lasers, excimer lasers), semiconductor lasers A known laser such as can be used.

The semiconductor laser uses a light emitting diode that induces and emits coherent light at the pn junction when electrons and holes flow out to the junction due to carrier injection, excitation by an electron beam, ionization by collision, optical excitation, and the like. It is a laser. The wavelength of the emitted coherent light is determined by the semiconductor compound.
The wavelength of the laser is selected from the range of 350 nm to 420 nm.
In the semiconductor excitation solid-state laser, 355 nm is exemplified, and 355 nm is preferably selected from the viewpoint that the conventional photopolymerization initiator for resist has sensitivity.
Among these light sources, considering the case where the photosensitive material is exposed in the manufacturing process of the display device, it is preferable to select a light source having an exposure wavelength of 410 nm from the viewpoint of increasing the transmittance of the display region. .

A method of relative scanning while modulating light according to the present invention will be described.
One typical method is a two-dimensional micromirror such as DMD (digital micromirror device, for example, an optical semiconductor developed in 1987 by Dr. Larry Hornbeck et al., Texas Instruments, USA). This is a method of using spatial modulation elements arranged in line.
In this case, the light from the light source is irradiated onto the DMD by an appropriate optical system, and the reflected light from each mirror arranged two-dimensionally on the DMD passes through another optical system on the photosensitive layer in a two-dimensional manner. An image of light spots arranged in a row is formed. If the light spot is not exposed between the light spots, the image of the light spots arranged in two dimensions is moved in a direction slightly inclined with respect to the two-dimensional arrangement direction. The entire surface of the photosensitive layer can be exposed in such a manner that the light spots in the rear row are exposed between the light spots. An image pattern can be formed by controlling the angle of each mirror of the DMD and turning the light spot on and off. By aligning and using exposure heads having such DMDs, it is possible to deal with substrates of various widths.
In the DMD, the brightness of the light spot has only two gradations, ON or OFF, but exposure with 256 gradations can be performed by using a mirror gradation spatial modulation element.

  On the other hand, another representative method of relative scanning while modulating light according to the present invention is a method using a polygon mirror. A polygon mirror is a rotating member having a series of planar reflecting surfaces around it. The light from the light source is reflected and irradiated onto the photosensitive layer, and the light spot of the reflected light is scanned by the rotation of the plane mirror. By moving the substrate at right angles to the scanning direction, the entire surface of the photosensitive layer on the substrate can be exposed. An image pattern can be formed by controlling the intensity of light from the light source to ON-OFF or halftone by an appropriate method. By using a plurality of light from the light source, the scanning time can be shortened.

As a method of performing relative scanning while modulating light, which is employed in the present invention, for example, the following method can also be applied.
An example of drawing using a polygon mirror described in JP-A-5-150175, an apparatus using a polygon mirror by visually acquiring a part of an image of a lower layer described in JP-T-2004-523101 (WO2002 / 039793) In this example, exposure is performed with the position of the upper layer aligned with the position of the lower layer, an example of exposure with DMD described in JP-A-2004-56080, an exposure apparatus equipped with a polygon mirror described in JP-T-2002-523905, and JP-A-2001-255661. An exposure apparatus including a polygon mirror described in JP-A-2003-50469, an example of a combination of DMD, LD, and multiple exposure described in JP-A-2003-50469, an example of an exposure method that changes the exposure amount depending on the part of the substrate described in JP-A-2003-156893, This is an example of an exposure method for performing misalignment adjustment described in Japanese Patent Application Laid-Open No. 2005-43576.

Hereinafter, the relative scanning exposure will be described in detail.
(Relative scanning exposure)
The exposure method of the present invention includes a method using an ultrahigh pressure mercury lamp and a method using a laser, but the latter is preferred.
As the laser used in the present invention, known lasers such as an argon laser, a He—Ne laser, a semiconductor laser, a carbon dioxide gas laser, and a YAG laser can be used.
The wavelength of the laser is selected from the range of 350 nm to 420 nm. Among these, the range of 380 nm to 420 nm is preferable.
The beam diameter of the laser is not particularly limited, but among them, from the viewpoint of the resolution of the photo spacer, the 1 / e ² value of the Gaussian beam is preferably 5 to 30 μm, and more preferably 7 to 20 μm.
The energy amount of the laser beam is not particularly limited, but in particular, from the viewpoint of exposure time and resolution, 1 to 100 mJ / cm ² is preferable, and 5 to 20 mJ / cm ² is more preferable.
The scanning speed of the laser is not particularly limited as long as it satisfies the condition that the display characteristics of the color filter can be improved and the productivity is high, but is preferably 5 mm / second to 3000 m / second, more preferably 10 mm. / Second to 2000 m / second, most preferably 15 mm / second to 1000 m / second. 5 mm / second or less is not preferable because the number of exposure heads must be remarkably increased in the highly productive exposure system aimed at by the present invention. Further, at 3000 m / sec or more, the illuminance must be remarkably increased, which is not practical.

  In the present invention, it is necessary to spatially modulate laser light according to image data. For this purpose, it is preferable to use a digital micro device which is a spatial light modulation element. The exposure step is an exposure head provided with a light irradiation means and a light modulation means for the photosensitive layer, and the column direction of the picture element portions is a predetermined set inclination angle with respect to the scanning direction of the exposure head. An exposure head arranged so as to form θ is used, and the exposure head is subjected to N multiple exposures (where N is a natural number of 2 or more) of the usable pixel parts by the use pixel part specifying means. The pixel part to be used is specified, and for the exposure head, the pixel part is specified by the pixel part control unit so that only the pixel part specified by the used pixel part specifying unit is involved in the exposure. And performing exposure by moving the exposure head relative to the photosensitive layer in the scanning direction.

In the present invention, “N double exposure” means that the exposed surface is irradiated with a straight line parallel to the scanning direction of the exposure head in almost all of the exposed region on the exposed surface of the photosensitive layer. This means exposure by setting that intersects N light spot rows (pixel rows). Here, the “light spot array (pixel array)” is a direction in which the angle formed with the scanning direction of the exposure head is smaller in the array of light spots (pixels) as pixel units generated by the pixel unit. Refers to a sequence of Note that the arrangement of the picture element portions is not necessarily a rectangular lattice shape, and may be, for example, an arrangement of parallelograms.
Here, “substantially all areas” of the exposure area is described as a straight line parallel to the scanning direction of the exposure head by tilting the pixel part rows at both side edges of each picture element part. Since the number of drawing element rows of the used drawing element parts to be crossed decreases, even if it is used to connect a plurality of exposure heads in such a case, it is parallel to the scanning direction due to errors in the mounting angle and arrangement of the exposure heads. The number of pixel parts in the used pixel part that intersect with a straight line may slightly increase or decrease, and the connection between the pixel parts in each used pixel part is only a fraction of the resolution. However, due to errors such as the mounting angle and the arrangement of the picture element parts, the pitch of the picture element parts along the direction orthogonal to the scanning direction does not exactly match the pitch of the picture element parts of other parts, and is parallel to the scanning direction. The number of used pixel parts that intersect with the straight line may increase or decrease within a range of ± 1. It is an order. In the following description, N multiple exposures where N is a natural number of 2 or more are collectively referred to as “multiple exposure”. Further, in the following description, “N multiple drawing” and “multiple exposure” are used as terms corresponding to “N double exposure” and “multiple exposure” for an embodiment in which the exposure apparatus or exposure method of the present invention is implemented as a drawing apparatus or drawing method. The term “multiple drawing” shall be used.
N in the N-fold exposure is not particularly limited as long as it is a natural number of 2 or more, and can be appropriately selected according to the purpose. However, a natural number of 3 or more is preferable, and a natural number of 3 or more and 7 or less is more preferable. .

As the exposure apparatus, for example, exposure can be performed using the following apparatus.
An example of a three-dimensional exposure apparatus using laser light is shown below, but the exposure apparatus in the present invention is not limited to this.
As shown in FIG. 1, the exposure unit includes a flat stage 152 that holds a photosensitive material 150 by adsorbing a glass substrate to the surface. Two guides 158 extending along the stage moving direction are installed on the upper surface of the thick plate-like installation table 156 supported by the four legs 154. The stage 152 is arranged so that the longitudinal direction thereof faces the stage moving direction, and is supported by a guide 158 so as to be reciprocally movable. The exposure apparatus is provided with a drive device (not shown) for driving the stage 152 along the guide 158.

  A U-shaped gate 160 is provided at the center of the installation table 156 so as to straddle the movement path of the stage 152. Each of the ends of the U-shaped gate 160 is fixed to both side surfaces of the installation table 156. A scanner 162 is provided on one side of the gate 160, and a plurality of (for example, two) detection sensors 164 for detecting the front and rear ends of the photosensitive material 150 are provided on the other side. The scanner 162 and the detection sensor 164 are respectively attached to the gate 160 and fixedly arranged above the moving path of the stage 152. The scanner 162 and the detection sensor 164 are connected to a controller (not shown) that controls them.

As shown in FIGS. 2 and 3B, the scanner 162 includes a plurality of (for example, 14) exposure heads 166 arranged in an approximately matrix of m rows and n columns (for example, 3 rows and 5 columns). ing. In this example, four exposure heads 166 are arranged in the third row in relation to the width of the photosensitive material 150. In addition, when showing each exposure head arranged in the m-th row and the n-th column, it is expressed as an exposure head 166 _mn .

An exposure area 168 by the exposure head 166 has a rectangular shape with a short side in the sub-scanning direction. Therefore, as the stage 152 moves, a strip-shaped exposed area 170 is formed for each exposure head 166 in the photosensitive material 150. In addition, when showing the exposure area by each exposure head arranged in the m-th row and the n-th column, it is expressed as an exposure area 168 _mn .

Further, as shown in FIGS. 3A and 3B, each of the exposure heads in each row arranged in a line so that the strip-shaped exposed areas 170 are arranged without gaps in the direction orthogonal to the sub-scanning direction. In the arrangement direction, they are shifted by a predetermined interval (a natural number times the long side of the exposure area, twice here). Therefore, can not be exposed portion between the exposure area _{168 11} in the first row and the exposure area _{168 12,} it can be exposed by the second row of the exposure area _{168 21} and the exposure area _{168 31} in the third row.

Each of the exposure heads 166 _{11 to} 166 _mn is a spatial light modulation element that modulates an incident light beam for each pixel according to image data, as shown in FIGS. 4, 5 (A) and (B). A digital micromirror device (DMD) 50 is provided. The DMD 50 is connected to a controller (not shown) including a data processing unit and a mirror drive control unit. The data processing unit of this controller generates a control signal for driving and controlling each micromirror in the region to be controlled by the DMD 50 for each exposure head 166 based on the input image data. The area to be controlled will be described later. The mirror drive control unit controls the angle of the reflection surface of each micromirror of the DMD 50 for each exposure head 166 based on the control signal generated by the image data processing unit. The control of the angle of the reflecting surface will be described later.

  On the light incident side of the DMD 50, a fiber array light source 66 including a laser emitting portion in which an emitting end portion (light emitting point) of an optical fiber is arranged in a line along a direction corresponding to the long side direction of the exposure area 168, a fiber A lens system 67 for correcting the laser light emitted from the array light source 66 and condensing it on the DMD, and a mirror 69 for reflecting the laser light transmitted through the lens system 67 toward the DMD 50 are arranged in this order.

  The lens system 67 includes a pair of combination lenses 71 that collimate the laser light emitted from the fiber array light source 66 and a pair of combination lenses that correct the light quantity distribution of the collimated laser light to be uniform. 73 and a condensing lens 75 that condenses the laser light whose light intensity distribution is corrected on the DMD. With respect to the arrangement direction of the laser emitting end, the combination lens 73 spreads the light beam at a portion close to the optical axis of the lens and contracts the light beam at a portion away from the optical axis, and with respect to a direction orthogonal to the arrangement direction. Has a function of allowing light to pass through as it is, and corrects the laser light so that the light quantity distribution is uniform.

  Further, on the light reflection side of the DMD 50, lens systems 54 and 58 that form an image of the laser light reflected by the DMD 50 on the scanning surface (exposed surface) 56 of the photosensitive material 150 are arranged. The lens systems 54 and 58 are arranged so that the DMD 50 and the exposed surface 56 are in a conjugate relationship.

  As shown in FIG. 6, the DMD 50 is configured such that a micromirror 62 is supported by a support column on an SRAM cell (memory cell) 60, and a large number of (pixels) (pixels) are formed. For example, it is a mirror device configured by arranging 1024 × 768 micromirrors in a lattice pattern. Each pixel is provided with a micromirror 62 supported by a support column at the top, and a material having a high reflectance such as aluminum is deposited on the surface of the micromirror 62. The reflectance of the micromirror 62 is 90% or more. A silicon gate CMOS SRAM cell 60 manufactured in a normal semiconductor memory manufacturing line is disposed directly below the micromirror 62 via a support including a hinge and a yoke, and is entirely monolithic (integrated type). ).

  When a digital signal is written in the SRAM cell 60 of the DMD 50, the micromirror 62 supported by the support is inclined within a range of ± α degrees (for example, ± 10 degrees) with respect to the substrate side on which the DMD 50 is disposed with the diagonal line as the center. It is done. FIG. 7A shows a state in which the micromirror 62 is tilted to + α degrees in the on state, and FIG. 7B shows a state in which the micromirror 62 is tilted to −α degrees in the off state. Therefore, by controlling the inclination of the micromirror 62 in each pixel of the DMD 50 as shown in FIG. 6 according to the image signal, the light incident on the DMD 50 is reflected in the inclination direction of each micromirror 62. .

  FIG. 6 shows an example of a state in which a part of the DMD 50 is enlarged and the micromirror 62 is controlled to + α degrees or −α degrees. On / off control of each micromirror 62 is performed by a controller (not shown) connected to the DMD 50. A light absorber (not shown) is arranged in the direction in which the light beam is reflected by the micromirror 62 in the off state.

  Further, it is preferable that the DMD 50 be arranged with a slight inclination so that the short side thereof forms a predetermined angle θ (for example, 1 ° to 5 °) with the sub-scanning direction. 8A shows the scanning trajectory of the reflected light image (exposure beam) 53 by each micromirror when the DMD 50 is not tilted, and FIG. 8B shows the scanning trajectory of the exposure beam 53 when the DMD 50 is tilted. Show.

In the DMD 50, a plurality of micromirror arrays (for example, 768 pairs) arranged in the short direction are arranged in a long direction (see FIG. 8B). as shown, by tilting the DMD 50, the pitch P ₂ scanning locus of the exposure beams 53 from each micromirror (scan line), it becomes narrower than the pitch P ₁ of the scanning line in the case of not tilting the DMD 50, significant resolution Can be improved. On the other hand, the inclination angle of the DMD 50 is small, the scanning width _{W 2} in the case of tilting the DMD 50, which is substantially equal to the scanning width _{W 1} when not inclined DMD 50.

Further, the same scanning line is overlapped and exposed (multiple exposure) by different micromirror rows. In this way, by performing multiple exposure, it is possible to control a minute amount of the exposure position and to realize high-definition exposure. Further, joints between a plurality of exposure heads arranged in the main scanning direction can be connected without a step by controlling a very small amount of exposure position.
Note that the same effect can be obtained by arranging the micromirror rows in a staggered manner by shifting the micromirror rows by a predetermined interval in a direction orthogonal to the sub-scanning direction instead of inclining the DMD 50.

  As shown in FIG. 9A, the fiber array light source 66 includes a plurality of (for example, six) laser modules 64, and one end of the multimode optical fiber 30 is coupled to each laser module 64. Yes. The other end of the multimode optical fiber 30 is coupled with an optical fiber 31 having the same core diameter as the multimode optical fiber 30 and a cladding diameter smaller than the multimode optical fiber 30, as shown in FIG. A laser emission portion 68 is configured by arranging emission ends (light emission points) of the optical fiber 31 in a line along a main scanning direction orthogonal to the sub-scanning direction. As shown in FIG. 9D, the light emitting points can be arranged in two rows along the main scanning direction.

  As shown in FIG. 9B, the emission end of the optical fiber 31 is sandwiched and fixed between two support plates 65 having a flat surface. Further, a transparent protective plate 63 such as glass is disposed on the light emitting side of the optical fiber 31 in order to protect the end face of the optical fiber 31. The protective plate 63 may be disposed in close contact with the end surface of the optical fiber 31 or may be disposed so that the end surface of the optical fiber 31 is sealed. The light emitting end portion of the optical fiber 31 has a high light density and is likely to collect dust and easily deteriorate. However, by disposing the protective plate 63, it is possible to prevent the dust from adhering to the end face and to delay the deterioration.

  Here, in order to arrange the output ends of the optical fibers 31 with a small cladding diameter in a line without any gaps, the multi-mode optical fibers 30 are stacked between two adjacent multi-mode optical fibers 30 at a portion with a large cladding diameter. The exit ends of the optical fibers 31 coupled to the stacked multi-mode optical fibers 30 are the two exit ends of the optical fibers 31 coupled to the two adjacent multi-mode optical fibers 30 in the portion where the cladding diameter is large. They are arranged so that they are sandwiched between them.

  For example, as shown in FIG. 10, an optical fiber 31 having a length of 1 to 30 cm and having a small cladding diameter is coaxially connected to the tip of the multimode optical fiber 30 having a large cladding diameter on the laser light emission side. Can be obtained by linking them together. In the two optical fibers, the incident end face of the optical fiber 31 is fused and joined to the outgoing end face of the multimode optical fiber 30 so that the central axes of both optical fibers coincide. As described above, the diameter of the core 31 a of the optical fiber 31 is the same as the diameter of the core 30 a of the multimode optical fiber 30.

  In addition, a short optical fiber in which an optical fiber having a short cladding diameter and a large cladding diameter is fused to an optical fiber having a short cladding diameter and a large cladding diameter may be coupled to the output end of the multimode optical fiber 30 via a ferrule or an optical connector. Good. By detachably coupling using a connector or the like, the tip portion can be easily replaced when an optical fiber having a small cladding diameter is broken, and the cost required for exposure head maintenance can be reduced. Hereinafter, the optical fiber 31 may be referred to as an emission end portion of the multimode optical fiber 30.

  The multimode optical fiber 30 and the optical fiber 31 may be any of a step index type optical fiber, a graded index type optical fiber, and a composite type optical fiber. For example, a step index type optical fiber manufactured by Mitsubishi Cable Industries, Ltd. can be used. Here, the multimode optical fiber 30 and the optical fiber 31 are step index optical fibers, and the multimode optical fiber 30 has a cladding diameter = 125 μm, a core diameter = 25 μm, NA = 0.2, and transmission of the incident end face coating. The ratio is 99.5% or more, and the optical fiber 31 has a cladding diameter = 60 μm, a core diameter = 25 μm, and NA = 0.2.

  In general, in laser light in the infrared region, propagation loss increases as the cladding diameter of the optical fiber is reduced. For this reason, a suitable cladding diameter is determined according to the wavelength band of the laser beam. However, the shorter the wavelength, the smaller the propagation loss. In the case of laser light having a wavelength of 405 nm emitted from a GaN-based semiconductor laser, the cladding thickness {(cladding diameter−core diameter) / 2} is set to infrared light having a wavelength band of 800 nm. The propagation loss hardly increases even if it is about ½ of the case of propagating infrared light and about ¼ of the case of propagating infrared light in the 1.5 μm wavelength band for communication. Therefore, the cladding diameter can be reduced to 60 μm.

  However, the cladding diameter of the optical fiber 31 is not limited to 60 μm. The clad diameter of the optical fiber used in the conventional fiber light source is 125 μm, but the depth of focus becomes deeper as the clad diameter becomes smaller. Therefore, the clad diameter of the multimode optical fiber is preferably 80 μm or less, more preferably 60 μm or less. Preferably, it is 40 μm or less. On the other hand, since the core diameter needs to be at least 3 to 4 μm, the cladding diameter of the optical fiber 31 is preferably 10 μm or more.

  The laser module 64 includes a combined laser light source (fiber light source) shown in FIG. This combined laser light source includes a plurality of (for example, seven) chip-like lateral multimode or single mode GaN-based semiconductor lasers LD1, LD2, LD3, LD4, LD5, LD6, which are arrayed and fixed on the heat block 10. And LD7, collimator lenses 11, 12, 13, 14, 15, 16, and 17 provided corresponding to each of the GaN-based semiconductor lasers LD1 to LD7, one condenser lens 20, and one multi-lens. Mode optical fiber 30. The number of semiconductor lasers is not limited to seven. For example, as many as 20 semiconductor laser beams can be incident on a multimode optical fiber having a clad diameter = 60 μm, a core diameter = 50 μm, and NA = 0.2. In addition, the number of optical fibers can be further reduced.

  The GaN-based semiconductor lasers LD1 to LD7 all have a common oscillation wavelength (for example, 405 nm), and all the maximum outputs are also common (for example, 100 mW for a multimode laser and 30 mW for a single mode laser). As the GaN-based semiconductor lasers LD1 to LD7, lasers having an oscillation wavelength other than the above-described 405 nm in a wavelength range of 350 nm to 420 nm may be used.

  As shown in FIGS. 12 and 13, the above-described combined laser light source is housed in a box-shaped package 40 having an upper opening together with other optical elements. The package 40 includes a package lid 41 created so as to close the opening thereof. After the deaeration process, a sealing gas is introduced, and the package 40 and the package lid 41 are closed by closing the opening of the package 40 with the package lid 41. 41. The combined laser light source is hermetically sealed in a closed space (sealed space) formed by 41.

  A base plate 42 is fixed to the bottom surface of the package 40, and the heat block 10, a condensing lens holder 45 that holds the condensing lens 20, and the multimode optical fiber 30 are disposed on the top surface of the base plate 42. A fiber holder 46 that holds the incident end is attached. The exit end of the multimode optical fiber 30 is drawn out of the package from an opening formed in the wall surface of the package 40.

  Further, a collimator lens holder 44 is attached to the side surface of the heat block 10, and the collimator lenses 11 to 17 are held. An opening is formed in the lateral wall surface of the package 40, and a wiring 47 for supplying a driving current to the GaN-based semiconductor lasers LD1 to LD7 is drawn out of the package through the opening.

  In FIG. 13, in order to avoid complication of the drawing, only the GaN semiconductor laser LD7 is numbered among the plurality of GaN semiconductor lasers, and only the collimator lens 17 is numbered among the plurality of collimator lenses. is doing.

  FIG. 14 shows the front shape of the attachment part of the collimator lenses 11-17. Each of the collimator lenses 11 to 17 is formed in a shape obtained by cutting a region including the optical axis of a circular lens having an aspherical surface into a long and narrow plane. This elongated collimator lens can be formed, for example, by molding resin or optical glass. The collimator lenses 11 to 17 are closely arranged in the arrangement direction of the light emitting points so that the length direction is orthogonal to the arrangement direction of the light emitting points of the GaN-based semiconductor lasers LD1 to LD7 (left and right direction in FIG. 14).

  On the other hand, each of the GaN-based semiconductor lasers LD1 to LD7 includes an active layer having a light emission width of 2 μm, and each of the laser beams B1 in a direction parallel to the active layer and a divergence angle in a direction perpendicular to, for example, 10 ° and 30 °. A laser emitting ~ B7 is used. These GaN-based semiconductor lasers LD1 to LD7 are arranged so that the light emitting points are arranged in a line in a direction parallel to the active layer.

Accordingly, in the laser beams B1 to B7 emitted from the respective light emitting points, the direction in which the divergence angle is large coincides with the length direction and the divergence angle is small with respect to the elongated collimator lenses 11 to 17 as described above. Incident light is incident in a state where the direction coincides with the width direction (direction perpendicular to the length direction). That is, the collimator lenses 11 to 17 have a width of 1.1 mm and a length of 4.6 mm, and the horizontal and vertical beam diameters of the laser beams B1 to B7 incident thereon are 0.9 mm and 2. 6 mm. In addition, each of the collimator lenses 11 to 17 has a focal length f ₁ = 3 mm, NA = 0.6, and a lens arrangement pitch = 1.25 mm.

The condensing lens 20 is obtained by cutting an area including the optical axis of a circular lens having an aspheric surface into a long and narrow shape in parallel planes, and is long in the arrangement direction of the collimator lenses 11 to 17, that is, in the horizontal direction and short in the direction perpendicular thereto. Is formed. This condenser lens 20 has a focal length f ₂ = 23 mm and NA = 0.2. This condensing lens 20 is also formed by molding resin or optical glass, for example.

Next, the operation of the exposure apparatus will be described.
In each exposure head 166 of the scanner 162, laser beams B1, B2, B3, B4, B5, B6 emitted in a divergent light state from each of the GaN-based semiconductor lasers LD1 to LD7 constituting the combined laser light source of the fiber array light source 66. , And B7 are collimated by corresponding collimator lenses 11-17. The collimated laser beams B <b> 1 to B <b> 7 are collected by the condenser lens 20 and converge on the incident end face of the core 30 a of the multimode optical fiber 30.

  Here, a condensing optical system is configured by the collimator lenses 11 to 17 and the condensing lens 20, and a multiplexing optical system is configured by the condensing optical system and the multimode optical fiber 30. That is, the laser beams B1 to B7 condensed as described above by the condenser lens 20 are incident on the core 30a of the multimode optical fiber 30 and propagate through the optical fiber to be combined with one laser beam B. The light is emitted from the optical fiber 31 coupled to the output end of the multimode optical fiber 30.

  In each laser module, when the coupling efficiency of the laser beams B1 to B7 to the multimode optical fiber 30 is 0.85 and each output of the GaN-based semiconductor lasers LD1 to LD7 is 30 mW, the light arranged in an array For each of the fibers 31, a combined laser beam B with an output of 180 mW (= 30 mW × 0.85 × 7) can be obtained. Therefore, the output from the laser emitting unit 68 in which the six optical fibers 31 are arranged in an array is about 1 W (= 180 mW × 6).

  In the laser emitting portion 68 of the fiber array light source 66, light emission points with high luminance are arranged in a line along the main scanning direction as described above. A conventional fiber light source that couples laser light from a single semiconductor laser to a single optical fiber has low output, so a desired output cannot be obtained unless multiple rows are arranged. Since the light source has a high output, a desired output can be obtained even with a small number of columns, for example, one column.

For example, in a conventional fiber light source in which a semiconductor laser and an optical fiber are coupled one-on-one, a laser having an output of about 30 mW (milliwatt) is usually used as the semiconductor laser, and the core diameter is 50 μm and the cladding diameter is 125 μm. Since a multimode optical fiber having a numerical aperture (NA) of 0.2 is used, if an output of about 1 W (watt) is to be obtained, 48 multimode optical fibers (8 × 6) must be bundled. Since the area of the light emitting region is 0.62 mm ² (0.675 mm × 0.925 mm), the luminance at the laser emitting portion 68 is 1.6 × 10 ⁶ (W / m ² ) and one optical fiber is used. The luminance per hit is 3.2 × 10 ⁶ (W / m ² ).

On the other hand, as described above, an output of about 1 W can be obtained with the six multimode optical fibers, and the area of the light emitting region at the laser emitting unit 68 is 0.0081 mm ² (0.325 mm × 0.025 mm). Therefore, the luminance at the laser emitting portion 68 is 123 × 10 ⁶ (W / m ² ), and the luminance can be increased about 80 times as compared with the conventional case. Further, the luminance per optical fiber is 90 × 10 ⁶ (W / m ² ), and the luminance can be increased by about 28 times compared to the conventional one.

  Here, with reference to FIGS. 15A and 15B, the difference in the depth of focus by the exposure head will be described. In FIG. 15A, the diameter of the light emission region of the bundled fiber light source of the exposure head in the sub-scanning direction is 0.675 mm. In FIG. 15B, the light emission region of the fiber array light source of the exposure head in the sub-scanning direction. The diameter is 0.025 mm. As shown in FIG. 15A, in this exposure head, since the light emitting area of the light source (bundle-shaped fiber light source) 1 is large, the angle of the light beam incident on the DMD 3 increases, and as a result, the light beam incident on the scanning surface 5. The angle becomes larger. For this reason, the beam diameter tends to increase with respect to the light condensing direction (shift in the focus direction).

  On the other hand, as shown in FIG. 15B, in this exposure head, since the diameter of the light emitting region of the fiber array light source 66 is small in the sub-scanning direction, the angle of the light beam that passes through the lens system 67 and enters the DMD 50 is small. As a result, the angle of the light beam incident on the scanning surface 56 is reduced. That is, the depth of focus becomes deep. In this example, the diameter of the light emitting region in the sub-scanning direction is about 30 times that of the conventional one, and a depth of focus substantially corresponding to the diffraction limit can be obtained. Therefore, it is suitable for exposure of a minute spot. This effect on the depth of focus is more prominent and effective as the required light quantity of the exposure head is larger. In this example, the size of one pixel projected on the exposure surface is 10 μm × 10 μm. DMD is a reflective spatial modulation element, but FIGS. 15A and 15B are developed views for explaining the optical relationship.

  Image data corresponding to the exposure pattern is input to a controller (not shown) connected to the DMD 50 and temporarily stored in a frame memory in the controller. This image data is data representing the density of each pixel constituting the image by binary values (whether or not dots are recorded).

  The stage 152 that has adsorbed the photosensitive material 150 to the surface is moved at a constant speed from the upstream side to the downstream side of the gate 160 along the guide 158 by a driving device (not shown). When the leading edge of the photosensitive material 150 is detected by the detection sensor 164 attached to the gate 160 when the stage 152 passes under the gate 160, the image data stored in the frame memory is sequentially read out for a plurality of lines. A control signal is generated for each exposure head 166 based on the image data read by the data processing unit. Then, each of the micromirrors of the DMD 50 is controlled on and off for each exposure head 166 based on the generated control signal by the mirror drive control unit.

  When the DMD 50 is irradiated with laser light from the fiber array light source 66, the laser light reflected when the micro mirror of the DMD 50 is in an on state forms an image on the exposed surface 56 of the photosensitive material 150 by the lens systems 54 and 58. Is done. In this way, the laser light emitted from the fiber array light source 66 is turned on and off for each pixel, and the photosensitive material 150 is exposed in pixel units (exposure area 168) that is approximately the same number as the number of pixels used in the DMD 50. Further, when the photosensitive material 150 is moved at a constant speed together with the stage 152, the photosensitive material 150 is sub-scanned in the direction opposite to the stage moving direction by the scanner 162, and a strip-shaped exposed region 170 is formed for each exposure head 166. It is formed.

  As shown in FIGS. 16A and 16B, in the DMD 50, 768 sets of micromirror arrays in which 1024 micromirrors are arranged in the main scanning direction are arranged in the sub-scanning direction. Thus, only a part of the micro mirror rows (for example, 1024 × 128 rows) is driven.

  As shown in FIG. 16A, a micromirror array arranged at the center of the DMD 50 may be used, and as shown in FIG. 16B, the micromirror array arranged at the end of the DMD 50 is used. May be used. In addition, when a defect occurs in some of the micromirrors, the micromirror array to be used may be appropriately changed depending on the situation, such as using a micromirror array in which no defect has occurred.

  Since the data processing speed of the DMD 50 is limited and the modulation speed per line is determined in proportion to the number of pixels used, the modulation speed per line can be increased by using only a part of the micromirror rows. Get faster. On the other hand, in the case of an exposure method in which the exposure head is continuously moved relative to the exposure surface, it is not necessary to use all the pixels in the sub-scanning direction.

  For example, in the case of using only 384 sets out of 768 sets of micromirror arrays, the modulation can be performed twice as fast per line as compared with the case of using all 768 sets. Also, when only 256 pairs are used in the 768 sets of micromirror arrays, modulation can be performed three times faster per line than when all 768 sets are used. That is, an area of 500 mm in the sub-scanning direction can be exposed in 17 seconds. Further, when only 128 sets are used, modulation can be performed 6 times faster per line. That is, an area of 500 mm in the sub-scanning direction can be exposed in 9 seconds.

  The number of micromirror rows to be used, that is, the number of micromirrors arranged in the sub-scanning direction is preferably 10 or more and 200 or less, and more preferably 10 or more and 100 or less. Since the area per micromirror corresponding to one pixel is 15 μm × 15 μm, when converted to the use area of DMD50, an area of 12 mm × 150 μm or more and 12 mm × 3 mm or less is preferable, 12 mm × 150 μm or more and 12 mm A region of × 1.5 mm or less is more preferable.

  If the number of micromirror rows to be used is within the above range, as shown in FIGS. 17A and 17B, the laser light emitted from the fiber array light source 66 is made into substantially parallel light by the lens system 67, and the DMD 50 Can be irradiated. It is preferable that the irradiation area where the laser beam is irradiated by the DMD 50 coincides with the use area of the DMD 50. When the irradiation area is wider than the use area, the utilization efficiency of the laser light is lowered.

  On the other hand, the diameter of the light beam condensed on the DMD 50 in the sub-scanning direction needs to be reduced according to the number of micromirrors arranged in the sub-scanning direction by the lens system 67, but the number of micromirror rows to be used. Is less than 10, it is not preferable because the angle of the light beam incident on the DMD 50 increases and the depth of focus of the light beam on the scanning surface 56 becomes shallow. Further, the number of micromirror rows to be used is preferably 200 or less from the viewpoint of modulation speed. DMD is a reflective spatial modulation element, but FIGS. 17A and 17B are developed views for explaining the optical relationship.

  When the sub scanning of the photosensitive material 150 by the scanner 162 is completed and the rear end of the photosensitive material 150 is detected by the detection sensor 164, the stage 152 is moved along the guide 158 by the driving device (not shown) on the most upstream side of the gate 160. Returned to the origin at the point, and again moved along the guide 158 from the upstream side to the downstream side of the gate 160 at a constant speed.

  As described above, the exposure unit (exposure apparatus) includes the DMD in which 768 micromirror arrays in which 1024 micromirrors are arranged in the main scanning direction are arranged in the subscanning direction. Since the control is performed so that only the micromirror array is driven, the modulation speed per line becomes faster than when all the micromirror arrays are driven. This enables high-speed exposure.

  By using such an apparatus, pattern exposure is performed, and then development is performed. Unexposed portions, that is, uncured photosensitive layers are removed by development to form a pattern. When the photosensitive layer is formed by the transfer method, a thermoplastic resin layer existing on the surface of the photosensitive layer, or, if there is an intermediate layer, a thermoplastic resin layer and an intermediate layer are dissolved in the photosensitive layer. It is removed together with the area (unexposed area). As a result, a pattern-like structure made of a cured resin is formed on the substrate surface.

(Development process)
Development can be carried out in accordance with a known alkali development method. For example, using a solvent or an aqueous developer, particularly an alkaline aqueous solution (alkaline developer), the photosensitive transfer material after exposure is stored in the developer. The film can be immersed in the developing bath or sprayed on the photosensitive transfer material with a spray or the like, and further rubbed with a rotating brush, a wet sponge, etc., or processed while being irradiated with ultrasonic waves. . The liquid temperature of the developer is preferably 20 ° C. to 40 ° C., and the pH of the developer is preferably 8 to 13. Moreover, it is preferable to perform a water washing process after image development.

As a development method, a known method such as paddle development, shower development, shower & spin development, dip development or the like can be used.
In the case of shower development, an uncured portion can be removed by spraying a developer onto the exposed photosensitive layer by shower. In addition, before development, it is preferable to previously spray an alkaline aqueous solution having a low solubility of the photosensitive layer with a shower or the like to remove the thermoplastic resin layer, the intermediate layer, and the like.

In the process of development after exposure and removal of unnecessary parts, the alkaline aqueous solution used for dissolving the photosensitive layer, the thermoplastic resin layer, and the intermediate layer is preferably, for example, a dilute aqueous solution of an alkaline substance and more miscible with water. What added a small amount of organic solvent is also preferable.
The alkaline substance is not particularly limited and can be appropriately selected according to the purpose. For example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, Alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate, alkali metal silicates such as sodium silicate and potassium silicate, alkali metal metasilicates such as sodium metasilicate and potassium metasilicate, triethanolamine, diethanolamine , Tetraalkylammonium hydroxides such as monoethanolamine, morpholine, tetramethylammonium hydroxide, or trisodium phosphate. These may be used in combination of two or more, in addition to being used alone.
As alkaline aqueous solution, it is preferable that the density | concentration of an alkaline substance is 0.01-30 mass%, and it is preferable that pH is 8-14.

A roller conveyor or the like is installed in the developing tank, and the substrate moves horizontally. In order to prevent scratches on the roller conveyor, the photosensitive layer is preferably formed on the upper surface of the substrate. When the substrate size exceeds 1 meter, when the substrate is transported horizontally, the developer stays in the vicinity of the center of the substrate, and a difference in development between the center of the substrate and the peripheral portion becomes a problem. In order to avoid this, it is desirable to incline the substrate diagonally. The inclination angle is preferably 5 ° to 30 °.
In addition, it is preferable to spray pure water before development and moisten the photosensitive layer because a uniform development result is obtained.
Further, after the development, if air is blown lightly on the substrate to remove the excess liquid substantially and then washing with shower water is performed, a more uniform development result is obtained. Further, if the residue is removed by spraying ultrapure water at a pressure of 3 to 10 MPa with an ultra-high pressure cleaning nozzle before washing with water, a high-quality image without residue can be obtained. If the substrate is transported to a subsequent process with water droplets attached thereto, the process is soiled or stains remain on the substrate. Therefore, it is preferable to drain water with an air knife to remove excess water or water droplets.

(Post exposure)
Post-exposure is preferably performed between development and heat treatment from the viewpoints of controlling the cross-sectional shape of the image, controlling the hardness of the image, controlling the surface unevenness of the image, and controlling the film thickness reduction of the image. Examples of the light source used for the post-exposure include an ultra-high pressure mercury lamp, a high-pressure mercury lamp, and a metal halide lamp described in paragraph No. 0074 of JP-A-2005-3861. In the post-exposure, it is preferable from the viewpoint of simplification of equipment and power saving that the substrate is directly irradiated with light from a light source such as an ultra-high pressure mercury lamp or a metal halide without using an exposure mask. Implement from both sides as needed. The exposure amount is also adjusted as appropriate according to the control purpose in the range of the upper surface: 100 to 2000 mJ / square centimeter and the lower surface: 100 to 2000 mJ / square centimeter.

  The water-miscible organic solvent can be appropriately selected according to the purpose. For example, methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, ethylene glycol mono n-butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N- Examples include methyl pyrrolidone. The addition amount of the organic solvent having water miscibility is preferably 0.1 to 30% by mass.

  In addition, a well-known various surfactant can be added to alkaline aqueous solution, and it is preferable that the addition amount in the case of adding this surfactant is 0.01-10 mass%.

[Heat treatment process]
A heat treatment process in which the photosensitive layer patterned by the above-described process is heat-treated so that the crosslinking reaction rate is 86 to 100% for the purpose of accelerating polymerization in the cured region or promoting the crosslinking reaction and improving the strength of the pattern. Can be applied. By this step, crosslinking of the crosslinkable group of the resin portion (polymeric monomer such as a polymer substance, monomer, oligomer, etc.) in the layer is promoted to form a hard film. At this time, it can adjust so that a crosslinking reaction rate may be in the range of 86 to 100% by adjusting heating temperature and heating time.
The crosslinking reaction rate is more preferably 90 to 100%, and most preferably 95 to 100%.

The heating temperature and heating time can be set at a high temperature and a short time so that yellowing due to heat treatment is small and production tact is not lost.
The temperature of the heat treatment is preferably in the range of 150 ° C to 250 ° C. When the temperature is 150 ° C. or lower, the hardness is insufficient, and when the temperature is 250 ° C. or higher, the resin may be colored. The heat treatment time is preferably 10 minutes to 150 minutes. If it is less than 10 minutes, the hardness is insufficient, and if it is 150 minutes or more, the resin may be colored.
As described above, a pattern having high strength and excellent deformation recovery property when plastically deformed can be formed. Such a pattern is useful for forming a photo spacer.

  To prepare a photospacer, prepare a photosensitive material having a photosensitive layer composed of a photosensitive resin composition containing an ethylenically unsaturated compound, a photopolymerization initiator, and a binder, and remove the protective film. The exposed surface of the photosensitive layer is superimposed on the substrate surface, laminated and bonded, and the temporary support is peeled off at the interface with the thermoplastic resin layer to transfer the photosensitive layer onto the substrate (photosensitive layer forming step). . Thereafter, the photosensitive layer is exposed through a predetermined mask through a thermoplastic resin layer and an intermediate layer, and an unexposed portion of the photosensitive layer is developed and removed using an alkaline aqueous solution to form a spacer pattern (patterning step). ). A photo spacer can be obtained by heat-treating the formed spacer pattern to cure the exposed portion so that the crosslinking reaction rate is 86 to 100% (heat treatment step).

<Liquid crystal display device>
The liquid crystal display device of the present invention has a substrate with a spacer obtained by the method for producing a substrate with a spacer of the present invention. As one of the liquid crystal display devices, at least one includes a liquid crystal layer and liquid crystal driving means (simple matrix driving method and active matrix driving method) between a pair of substrates that are light transmissive (including the substrate with a spacer of the present invention). ) At least.

Since the photo-spacer having a uniform height and excellent deformation recovery property is provided on the substrate with the spacer, the liquid crystal display device including the substrate with the spacer has a cell gap unevenness between the substrate with the spacer and the counter substrate ( Occurrence of cell thickness fluctuations) can be suppressed, and display unevenness such as color unevenness can be effectively prevented. Thereby, the produced liquid crystal display device can display a vivid image.
In the substrate with spacers of the present invention, the photo spacer is preferably formed on a display light-shielding portion such as a black matrix formed on the substrate or on a driving element such as a TFT. A transparent conductive layer (transparent electrode) such as ITO or a liquid crystal alignment film such as polyimide may be present between the light-shielding portion for display such as TFT or a driving element such as TFT and the photo spacer.

  For example, when the photo spacer is provided on the display light-shielding portion or the driving element, the display light-shielding portion (black matrix or the like) or the driving element previously disposed on the substrate is covered with, for example, a photosensitive transfer material. The photosensitive layer is laminated on the substrate surface, peeled and transferred to form a photosensitive layer, and then subjected to exposure, development, heat treatment, etc. to form a photo spacer, whereby the substrate with a spacer of the present invention (liquid crystal display) Device substrate) can be manufactured.

  As another aspect of the liquid crystal display device, at least one of them includes a liquid crystal layer and a liquid crystal driving means between a pair of light-transmitting substrates (including the substrate with a spacer of the present invention), and the liquid crystal driving means It has an active element (for example, TFT) and is configured to be regulated to a predetermined width by a photo spacer having a uniform height between a pair of substrates and excellent deformation recovery. Also in this case, the substrate with spacer according to the present invention is configured as a color filter substrate having a plurality of RGB pixel groups, and each pixel constituting the pixel group is separated from each other by a black matrix.

Examples of the liquid crystal usable in the present invention include nematic liquid crystal, cholesteric liquid crystal, smectic liquid crystal, and ferroelectric liquid crystal.
The substrate with spacers preferably has colored pixels as a color filter, and the pixel group is composed of two-color pixels having different colors or three-color pixels, four-color pixels or more. It may be. For example, in the case of three colors, it is composed of three hues of red (R), green (G), and blue (B). When arranging pixel groups of three colors of RGB, arrangement of mosaic type, triangle type, etc. is preferable, and when arranging pixel groups of four colors or more, any arrangement may be used. For producing the color filter, for example, a black matrix may be formed after forming a pixel group of two or more colors, or conversely, a pixel group may be formed after forming a black matrix. Regarding the formation of RGB pixels, JP 2004-347831 A can be referred to.

  The liquid crystal display device of the present invention is suitably used for an LED display device. The liquid crystal display mode in the liquid crystal display device includes STN type, TN type, GH type, ECB type, ferroelectric liquid crystal, antiferroelectric liquid crystal, VA type, IPS type, OCB type, ASM type, and various other types. Preferably mentioned. As a liquid crystal display device of the present invention, by forming a spacer by the method of the present invention, a display mode in which display unevenness is likely to occur due to variations in the cell thickness of the liquid crystal cell, for example, a VA display mode in which the cell thickness is 2 to 4 μm When used in the display mode of the IPS type display mode and the OCB type display mode, it is preferable because effective display unevenness suppression is achieved.

  The basic configuration of the liquid crystal display device includes: (a) a driving side substrate in which driving elements such as thin film transistors (TFTs) and pixel electrodes (conductive layers) are arranged; and a counter electrode (conductive layer). The counter substrate is arranged to be opposed to each other with a photo spacer interposed therebetween, and a liquid crystal material is sealed in the gap, and (b) the driving substrate and the counter substrate having the counter electrode (conductive layer) are arranged as a photo spacer. The liquid crystal display device of the present invention can be suitably applied to various types of liquid crystal display devices.

  The liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, side industry research committee, published in 1994)”. The liquid crystal display device of the present invention is not particularly limited other than having the substrate with a spacer of the present invention, and can be configured into various types of liquid crystal display devices described in, for example, the “next generation liquid crystal display technology”. . In particular, it is effective in constructing a color TFT liquid crystal display device. The color TFT liquid crystal display device is described, for example, in “Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)”.

  The liquid crystal display device has various substrates such as an electrode substrate, a polarizing film, a retardation film, a backlight, a viewing angle compensation film, an antireflection film, a light diffusion film, and an antiglare film, except for having the substrate with a spacer of the present invention. It can be generally constructed using members. Regarding these components, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC Co., Ltd., published in 1994)”, “Current Status and Future Prospects of the 2003 Liquid Crystal Related Market (Volume 2)” (Fuji Chimera Research Institute, Inc., 2003, etc.) ”.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass. Further, “weight average molecular weight” in the text is measured by SEC (Size Exclusion Chromatography) method unless otherwise specified.

  In the present embodiment, the combination of the transfer method and the LED backlight will be described in detail. However, in the present invention, it may be performed by a coating method using a slit coater or the like, and the backlight uses a cold cathode tube. May be configured.

Example 1 Transfer Method An MVA mode liquid crystal display device configured as shown in FIG. 18 was produced as follows.
-Fabrication of color filter substrate-
<Preparation of photosensitive transfer material>
Using a slit-like nozzle on a 75 μm thick polyethylene terephthalate film temporary support (PET temporary support), a thermoplastic resin layer coating solution having the following formulation H1 is applied and dried to form a thermoplastic resin layer. Formed. Next, an intermediate layer coating solution having the following formulation P1 was applied onto the thermoplastic resin layer and dried to laminate the intermediate layer. On this intermediate layer, a colored photosensitive resin composition K1 having the composition described in Table 1 (transfer method) below was further applied and dried to laminate a photosensitive layer. Thus, a thermoplastic resin layer having a dry film thickness of 15 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a photosensitive layer having a dry film thickness of 2.4 μm are provided on the PET temporary support, A protective film (12 μm thick polypropylene film) was pressure-bonded on the top.

Note 1) B-CIM (2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, manufactured by Hodogaya Chemical Co., Ltd.)
Note 2) NBCA (10-n-butyl-2-chloroacridone, manufactured by Kurokin Kasei)

  In the manner described above, a temporary transfer support, a thermoplastic resin layer, an intermediate layer (oxygen barrier film), and a black (K) photosensitive layer were laminated to produce a photosensitive transfer material configured as a laminate (hereinafter referred to as a laminate). , Referred to as photosensitive transfer material K1).

[Prescription H1 of coating solution for thermoplastic resin layer]
-Methanol 11.1 parts-Propylene glycol monomethyl ether acetate 6.4 parts-Methyl ethyl ketone 52.4 parts-Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer 5.83 parts [Copolymerization ratio (molar ratio) ) = 55 / 11.7 / 4.5 / 28.8,
Weight average molecular weight = 100,000, Tg≈70 ° C.)
Styrene / acrylic acid copolymer 13.6 parts [copolymerization ratio (molar ratio) = 63/37, weight average molecular weight = 10,000, Tg≈100 ° C.]
・ 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane (manufactured by Shin-Nakamura Chemical Co., Ltd.) 9.1 parts Surfactant 1 0.54 parts

* Surfactant 1:
MegaFuck F-780-F (Dainippon Ink Chemical Co., Ltd.)
〔composition〕
C ₆ F ₁₃ CH ₂ CH ₂ OCOCH═CH ₂ (40 parts) and H (OCH (CH ₃ ) CH ₂ ) ₇ OCOCH═CH ₂ (55 parts) and H (OCH ₂ CH ₂ ) ₇ OCOCH═CH ₂ (5 parts) Copolymer (weight average molecular weight 30,000) 30 parts ・ Methyl ethyl ketone 70 parts

[Prescription P1 of coating solution for intermediate layer]
2.1 parts of polyvinyl alcohol (PVA-205 (saponification rate = 88%), manufactured by Kuraray Co., Ltd.)
-Polyvinylpyrrolidone 0.95 part (PVP, K-30; made by IS Japan)
・ Methanol 44 parts ・ Distilled water 53 parts

  Next, the colored photosensitive resin composition K1 used in the production of the obtained photosensitive transfer material K1 was used as the colored photosensitive resin composition R1, G1, and B1 having the composition described in Table 1 (transfer method). Photosensitive transfer materials R1, G1, and B1 were produced in the same manner as described above except that they were replaced with.

<Preparation of color filter substrate>
-Formation of black (K) image-
A non-alkali glass substrate having a size of 680 × 880 mm was washed with a rotating brush having nylon bristles while spraying a glass detergent solution adjusted to 25 ° C. with a shower for 20 seconds, washed with pure water, and then washed with a silane coupling solution by a shower. (N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane 0.3 mass% aqueous solution; trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds and washed with pure water shower. After cleaning, the glass substrate was heated at 100 ° C. for 2 minutes with a substrate preheating device.

  Next, after the protective film of the photosensitive transfer material K1 is peeled off, the exposed photosensitive layer is overlaid so as to be in contact with the surface of the glass substrate heated at 100 ° C. for 2 minutes to form a laminator Lamic II type [Hitachi Industry Co., Ltd. Using a rubber roller temperature of 130 ° C., a linear pressure of 100 N / cm, and a conveying speed of 2.2 m / min. Next, the PET temporary support was peeled off and transferred onto a glass substrate.

Next, the photosensitive layer on the substrate was exposed at 30 mJ / cm ² . At that time, it was performed at 405 nm using a pattern forming apparatus described below.

-Pattern forming device-
A pattern forming apparatus provided with the exposure head shown in FIG. 19 was used. FIG. 19 shows DMD 50, light irradiating means 144 for irradiating the DMD 50 with laser light, lens systems (imaging optical systems) 454, 458, and DMD 50 for enlarging and imaging the laser light reflected by the DMD 50. A microlens array 472 in which a large number of microlenses 474 are arranged in correspondence with each other, an aperture array 476 in which a large number of apertures 478 are provided in correspondence with each microlens of the microlens array 472, and laser light that has passed through the apertures An exposure head composed of lens systems (imaging optical systems) 480 and 482 for forming an image on the exposure surface 56 (composition composition layer) is shown.
In FIG. 19, a combined laser light source shown in FIGS. As the DMD 50, only 800 × the number of columns in the use area among the light modulation means in which 1024 micromirror rows arranged in the main scanning direction shown in FIG. A DMD controlled to drive was used. In addition, the aperture array 476 disposed in the vicinity of the condensing position of the microlens array 472 is disposed so that only light that has passed through the corresponding microlens 474 is incident on each aperture 478.

A toric lens is used as the microlens 474, and the radius of curvature Rx = −0.125 mm in the direction optically corresponding to the x direction and the radius of curvature Ry = −0.1 mm in the direction corresponding to the y direction. is there.
Hereinafter, this pattern forming apparatus may be referred to as a “DI exposure apparatus according to the present invention”.

  Next, a triethanolamine developer (triethanolamine 30% by mass, polypropylene glycol, glycerol monostearate, polyoxyethylene sorbitan monostearate, stearyl ether in total 0.1% by mass, the balance of pure water The prepared and stored stock solution was diluted 12 times with pure water (a solution obtained by diluting 1 part by weight of the stock solution and 11 parts by weight of pure water) at 30 ° C. for 50 seconds with a flat nozzle. Shower development was performed at a pressure of 0.04 MPa, and the thermoplastic resin layer and the intermediate layer were removed. Subsequently, after air was blown off on the upper surface of the substrate, pure water was sprayed for 10 seconds by a shower, pure water shower cleaning was performed, and air was blown to reduce a liquid pool on the substrate.

  Next, a sodium carbonate developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% by weight sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, stable Agent developed, trade name: T-CD1, Fuji Photo Film Co., Ltd. solution diluted 5 times with pure water) at 29 ° C. for 30 seconds, cone-type nozzle pressure 0.15 MPa, shower developed, A pattern pixel was obtained.

Next, using a detergent (phosphate, silicate, nonionic surfactant, antifoaming agent, and stabilizer; trade name: T-SD1, manufactured by Fuji Photo Film Co., Ltd.) at 33 ° C. for 20 seconds The residue was removed using a rotating brush having a shower and nylon bristles at a cone type nozzle pressure of 0.02 MPa, thereby forming a black (K) image 916 on a glass substrate 911 as shown in FIG. Thereafter, the substrate was further post-exposed with 500 mJ / cm ² light from the side on which the K image was formed with an ultrahigh pressure mercury lamp, and then heat-treated at 220 ° C. for 15 minutes.

  After that, the glass substrate 911 on which the K image 916 is formed is again washed with a brush as described above and washed with a pure water shower. After that, without using a silane coupling liquid, the substrate preheating device is used at 100 ° C. for 2 minutes. Heated.

-Formation of red (R) pixels-
The same process as the formation of the K image 916 is performed on the glass substrate 911 on which the K image 916 is formed using the photosensitive transfer material R1 obtained as described above, and the K image 916 of the glass substrate 911 is formed. A red pixel (R pixel) was formed on the side. However, the exposure amount in the exposure step was 15 mJ / cm ^2, and shower development with a sodium carbonate-based developer was performed at 35 ° C. for 35 seconds.
The thickness of the R pixel is 2.0 μm. I. Pigment Red (C.I.P.R.) 254, C.I. I. P. R. The coating amount of 177 was 0.88 g / m ² and 0.22 g / m ² , respectively.
Thereafter, the glass substrate 911 on which the R pixels are formed is again cleaned with a brush using a cleaning agent as described above, and shower-washed with pure water. Then, without using a silane coupling solution, the substrate preheating device is used. Heated at 100 ° C. for 2 minutes.

-Formation of green (G) pixels-
Next, using the photosensitive transfer material G1 obtained above, the same process as the formation of the K image 916 is performed, and a green pixel (G) is formed on the side of the glass substrate 911 where the K image 916, the R pixel, and the like are formed. Pixel). However, the exposure amount in the exposure step was 15 mJ / cm ² , and shower development with a sodium carbonate-based developer was performed at 34 ° C. for 45 seconds.
The G pixel has a thickness of 2.0 μm. I. Pigment green (C.I.P.G.) 36, C.I. I. Pigment Yellow (C.I.P.Y.) each coating amount of 150 1.12g ^/ m 2, was 0.48 g / ^{m 2.}
Thereafter, the glass substrate 911 on which the R pixel and the G pixel are formed is again cleaned with a brush using a cleaning agent as described above, shower-washed with pure water, and without using a silane coupling liquid. It heated at 100 degreeC with the heating apparatus for 2 minutes.

-Formation of blue (B) pixels-
Next, using the photosensitive transfer material B1 obtained above, the same process as the formation of the K image 916 is performed, and a blue pixel is formed on the side of the glass substrate 911 where the K image 916, R pixel, and G pixel are formed. (B pixel) was formed. However, the exposure amount in the exposure process was 15 mJ / cm ² , and shower development with a sodium carbonate-based developer was performed at 36 ° C. for 40 seconds.
The thickness of the B pixel is 2.0 μm. I. Pigment Blue (C.I.P.B.) 15: 6, C.I. I. Pigment Violet (C.I.P.V.) each coating amount of 23 0.63g ^/ m 2, was 0.07 g / ^{m 2.}

Thereafter, the glass substrate 911 on which the R, G, and B pixels were formed was baked at 240 ° C. for 50 minutes to obtain a color filter 912.
Further, an ITO (Indium Tin Oxide) film 913 was formed thereon as a transparent electrode by sputtering to obtain a color filter substrate 910.

Here, the preparation of the colored photosensitive resin compositions K1, R1, G1, and B1 described in Table 1 will be described.
<Preparation of colored photosensitive resin composition K1>
The colored photosensitive resin composition K1 was prepared by weighing out K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 above and mixing at 150 ° C. at a temperature of 24 ° C. (± 2 ° C.). p. m. Then, methyl ethyl ketone, binder 1, hydroquinone monomethyl ether, DPHA solution, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, sensitizing dye (in the amount shown in Table 1 above) A-2) (NBCA), N-phenyl-2-mercaptobenzimidazole, and surfactant 1 are weighed and added in this order at a temperature of 25 ° C. (± 2 ° C.), and a temperature of 40 ° C. (± 2 ° C.). 150r. p. m. For 30 minutes.

The detail of each composition in the composition of the said Table 1 is as follows. The surfactant 1 is as described above.
* Composition of K pigment dispersion 1-13.1 parts of carbon black (Special Black 250, manufactured by Degussa)
5- [3-oxo-2- [4- [3,5-bis (3-diethylaminopropylaminocarbonyl) phenyl] aminocarbonyl] phenylazo] -butyroylaminobenzimidazolone 0.65 parts Polymer [benzyl methacrylate / Random copolymer of methacrylic acid (= 72/28 [molar ratio]) (weight average molecular weight 37,000)] 6.72 parts Propylene glycol monomethyl ether acetate 79.53 parts

* Binder 1 composition -Random copolymer of polymer [benzyl methacrylate / methacrylic acid (= 78/22 [molar ratio]) (weight average molecular weight 40,000)] 27 parts -Propylene glycol monomethyl ether acetate 73 parts * DPHA solution Composition of dipentaerythritol hexaacrylate (containing 500 ppm of polymerization inhibitor MEHQ, trade name: KAYARAD DPHA, Nippon Kayaku Co., Ltd.) 76 parts Propylene glycol monomethyl ether 24 parts

<Preparation of colored photosensitive resin composition R1>
The colored photosensitive resin composition R1 weighs the R pigment dispersion 1, the R pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts described in Table 1 (transfer method), and the temperature is 24 ° C. (± 2 ° C.). ) For 150 r. p. m. And then, the amount of methyl ethyl ketone, binder 2, DPHA solution, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, and sensitizing dye (A-2) shown in Table 1 above. (NBCA), N-phenyl-2-mercaptobenzimidazole, and phenothiazine were weighed out and added in this order at a temperature of 24 ° C. (± 2 ° C.). p. m. At a temperature of 24 ° C. (± 2 ° C.) and mixed for 150 r. p. m. And the surfactant 1 in the amount shown in Table 1 above is weighed out and added at a temperature of 24 ° C. (± 2 ° C.) for 30 r. p. m. For 30 minutes and filtered through nylon mesh # 200.

In addition, the detail of each composition in composition R1 of the said Table 1 is as follows. The compositions of the DPHA liquid and the surfactant 1 are the same as those of the colored photosensitive resin composition K1.
* Composition of R pigment dispersion 1-C.I. I. Pigment Red 254 8.0 parts 5- [3-oxo-2- [4- [3,5-bis (3-diethylaminopropylaminocarbonyl) phenyl] aminocarbonyl] phenylazo] -butyroylaminobenzimidazolone 0 .8 parts Random copolymer of polymer [benzyl methacrylate / methacrylic acid (= 72/28 [molar ratio]) (weight average molecular weight 37,000)] 8.0 parts ・ Propylene glycol monomethyl ether acetate 83.2 parts

* Composition of R pigment dispersion 2-C.I. I. Pigment Red 177 18 parts Polymer (benzyl methacrylate / methacrylic acid (= 72/28 [molar ratio]) random copolymer (weight average molecular weight 37,000)] 12 parts Propylene glycol monomethyl ether acetate 70 parts * Binder Composition of 2 ・ Random copolymer of benzyl methacrylate / methacrylic acid / methyl methacrylate (= 38/25/37 [molar ratio]) (weight average molecular weight 30,000) 27 parts ・ Propylene glycol monomethyl ether acetate 73 parts * Additive 1: Phosphate ester special activator (HIPLAAD ED152, manufactured by Enomoto Kasei Co., Ltd.)

<Preparation of colored photosensitive resin composition G1>
The colored photosensitive resin composition G1 weighs the G pigment dispersion 1, the Y pigment dispersion 1, and propylene glycol monomethyl ether acetate in the amounts described in Table 1 (transfer method), and the temperature is 24 ° C. (± 2 ° C.). ) For 150 r. p. m. Then, methyl ethyl ketone, cyclohexanone, binder 1, DPHA solution, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, sensitizing dye (A- 2) Weigh out (NBCA), N-phenyl-2-mercaptobenzimidazole, and phenothiazine and add them in this order at a temperature of 24 ° C. (± 2 ° C.). p. m. The surfactant 1 in the amount shown in Table 1 above is weighed and added at a temperature of 24 ° C. (± 2 ° C.) and added for 30 r. p. m. For 5 minutes and filtered through nylon mesh # 200.

In addition, the detail of each composition in the composition G1 of the said Table 1 is as follows. Moreover, the composition of the binder 1, the DPHA liquid, and the surfactant 1 is the same as that of the colored photosensitive resin composition K1.
* Composition of G pigment dispersion 1-C.I. I. Pigment Green 36 18 parts Polymer (benzyl methacrylate / methacrylic acid (= 72/28 [molar ratio]) random copolymer (weight average molecular weight 37,000)] 12 parts Cyclohexanone 35 parts Propylene glycol monomethyl ether acetate 35 parts * Y pigment dispersion 1
Product name: CF Yellow EX3393 (manufactured by Gokoku Color Co., Ltd.)

<Preparation of colored photosensitive resin composition B1>
The colored photosensitive resin composition B1 weighs out the B pigment dispersion 1, the B pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts described in Table 1 (transfer method), and the temperature is 24 ° C. (± 2 ° C.). ) For 150 r. p. m. And then, the amount of methyl ethyl ketone, binder 3, DPHA solution, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, and sensitizing dye (A-2) shown in Table 1 above. (NBCA), N-phenyl-2-mercaptobenzimidazole, and phenothiazine were weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.), and 150 r. p. m. The surfactant 1 in the amount shown in Table 1 above is weighed and added at a temperature of 24 ° C. (± 2 ° C.) and added for 30 r. p. m. For 5 minutes and filtered through nylon mesh # 200.

In addition, the detail of each composition in composition B1 of the said Table 1 is as follows. Moreover, the composition of DPHA liquid and surfactant 1 is the same as that of the colored photosensitive resin composition K1.
* B Pigment dispersion 1
Product name: CF Blue EX3357 (manufactured by Gokoku Dye)
* B Pigment dispersion 2
Product name: CF Blue EX3383 (manufactured by Gokoku Dye)
* Composition of binder 3-Random copolymer (weight average molecular weight 30,000) of benzyl methacrylate / methacrylic acid / methyl methacrylate (= 36/22/42 [molar ratio]) 27 parts-73 parts of propylene glycol monomethyl ether acetate

-Production of photosensitive transfer sheet for spacers-
On a 75 μm thick polyethylene terephthalate film temporary support (PET temporary support), the thermoplastic resin layer coating solution comprising the above formulation H1 is applied and dried to form a thermoplastic resin layer having a dry layer thickness of 6.0 μm. did.

  Next, on the formed thermoplastic resin layer, the intermediate layer coating liquid composed of the above-mentioned formulation P1 was applied and dried to laminate an intermediate layer having a dry layer thickness of 1.5 μm.

  Next, the following photosensitive layer coating solution (1) for forming a spacer was further applied on the formed intermediate layer and dried to laminate a photosensitive layer having a dry layer thickness of 4.1 μm.

[Photosensitive layer coating solution (1)]
-Pigment 93.3 parts-1-methoxy-2-propyl acetate 485.2 parts-Methyl ethyl ketone 278.2 parts-Methanol 4.5 parts-Binder 4 56.5 parts-DPHA solution 55.8 parts-2- (o -Chlorophenyl) -4,5-diphenylimidazole dimmer
(Initiator: Lophine dimer) 9.8 parts. Sensitizing dye (A-2) (NBCA) 1.51 parts. Hydrogen donor NPhMBI (N-phenylmercaptobenzimidazole) 0.84 parts. Hydroquinone monomethyl ether. 02 parts ・ Surfactant 1 0.67 parts ・ Discoloring dye 13.6 parts

In addition, the detail of each composition in the said prescription is as follows.
* Pigment-30% methyl isobutyl ketone dispersion of silica sol (trade name: MIBK-ST, manufactured by Nissan Chemical Industries, Ltd.)
* Binder 4
-Methacrylic acid / allyl methacrylate copolymer (= 20/80 [molar ratio], weight average molecular weight 36000; polymer substance)
* Decoloring dyes ・ Victoria Pure Blue BOH-M (Hodogaya Chemical Co., Ltd.)

  As described above, a laminated structure of PET temporary support / thermoplastic resin layer / intermediate layer / photosensitive layer (total thickness of 3 layers is 11.6 μm) is formed, and then a cover film is further formed on the surface of the photosensitive layer. A polypropylene film having a thickness of 12 μm was applied by heating and pressing to obtain a photosensitive transfer sheet (1) for spacers.

-Fabrication of photo spacers-
The cover film of the obtained photosensitive transfer sheet for spacer (1) is peeled off, and the exposed surface of the photosensitive layer is overlaid on the ITO film 913 of the color filter substrate 910 on which the ITO film prepared above is sputtered. Then, using a laminator type Lamic II [manufactured by Hitachi Industries, Ltd.], the films were bonded at a conveyance speed of 2 m / min under pressure and heating conditions of a linear pressure of 100 N / cm and 130 ° C. Thereafter, the PET temporary support was peeled and removed at the interface with the thermoplastic resin layer, and the photosensitive layer was transferred together with the thermoplastic resin layer and the intermediate layer (photosensitive layer forming step).

(Exposure process)
The photosensitive layer on the substrate was exposed to a spacer pattern corresponding to 10 mJ / cm ² . At that time, the above-described DI exposure apparatus according to the present invention was used and performed at 405 nm.

(Development process)
The exposed photosensitive layer was allowed to stand at room temperature for 10 minutes, and then the entire surface of the photosensitive layer was coated with KOH developer (KOH, containing nonionic surfactant, product name: CDK) manufactured by Fuji Film Electronics Materials Co., Ltd. -1), shower development was performed at 25 ° C. for 60 seconds with a flat nozzle pressure of 0.04 MPa to dissolve and remove uncured regions. Subsequently, ultrapure water is sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove residues, and ultrapure water is sprayed from both sides with a shower nozzle, and the attached developer and the above-mentioned The dissolved material of the photosensitive layer was removed, and liquid was removed with an air knife to obtain a spacer pattern. The obtained spacer pattern was a transparent column having a diameter of 16 μm and an average height of 3.7 μm.

  Next, the color filter substrate 910 provided with the spacer pattern was subjected to heat treatment at 230 ° C. for 30 minutes (heat treatment step), so that a photo spacer 914 was manufactured.

-Production of photosensitive transfer material for protrusions-
On a 75 μm thick polyethylene terephthalate film temporary support (PET temporary support), a thermoplastic resin layer coating solution having the same formulation as the formulation H1 is applied and dried, and a thermoplastic resin having a dry film thickness of 15 μm is dried. A layer was provided. Next, on the formed thermoplastic resin layer, an intermediate layer coating solution having the same formulation as the formulation P1 was applied and dried to provide an intermediate layer having a dry film thickness of 1.6 μm. Next, a protrusion-forming coating liquid having the following formulation C is prepared, and this protrusion-forming coating liquid is applied onto the intermediate layer and dried to provide a liquid crystal alignment control protrusion having a dry film thickness of 2.0 μm. A photosensitive layer was coated. Further, a 12 μm-thick polypropylene film was attached to the surface of the photosensitive layer as a protective film. In this way, a photosensitive transfer material for protrusions was prepared by laminating a thermoplastic resin layer, an intermediate layer, a photosensitive layer for protrusions, and a protective film in this order from the PET temporary support side.

[Formulation C of projection forming coating liquid]
・ Positive resist solution FH-2413F 53.3 parts (manufactured by FUJIFILM Electronics Materials Co., Ltd.)
・ Methyl ethyl ketone 46.7 parts ・ Surfactant 1 0.04 parts

-Formation of protrusions-
The protective film is peeled off from the photosensitive transfer material for protrusions obtained above, and the exposed surface of the exposed photosensitive layer for protrusions is superimposed on the surface of the color filter substrate 910 on which the ITO film 913 is provided (on the color filter). Laminator Lamic II type (manufactured by Hitachi Industries, Ltd.) was used for lamination (laminate) under the conditions of a linear pressure of 100 N / cm, a temperature of 130 ° C., and a conveying speed of 2.2 m / min. Thereafter, only the PET temporary support of the photosensitive transfer material for protrusions was peeled and removed at the interface with the thermoplastic resin layer. At this time, the photosensitive layer, the intermediate layer, and the thermoplastic resin layer are sequentially laminated on the color filter substrate from the substrate side.

  Next, pattern exposure was performed from above the thermoplastic resin layer, which is the outermost layer, in the same manner as the exposure step in the production of the photo spacer described above. Thereafter, development was performed in the same manner as described above, and the thermoplastic resin layer and the intermediate layer were dissolved and removed. At this stage, the photosensitive layer for protrusions was not substantially developed. Subsequently, an aqueous solution containing 0.085 mol / L sodium carbonate, 0.085 mol / L sodium hydrogen carbonate and 1% sodium dibutylnaphthalene sulfonate is further sprayed at 33 ° C. for 30 seconds using a shower type developing device. Development was performed to remove unnecessary portions (uncured portions) of the photosensitive layer for protrusions. As a result, a protrusion 915 made of a photosensitive layer for protrusion patterned into a desired shape was formed on the color filter (RGB pixel). Next, the color filter substrate on which the protrusions 915 are formed is baked at 240 ° C. for 50 minutes, thereby controlling the liquid crystal alignment with a height of 1.5 μm and a vertical cross-sectional shape on the color filter (RGB pixel). Protrusions were formed.

  Apart from the above, a TFT substrate 921 was prepared as a counter substrate. An ITO (Indium Tin Oxide) film 922 is formed on one surface of the TFT substrate by sputtering. Subsequently, an alignment film 924 made of polyimide was provided on the ITO film 922 of the TFT substrate and the ITO film 913 on the side of the color filter substrate 910 on which the photospacer 914 was provided.

  Thereafter, an epoxy resin sealant is printed at a position corresponding to the outer frame of the black matrix 916 provided around the pixel group of the color filter, and the color filter substrate 910 is bonded to the TFT substrate 921. . Next, the two bonded substrates were heat-treated to cure the sealing agent to obtain a laminate of the two substrates. The laminate was degassed under vacuum, then returned to atmospheric pressure, and liquid crystal was injected into the gap between the two glass substrates. After completion of the injection, a liquid crystal cell was obtained by applying an adhesive to the injection port portion and sealing by irradiation with ultraviolet rays.

  Polarizing plates (HLC2-2518, manufactured by Sanritsu Co., Ltd.) 925 and 923 were attached to both surfaces of the liquid crystal cell thus obtained. Next, although not shown in the drawing, a side light type is used by using FR1112H as a red (R) LED, DG1112H as a green (G) LED, and DB1112H as a blue (B) LED (both are chip-type LEDs manufactured by Stanley). The MVA mode liquid crystal display device of the present invention was produced by constituting a backlight and arranging it on the side of the liquid crystal cell provided with the polarizing plate.

(Evaluation)
The following evaluation was performed using the liquid crystal display device produced as described above. The results are shown in Table 2 below.
-1. Missing dots
The produced photo spacer was visually evaluated. The number of dots remaining after development was counted with respect to the target number of dots, and this ratio was defined as the dot remaining rate.
<Evaluation criteria>
：: No dot missing was observed (dot remaining rate of 99% or higher); very good ○: Dot missing was slightly recognized (dot remaining rate of 95% or higher); Good Δ: Slightly missing dot (Dot remaining rate of 90% or more): normal ×: dot missing was observed (dot remaining rate of 80% or more); somewhat bad XX: dot missing was noticeable (dot remaining rate of 70% or more) ;bad

-2. Display unevenness
Regarding the liquid crystal display device, the gray display when a gray test signal was input was observed visually and with a loupe, and the presence or absence of display unevenness was evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: No unevenness at all (very good)
B: Slight unevenness is observed on the edge of the glass substrate, but there is no problem in the display (good)
C: Slight unevenness on the display, but practical level (normal)
D: Display is uneven (somewhat bad)
E: Strong unevenness in display (very bad)

  As shown in Table 2, it was found that there was no dot missing after the formation of the photospacer, and according to the completed color filter, high-quality display without display unevenness was performed.

Example 2 Application (Liquid Registration) Method-Production of Color Filter (Application by Slit Nozzle)-
-Formation of black (K) image-
A non-alkali glass substrate having a size of 680 × 880 mm (hereinafter simply referred to as a glass substrate) was cleaned with a UV cleaning device, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The glass substrate was heat treated at 120 ° C. for 3 minutes to stabilize the surface state. Then, after cooling the glass substrate and adjusting the temperature to 23 ° C., a colored photosensitive resin having the above composition on a glass substrate coater MH-1600 (manufactured by FS Asia Co., Ltd.) having a slit-like nozzle. Composition K1 was applied. Subsequently, a part of the solvent was dried for 30 seconds using a vacuum dryer VCD (manufactured by Tokyo Ohka Kogyo Co., Ltd.) to eliminate the fluidity of the coating film, and then prebaked at 120 ° C. for 3 minutes to obtain a film thickness of 2. A 4 μm photosensitive layer K1 was formed.

Next, the photosensitive layer on the substrate was exposed at 100 mJ / cm ² . At that time, the exposure was performed at 405 nm using the DI exposure apparatus according to the present invention.
In addition, for the purpose of testing, the DI exposure apparatus according to the present invention is used to form a laser beam having a wavelength of 405 nm, a 15-step step wedge pattern (ΔlogE = 0.15), and a large number of holes having different diameters. Irradiation was performed so that a pattern was obtained, and a part of the photosensitive layer was cured.

  Next, pure water is sprayed from a shower nozzle to uniformly wet the surface of the photosensitive layer K1, and then a KOH developer (KOH, containing nonionic surfactant, trade name: CDK-1, Fuji Film Electromaterials) (Made by Co., Ltd.) was spray-developed from a flat nozzle at 23 ° C. and a nozzle pressure of 0.04 MPa for 80 seconds to obtain a black pattern (developing step). Subsequently, ultrapure water is sprayed onto the glass substrate on which the black pattern is formed at a pressure of 9.8 MPa by an ultrahigh pressure cleaning nozzle to remove the residue, and a black (K) image is formed on the alkali-free glass substrate. did. Thereafter, heat treatment (baking) was performed at 220 ° C. for 30 minutes.

-Formation of red (R) pixels-
Using the colored photosensitive resin composition R2 having the composition shown in Table 1 (Liquid Registration Method) on the glass substrate on which the K image was formed, coating, exposing, developing, and Baking was performed to form red pixels (R pixels) on the side of the glass substrate on which the K image was formed. However, the exposure amount in the exposure process was 80 mJ / cm ^2, and the shower development in the development process was performed at 23 ° C. for 60 seconds.
The thickness of the R pixel is 1.6 μm. I. Pigment Red (C.I.P.R.) 254, C.I. I. P. R. The coating amount of 177 was 0.88 g / m ² and 0.22 g / m ² , respectively.

-Green (G) image formation-
Next, a colored photosensitive resin composition G2 having the composition shown in Table 1 (liquid registration method) is applied to the glass substrate on which the K image and R pixel are formed in the same manner as the formation of the K image. Then, exposure, development, and baking were performed, and a green pixel (G pixel) was formed on the side of the glass substrate on which the K image, R pixel, and the like were formed. However, the exposure amount in the exposure process was 80 mJ / cm ^2, and the shower development in the development process was performed at 23 ° C. for 60 seconds.
The G pixel has a thickness of 1.6 μm. I. Pigment green (C.I.P.G.) 36, C.I. I. Pigment Yellow (C.I.P.Y.) each coating amount of 150 1.12g ^/ m 2, was 0.48 g / ^{m 2.}

-Formation of blue (B) image-
Next, using the colored photosensitive resin composition B2 having the composition shown in Table 1 (Liquid Registration Method) on the glass substrate on which the K image, R pixel, and G pixel are formed, the K image is formed. Similarly, coating, exposure, development, and baking were performed, and blue pixels (B pixels) were formed on the side of the glass substrate where the K image, R pixel, and G pixel were formed. However, the exposure amount in the exposure process was 80 mJ / cm ^2, and the shower development in the development process was performed at 23 ° C. for 60 seconds.
Note that the thickness of the B pixel is 1.6 μm. I. Pigment Blue (C.I.P.B.) 15: 6 and C.I. I. Pigment Violet (C.I.P.V.) each coating amount of 23 0.63g ^/ m 2, was 0.07 g / ^{m 2.}

In addition, preparation of colored photosensitive resin composition G2 and B2 shall be performed according to preparation of the said colored photosensitive resin composition G1 and B1, and preparation of colored photosensitive resin composition R2 is demonstrated below.
The colored photosensitive resin composition R2 weighs out the R pigment dispersion 1, R pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts described in Table 1 (liquid registration method), and the temperature is 24 ° C. (± 2 ° C.). ) For 150 r. p. m. And then the amount of methyl ethyl ketone, binder 2, DPHA solution, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, sensitizing dye (A -2) Weigh out (NBCA), N-phenyl-2-mercaptobenzimidazole, and phenothiazine and add them in this order at a temperature of 24 ° C. (± 2 ° C.). p. m. The surfactant 1 in the above amount is weighed and added at a temperature of 24 ° C. (± 2 ° C.) and added for 30 r. p. m. For 30 minutes and filtered through nylon mesh # 200.
The R pigment dispersion 1, the R pigment dispersion 2, the binder 2, the DPHA liquid, and the surfactant 1 in the colored photosensitive resin composition R2 are as described above.

  On the color filter produced as described above, an ITO film was formed by sputtering as a transparent electrode to obtain a color filter substrate.

-Production of photo spacer (liquid cash register method)-
On the ITO film of the color filter substrate on which the ITO film produced as described above is sputtered, the photosensitive layer coating is performed with a glass substrate coater MH-1600 (manufactured by FAS Asia) having a slit nozzle. Liquid (1) was applied. Subsequently, a part of the solvent was dried for 30 seconds using a vacuum dryer VCD (manufactured by Tokyo Ohka Kogyo Co., Ltd.) to eliminate the fluidity of the coating film, and then prebaked at 120 ° C. for 3 minutes to obtain a film thickness of 2. A 4 μm photosensitive layer was formed (layer forming step).
Subsequently, a photo spacer was formed on the color filter substrate by the same patterning process and heat treatment process as in Example 1. However, the exposure amount was 50 mJ / cm ² , and development with the developer was 23 ° C. for 60 seconds.

  After the production of the photospacer, the MVA mode liquid crystal display device of the present invention (see FIG. 18) was produced in the same manner as in Example 1 using this color filter substrate. The MVA mode liquid crystal display device obtained in Example 2 was evaluated in the same manner as in Example 1. The results are shown in Table 2. Also in this embodiment, it has been found that there is no missing dot after the formation of the photo spacer, and according to the completed color filter, high quality display without display unevenness is performed.

(Example 3)
In Example 1, except that the binder 4 was changed to the binder 5 below, RGBK and a photosensitive transfer material for spacer formation prepared by the same formulation and procedure were used, and the procedure of the present invention was performed in the same manner as in Example 1. An MVA mode liquid crystal display device was produced. This MVA mode liquid crystal display device was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Binder 5
・ Random copolymer of benzyl methacrylate / methacrylic acid / glycidyl methacrylate (= 47/21/32 [molar ratio]) (weight average molecular weight 40000) 27 parts ・ Propylene glycol monomethyl ether acetate 73 parts As clearly shown in Table 2, Also in this example, as in Example 1 or 2, it was found that there was no missing dot after the formation of the photospacer, and according to the completed color filter, high-quality display without display unevenness was performed.

Example 4
In Example 1, the binder 4 was changed to the following binder 6, and the addition amount of the sensitizing dye (A-2) (NBCA) in the photosensitive layer coating solution (1) was changed to the addition amount specified in Table 2 below. Other than this, the MVA mode liquid crystal display device of the present invention was produced in the same procedure as in Example 1 using RGBK and a spacer-forming photosensitive transfer material produced in the same formulation and procedure. This MVA mode liquid crystal display device was evaluated in the same manner as in Example 1. The results are shown in Table 2.

Binder 6
・ Random copolymer of benzyl methacrylate / methacrylic acid / 2-methacryloyloxyethyl methacrylate (= 53/20/27 [molar ratio]) (weight average molecular weight 42000) 27 parts ・ Propylene glycol monomethyl ether acetate 73 parts Obviously, in this embodiment as well, as in Embodiments 1 to 3, there are no missing dots after the formation of the photo spacer, and according to the completed color filter, high-quality display without display unevenness is performed. I understood.

(Examples 5 to 10)
In Example 1, except that the addition amount of the sensitizing dye (A-2) (NBCA) in the coating solution (1) for photosensitive layer formation for spacers was changed to the addition amount shown in Table 2 below, Example 1 The MVA mode liquid crystal display device of the present invention was produced in the same manner as described above. This MVA mode liquid crystal display device was evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 1)
In Example 1, except that the binder 4 was changed to the binder 1, RGBK and a photosensitive transfer material for forming a spacer prepared by the same formulation and procedure were used, and the MVA mode liquid crystal was prepared by the same procedure as in Example 1. A display device was produced. This MVA mode liquid crystal display device was evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Examples 2 and 3)
In Example 1, except that the addition amount of the sensitizing dye (A-2) (NBCA) in the coating solution (1) for photosensitive layer formation for spacers was changed to the addition amount shown in Table 2 below, Example 1 An MVA mode liquid crystal display device was produced in the same manner as described above. This MVA mode liquid crystal display device was evaluated in the same manner as in Example 1. The results are shown in Table 2.

  Table 2 also shows the types of crosslinkable groups contained in the binder in the photosensitive layer for spacer formation, the formation method of the photosensitive layer, the OD of the photosensitive layer, and the content of NBCA contained in the photosensitive layer. Describe.

* 1 ... Almost no dots remained on the substrate * 2 ... The spacer shape formed was not a columnar shape

As shown in Table 2, it was found that in Example 1, there was no missing dot after the formation of the photo spacer, and according to the completed color filter, high quality display without display unevenness was performed.
Further, as apparent from Table 2, in this comparative example, the dot missing after the formation of the photo spacers is remarkable, and the color filter after completion cannot be said to have high image quality due to the occurrence of display unevenness. It was.

It is a perspective view which shows the external appearance of the exposure unit which concerns on this invention. It is a perspective view which shows the structure of the scanner of the exposure unit which concerns on this invention. (A) is a top view which shows the exposed area | region formed in a photosensitive material, (B) is a figure which shows the arrangement | sequence of the exposure area by each exposure head. 1 is a perspective view showing a schematic configuration of an exposure head according to the present invention. (A) is sectional drawing of the subscanning direction along the optical axis which shows the structure of the exposure head shown in FIG. 4, (B) is a side view of (A). It is the elements on larger scale which show the structure of a digital micromirror device (DMD). (A) And (B) is explanatory drawing for demonstrating operation | movement of DMD. (A) And (B) is a top view which compares and shows the arrangement | positioning of an exposure beam, and a scanning line by the case where it does not arrange | position inclined DMD and the case where it arranges inclined. (A) is a perspective view showing a configuration of a fiber array light source, (B) is a partially enlarged view of (A), and (C) and (D) are plan views showing an arrangement of light emitting points in a laser emitting portion. is there. It is a figure which shows the structure of a multimode optical fiber. It is a top view which shows the structure of a combined laser light source. It is a top view which shows the structure of a laser module. It is a side view which shows the structure of the laser module shown in FIG. It is a partial side view which shows the structure of the laser module shown in FIG. (A) And (B) is sectional drawing which shows the depth of focus in exposure apparatus. (A) And (B) is a figure which shows the example of the use area | region of DMD. (A) is a side view when the use area of DMD is appropriate, (B) is a sectional view in the sub-scanning direction along the optical axis of (A). It is a schematic block diagram showing the liquid crystal display device of a MVA mode. It is a figure for demonstrating the pattern formation apparatus used for the Example.

Explanation of symbols

910 Color filter substrate 912 Colored pixel 914 Photo spacer 916 Black matrix 921 TFT substrate (counter substrate)

Claims (4)

A monochromatic light or emission line in the range of 350 nm to 420 nm is modulated based on image data using a spatial light modulation device containing at least an ethylenically unsaturated compound, a photopolymerization initiator and a binder and arranged in two dimensions. A photosensitive resin composition for a photospacer used in an exposure method for forming a two-dimensional image by performing relative scanning while
A photosensitive resin composition for a photospacer, wherein an OD at a wavelength of the monochromatic light or bright line is in a range of 0.05 to 1.2, and the binder contains a crosslinkable group. Forming a photosensitive layer comprising a photosensitive resin composition for a photospacer according to claim 1 on a substrate;
Curing the photosensitive layer by performing relative scanning while modulating monochromatic light or emission lines within a range of 350 nm to 420 nm based on image data using spatial light modulation devices arranged in two dimensions; and
The manufacturing method of the board | substrate with a spacer characterized by including these.   A substrate with spacers manufactured by the method for manufacturing a substrate with spacers according to claim 2.   A liquid crystal display device comprising the substrate with a spacer according to claim 3.

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