JP2007086692A - Method and material for forming structural material for liquid crystal display, substrate for a liquid crystal display device, liquid crystal display element and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and a material for forming a structural material for a liquid crystal display, with which images (for example, for structures such as spacers and ribs) with excellent profiles are formed, and a substrate for a liquid crystal display device, with which a high-quality image is displayed by suppressing deformation of the profile, a liquid crystal display element, and a liquid crystal display device. <P>SOLUTION: The method for forming the structural material for the liquid crystal display contains an exposure process in which a two-dimensional image is formed by relatively scanning a photosensitive resin layer while modulating light based on an image data and exposing the photosensitive resin layer, wherein the transmission optical density (OD) of the photosensitive resin layer with a single exposure wavelength of 405 nm±40 nm in the exposure process is set to be 0.1-1.5. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for forming a structural material for a liquid crystal display, a structural material forming material for a liquid crystal display, a substrate for a liquid crystal display device, a liquid crystal display element, and a liquid crystal display device, and more specifically, modulates light based on image data. Method for forming a structural material for liquid crystal display using an exposure method in which a two-dimensional image is formed by performing exposure while scanning relative to each other, a structural material forming material for liquid crystal display suitable for the same, and a liquid crystal display device using the same The present invention relates to a substrate, a liquid crystal display element, and a liquid crystal display device.

  Conventionally, liquid crystal display devices have been widely used for display devices that display high-quality images. 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, ie, the thickness of the liquid crystal layer, is an element that determines image quality. For this purpose, a spacer for keeping the thickness of the liquid crystal layer constant is provided. The thickness between the substrates is generally referred to as “cell thickness”, and the cell thickness usually indicates the thickness of the liquid crystal layer, in other words, the distance between two electrodes applying an electric field to the liquid crystal in the display region. Is.

  Spacers have been conventionally formed by bead dispersion (ball spacers), but in recent years, spacers with high positional accuracy have been formed by photolithography using a photosensitive resin composition. A spacer formed using such a photosensitive resin composition is called a photospacer.

  About the photo spacer produced through patterning, alkali development, and baking using the photosensitive resin composition, the compressive strength of the spacer dot is weak, and the plastic deformation tends to increase during panel 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.

  Conventionally, the TN mode has been adopted as the display mode of the liquid crystal display device (for example, see Non-Patent Document 1), but a VA mode with a wide viewing angle has been proposed due to the problem of a narrow viewing angle (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 fluctuations in the cell thickness of the liquid crystal cell tend to cause display unevenness, and the same tendency is shown in other display modes such as the IPS mode and the OCB mode.

Similar to the spacer described above, the ribs also tend to have a large plastic deformation when manufactured using the photosensitive resin composition.
"Liquid Crystal Business Frontline" by Yoshihiro Iwai, p. 41, published by Kogyo Kenkyukai (1993) "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

  However, when forming a structural material for a liquid crystal display such as a spacer using a photosensitive resin composition, particularly in the case of a digital exposure system that performs pattern exposure by a maskless exposure method using a laser or the like, It was found that the pattern shape which is the laser exposure part tends to deteriorate. That is, if the photosensitive layer of the photosensitive material has an optical density similar to that of an analog exposure system that performs conventional mask exposure, the optical density of the photosensitive material is too low, resulting in insufficient image forming properties, such as spacers and ribs. In the process of forming the structure, there is a problem that plastic deformation or sagging occurs due to the influence of heat treatment after development, and a good profile cannot be obtained.

  In other words, since the exposure wavelength range is different in the digital exposure system from the conventional analog exposure system, the exposure conditions required to obtain the pattern profile are also different. With the same configuration as the conventional analog exposure system, the film depth direction A rectangular shape with a favorable profile, such as an inverted trapezoidal shape (toward the substrate side), cannot be obtained.

  The present invention has been made in view of the above, and a method for forming a structural material for a liquid crystal display and a structural material forming material for a liquid crystal display capable of forming an image with a good profile (for example, a structure such as a spacer or a rib), Another object of the present invention is to provide a substrate for a liquid crystal display device, a liquid crystal display element, and a liquid crystal display device that can display a high-quality image while suppressing the collapse of the profile.

  The present invention may be referred to as an exposure method (hereinafter referred to as “maskless pattern exposure”) in which a two-dimensional image is formed by exposure by performing relative scanning while modulating light based on image data using a laser or the like. ), The pattern exposure (digital exposure) and analog exposure are different in that the wavelength used for exposure is a sum of a plurality of wavelengths in the latter, whereas the former is only a single wavelength. Therefore, the density (OD) region of the photosensitive layer suitable for exposure is also different, and maskless pattern exposure can be performed by specifying the optical density in the wavelength range within a predetermined range, resulting in profile collapse due to processing after development. It was obtained based on the knowledge that it was effective in avoiding the above. Specific means for achieving the above object are as follows.

  <1> A method for forming a structural material for a liquid crystal display including an exposure step of forming a two-dimensional image by exposing a photosensitive resin layer by performing relative scanning while modulating light based on image data, A method for forming a structural material for a liquid crystal display, wherein a transmission optical density (OD) of the photosensitive resin layer is 0.1 to 1.5 at a single exposure wavelength of 405 nm ± 40 nm in the exposure step It is.

<2> Photosensitivity used in the method for forming a structural material for a liquid crystal display according to <1>, wherein a transmission optical density (OD) at a single exposure wavelength of 405 nm ± 40 nm is 0.1 to 1.5. It is a structural material forming material for liquid crystal displays characterized by having a resin layer.
<3> The image forming material according to <2>, wherein the photosensitive resin layer includes a photopolymerizable compound and a photopolymerization initiator.

<4> A liquid crystal display substrate comprising a liquid crystal display structural material formed using the liquid crystal display structural material forming material according to <2> or <3>.
<5> A liquid crystal display element comprising the liquid crystal display device substrate according to <4>.
<6> A liquid crystal display device comprising the liquid crystal display element according to <5>.

  ADVANTAGE OF THE INVENTION According to this invention, the formation method of the structural material for liquid crystal displays which can form an image (for example, structures, such as a spacer and a rib) with a favorable profile, the structural material formation material for liquid crystal displays, and profile collapse are suppressed. Thus, it is possible to provide a substrate for a liquid crystal display device, a liquid crystal display element, and a liquid crystal display device that can display a high-quality image.

  Hereinafter, a method for forming a structural material for a liquid crystal display according to the present invention and a material for forming a structural material for a liquid crystal display used therein will be described in detail. Through the description, a substrate for a liquid crystal display device, a liquid crystal display element, and a liquid crystal according to the present invention The display device will also be described in detail.

The structural material forming material for a liquid crystal display of the present invention is a photosensitive material used in the method for forming a structural material for a liquid crystal display of the present invention, and is preferably a photosensitive resin (on a temporary support or a substrate for a liquid crystal display). An exposure system (maskless pattern exposure) in which at least one of the photosensitive resin layers is exposed by scanning with relative scanning while modulating light based on the image data. The transmission optical density (OD) at a single exposure wavelength of 405 nm ± 40 nm is 0.1 to 1.5. More preferably, at least a photosensitive resin layer is provided on the temporary support, and a transfer material capable of transferring the photosensitive resin layer to a desired transfer target can be formed.
In addition, the formation method of the structural material for liquid crystal displays of this invention is mentioned later.

  In the present invention, in particular, the photosensitive resin layer formed (preferably on a temporary support or a liquid crystal display substrate) is exposed by performing relative scanning while modulating light based on image data before exposure. A single exposure wavelength in maskless pattern exposure (for example, laser exposure) for forming a two-dimensional image, that is, a transmission optical density (OD) at a single exposure wavelength of 405 nm ± 40 nm is set within the above range that is neither too low nor too high. As a result, sufficient photocuring of the exposed area becomes possible, and it becomes difficult to be affected by the intensity of uneven (non-uniform) development, so the profile of the structural material for liquid crystal displays such as photo spacers and ribs can be developed. It is possible to effectively suppress collapse due to each process such as heat treatment after development as well as time. Thereby, the display nonuniformity resulting from profile deterioration can be eliminated. Therefore, it is effective in eliminating the display unevenness of the VA display mode liquid crystal display element that is easily affected by cell thickness fluctuations (especially when the cell thickness is 2 to 4 μm).

  In other words, if the OD is less than 0.1, the exposure sensitivity is insufficient because the OD is too low (for example, too little photopolymerization initiator), and the entire exposure region including the depth direction of the exposure region is sufficiently obtained. If it cannot be hardened and the OD exceeds 1.5, the OD is too high, and the light during exposure does not reach the photosensitive resin layer (on the substrate side away from the light source), resulting in insufficient curing. That is, when the OD exceeds 1.5, a low molecular weight substance (unreacted monomer, etc.) elutes into the developing solution when developed after exposure, resulting in an inverted trapezoid that narrows from the light source toward the depth of the film. Thus, a structural material for a liquid crystal display such as a photo spacer or rib having a good profile cannot be obtained.

  Especially, as said transmission optical density (OD), the range of 0.2-1.2 is more preferable.

  The exposure wavelength in the present invention is the wavelength of light in the exposure process during the production of a liquid crystal display structural material (photo spacer, liquid crystal alignment control protrusion, etc.) by maskless pattern exposure using a laser or the like, and is 405 nm. The region is ± 40 nm.

The transmission optical density (OD) in the present invention is measured, for example, by measuring the concentration D ⁰ of the substrate using a spectrophotometer, and then the photosensitive resin layer according to the present invention (with an exposure wavelength of 405 nm ± 40 nm) on the substrate. Is determined from the concentration difference (D ¹ -D ⁰ ) obtained by measuring the concentration D ¹ of the layer together with the substrate.

In order to make the transmission optical density (OD) at the exposure wavelength within the above range, there are methods such as (1) adjusting the concentration of the photopolymerization initiator, and (2) selecting the type of photopolymerization initiator as desired. It is effective.
Specifically, the concentration of the photopolymerization initiator is preferably from 0.1 to 20 mass%, more preferably from 0.5 to 15 mass%, particularly preferably 1 based on the total solid content of the photosensitive resin layer. 0.0 to 10% by mass. When the concentration is within the above range, the profile of the liquid crystal display structural material (photo spacer, liquid crystal alignment control protrusion, etc.) can be improved. In other words, if it is less than 0.1% by mass, an effect as an initiator may not be obtained, and curing may not proceed and an image may not be formed. If it exceeds 20% by mass, the photopolymerization initiator may be on the surface. This causes a phenomenon such as precipitation, causing failure.
In addition, when depending on the type of photopolymerization initiator, it is particularly preferable to select an acridine type or a triazine type from among the photopolymerization initiators described later.

The photosensitive resin layer is preferably configured to be transparent.
“Transparency” refers to a property having light transparency, which does not need to be colorless and transparent but is not substantially colored. Specifically, a colored pixel (red color) in which a photosensitive resin layer constitutes a color filter. , Green, blue, etc.) or a black matrix or the like.

  The structural material forming material for a liquid crystal display having a photosensitive resin layer is, for example, a transfer material having at least a photosensitive resin layer on a temporary support, preferably at least a thermoplastic resin in order from the temporary support side on the temporary support. It can comprise in the transfer material which has a layer and the photosensitive resin layer. Moreover, you may have other layers, such as an intermediate | middle layer and a protective film, as needed.

  The photosensitive resin layer includes at least two substrates, a liquid crystal provided between the substrates, two electrodes for applying an electric field to the liquid crystal, and a photo spacer for regulating a cell thickness between the substrates. In the liquid crystal display device including the above-described photo spacer, rib material, and PDP partition material.

  Specifically, the structure forming material for a liquid crystal display according to the present invention preferably has a configuration in which a photosensitive resin layer containing at least a photopolymerization initiator and a photopolymerizable compound is provided, and the photosensitive resin layer includes: If necessary, other components such as a colorant and a surfactant may be further contained.

  Next, each component of the photosensitive resin layer and other layers constituting the structural material forming material for a liquid crystal display of the present invention will be described in detail.

-Photopolymerization initiator-
The photosensitive resin layer which concerns on this invention can be comprised suitably using at least 1 type of a photoinitiator. That is, as described above, by appropriately selecting the type and amount of the photopolymerization initiator, the transmission optical density OD of the photosensitive resin layer is in the range of 0.1 to 1.5 at the exposure wavelength of 405 nm ± 40 nm. Can be adjusted.

  The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization reaction of the polymerizable compound described later, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable, and may be an activator that generates some kind of action with a photoexcited sensitizer and generates an active radical, depending on the type of monomer. It may be an initiator that initiates cationic polymerization.

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton), phosphine oxide, hexaarylbiimidazole, oxime derivatives, organic peroxides, Examples include thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, and the like.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3333724, F . C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), a compound described in JP-A-62-258241, a compound described in JP-A-5-281728, a compound described in JP-A-5-34920, and U.S. Pat. No. 4,221,976. And the compounds described in the specification.

  Further, vicinal polyketaldonyl compounds described in US Pat. No. 2,367,660, acyloin ether compounds described in US Pat. No. 2,448,828, and US Pat. No. 2,722,512 are described. An aromatic acyloin compound substituted with α-hydrocarbon, a polynuclear quinone compound described in US Pat. No. 3,046,127 and US Pat. No. 2,951,758, an organoboron compound described in JP-A-2002-229194, Radical generators, triarylsulfonium salts (for example, salts with hexafluoroantimony and hexafluorophosphate), phosphonium salt compounds (for example, (phenylthiophenyl) diphenylsulfonium salts) (effective as a cationic polymerization initiator), international publication 01/71428 Like onium salt compounds described in brochure.

  Wakabayashi et al., Bull. Chem. Soc. As a compound described in Japan, 42, 2924 (1969), for example, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4, 6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-tolyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 , 4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-n-nonyl-4,6 -Bis (trichloromethyl 1,3,5-triazine, and 2-(alpha, alpha, beta-trichloroethyl) -4,6-bis (trichloromethyl) -1,3,5-triazine.

Examples of the compound described in British Patent No. 1388492 include 2-styryl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylstyryl) -4, 6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxystyryl) ) -4-amino-6-trichloromethyl-1,3,5-triazine and the like.
Examples of the compound described in JP-A-53-133428 include 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like.

  Examples of the compound described in German Patent No. 3333724 include 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-Methoxystyryl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (1-naphthylvinylenephenyl) -4,6-bis (trichloromethyl) -1,3 , 5-triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-thiophen-2-vinylenephenyl) -4,6-bis (trichloromethyl) ) -1,3,5-triazine, 2- (4-thiophene-3-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-furan) 2-vinylenephenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, and 2- (4-benzofuran-2-vinylenephenyl) -4,6-bis (trichloromethyl) -1, 3,5-triazine and the like can be mentioned.

  F. above. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964) include, for example, 2-methyl-4,6-bis (tribromomethyl) -1,3,5-triazine, 2,4,6-tris (tribromomethyl); -1,3,5-triazine, 2,4,6-tris (dibromomethyl) -1,3,5-triazine, 2-amino-4-methyl-6-tri (bromomethyl) -1,3,5- Examples include triazine and 2-methoxy-4-methyl-6-trichloromethyl-1,3,5-triazine.

  Examples of the compound described in JP-A-62-258241 include 2- (4-phenylethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4 -Naphtyl-1-ethynylphenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-tolylethynyl) phenyl) -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (4- (4-methoxyphenyl) ethynylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-isopropyl) Phenylethynyl) phenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- (4-ethylphenylethynyl) phenyl) -4,6-bis (trichloro Chill) -1,3,5-triazine.

  Examples of the compound described in JP-A-5-281728 include 2- (4-trifluoromethylphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2 , 6-Difluorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,6-dichlorophenyl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2- (2,6-dibromophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine and the like.

  Examples of the compound described in JP-A-5-34920 include 2,4-bis (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl]-. 1,3,5-triazine, trihalomethyl-s-triazine compounds described in US Pat. No. 4,239,850, 2,4,6-tris (trichloromethyl) -s-triazine, 2- (4- Chlorophenyl) -4,6-bis (tribromomethyl) -s-triazine and the like.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2-trichloromethyl). -5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- ( 2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1 , 3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1, , 4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4- Oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromemethyl-5-styryl-1,3,4-oxadiazole, etc. ) And the like.

  Examples of the oxime derivative include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutan-2-one, and 2-acetoxyiminopentane-3-one. 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxy And carbonyloxyimino-1-phenylpropan-1-one.

  Further, as photopolymerization initiators other than the above, acridine derivatives (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine, and the like, polyhalogen compounds (for example, Carbon tetrabromide, phenyltribromomethylsulfone, phenyltrichloromethylketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′-carbonylbi (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP-A-2002-363206 , Coumarin compounds described in JP-A No. 2002-363207, JP-A No. 2002-363208, JP-A No. 2002-363209, etc.), amines (for example, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate) Acid n-butyl, 4-dimethylaminobenzoic acid phenetic acid 4-dimethylimidobenzoic acid 2-phthalimidoethyl, 4-dimethylaminobenzoic acid 2-methacryloyloxyethyl, pentamethylenebis (4-dimethylaminobenzoate), phenethyl of 3-dimethylaminobenzoic acid, pentamethylene ester, 4- Dimethylaminobenzaldehyde, 2-chloro-4-dimethylaminobenzaldehyde,

4-dimethylaminobenzyl alcohol, ethyl (4-dimethylaminobenzoyl) acetate, 4-piperidinoacetophenone, 4-dimethylaminobenzoin, N, N-dimethyl-4-toluidine, N, N-diethyl-3-phenetidine, Tribenzylamine, dibenzylphenylamine, N-methyl-N-phenylbenzylamine, 4-bromo-N, N-dimethylaniline, tridodecylamine, aminofluoranes (ODB, ODBII, etc.), crystal violet lactone, leuco Crystal violet), acylphosphine oxides (for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine) Oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium) , Η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.), JP-A-53-133428, JP-B-57-1819, JP-A-57-6096 And compounds described in US Pat. No. 3,615,455.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, In propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

As content of the said photoinitiator, 0.1-20 mass% is preferable with respect to the total solid component in the said photosensitive resin layer, 0.5-15 mass% is more preferable, 1-10 mass% Is particularly preferred.
The content of the photopolymerization initiator is preferably a photopolymerization initiator / polymerizable compound = 0.01 to 0.2, expressed as a mass ratio with a photopolymerizable compound described later, and 0.02 to 0.1. Is more preferable, and 0.03-0.08 is particularly preferable. Within this range, development residue can be suppressed, and precipitation sensitivity does not occur, and sufficient sensitivity can be obtained.

In addition to the photopolymerization initiator, a sensitizer can be added for the purpose of adjusting the exposure sensitivity and the photosensitive wavelength during exposure in the photosensitive layer. The sensitizer can be appropriately selected by a laser described later.
The sensitizer is excited by active energy rays and interacts with other substances (for example, radical generator, acid generator, etc.) (for example, energy transfer, electron transfer, etc.), thereby generating radicals, acids, etc. It is possible to generate a useful group of

  The sensitizer is not particularly limited and may be appropriately selected from known sensitizers according to the purpose. For example, known polynuclear aromatics (for example, pyrene, perylene, triphenylene), Xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (for example, indocarbocyanine, thiacarbocyanine, oxacarbocyanine), merocyanines (for example, merocyanine, carbomerocyanine), thiazines ( For example, thionine, methylene blue, toluidine blue), acridines (for example, acridine orange, chloroflavin, acriflavine), anthraquinones (for example, anthraquinone), squariums (for example, squalium), acridones (for example, acridone) Chloroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, etc.), coumarins (eg, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) ) -7- (1-pyrrolidinyl) coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3 , 3′-carbonylbis (5,7-di-n-propoxycoumarin), 3,3′-carbonylbis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl)- 7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethyl Examples include minocoumarin, 7-methoxy-3- (3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, and others. JP-A-5-19475, JP-A-7-271028, JP 2002-363206, JP-A-2002-363207, JP-A-2002-363208, JP-A-2002-363209, and the like.

  Examples of the combination of the photopolymerization initiator and the sensitizer include, for example, an electron transfer start system described in JP-A-2001-305734 [(1) an electron donating initiator and a sensitizing dye, (2) A combination of an electron-accepting initiator and a sensitizing dye, (3) an electron-donating initiator, a sensitizing dye and an electron-accepting initiator (ternary initiation system)], and the like.

  As content of the said sensitizer, 0.05-30 mass% is preferable with respect to all the components in the photosensitive resin layer, 0.1-20 mass% is more preferable, 0.2-10 mass% is Particularly preferred. When the content is less than 0.05% by mass, the sensitivity to active energy rays is reduced, the exposure process takes time, and productivity may be reduced. The sensitizer may be precipitated from the photosensitive layer.

A photoinitiator may be used individually by 1 type and may use 2 or more types together.
Particularly preferable examples of the photopolymerization initiator include halogens having the phosphine oxides, the α-aminoalkyl ketones, and the triazine skeleton, which are capable of supporting laser light having a wavelength of 405 ± 40 nm in the later-described exposure. A composite photoinitiator, a hexaarylbiimidazole compound, or titanocene, which is a combination of a fluorinated hydrocarbon compound and an amine compound as a sensitizer described later.

-Photopolymerizable compound-
The photosensitive resin layer which concerns on this invention can be comprised suitably using at least 1 type of a photopolymerizable compound. This photopolymerizable compound is a compound that cures by causing a polymerization reaction by the action of the above-described photopolymerization initiator, specifically, an active species generated during light irradiation. As the photopolymerizable compound, a monomer or oligomer that has two or more ethylenically unsaturated double bonds and undergoes addition polymerization upon irradiation with light is preferable.

  Examples of the monomer or oligomer include a compound having at least one addition-polymerizable ethylenically unsaturated group in the molecule and having a boiling point of 100 ° C. or higher at normal pressure. Specific examples include monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, polypropylene glycol di ( (Meth) acrylate, trimethylolethane triacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane diacrylate, neopentylglycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexane All di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate; multifunctional such as trimethylolpropane and glycerin Polyfunctional acrylates and polyfunctional methacrylates such as those obtained by adding ethylene oxide or propylene oxide to alcohol and then (meth) acrylated can be mentioned.

  Further, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, and JP-A-51-37193; JP-A-48-64183, JP-B-49-43191 And polyester acrylates described in JP-B-52-30490; polyfunctional acrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid, and methacrylates.

Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable.
In addition to the above, “polymerizable compound B” described in JP-A-11-133600 can also be mentioned as a preferable example.

Two or more types of monomers or oligomers may be mixed and used in addition to a single type.
5-50 mass% is common with respect to solid content (mass) of this composition or this layer, and, as for content in the photosensitive resin layer of a monomer or an oligomer, 10-40 mass% is preferable.

-Polymeric substances-
The photosensitive resin layer according to the present invention can be suitably configured using at least one kind of polymer substance. The polymer substance has a function as a binder component in the case of forming a liquid crystal display structural material such as a photospacer or a rib, and itself preferably has a crosslinking group.

  The polymer substance 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 (I) 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 monomers described in paragraphs [0036] to [0039] of JP-A No. 2003-131379.
Among these, allyl (meth) acrylate is particularly preferable in terms of curability and raw material price.

Examples of the “(meth) acrylate having one or more aromatic rings and / or aliphatic rings” include those described in paragraph [0040] of JP-A No. 2003-131379.
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 “other monomers” copolymerizable with these structural units include the monomers described in paragraphs [0041] to [0042] of JP-A No. 2003-131379.

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.

  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%, and 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. The “structural unit represented by the general formula (I)” is preferably 20 to 80 mol%, more preferably 20 to 75 mol%, particularly preferably 25 to 75 mol%. When the structural unit represented by the general formula (I) is within the above range, good curability and developability can be obtained. The “structural unit comprising (meth) acrylate having at least one aromatic ring and / or aliphatic ring” is preferably 10 to 70 mol%, more preferably 10 to 60 mol%, and particularly preferably 10 to 50 mol%. preferable. When the structural unit composed of (meth) acrylate having at least one aromatic ring and / or aliphatic ring is within the above range, the dispersibility is excellent, and the developability and curability are also good.

  The weight average molecular weight of the copolymer suitable as a polymer substance 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 polymer material, paragraphs [0047] to [0052] of JP-A No. 2003-131379 and paragraphs [0011] to [0037] of JP-A No. 2003-207787 are described. And the copolymers described. However, the present invention is not limited to these.

  As content in the photosensitive resin layer of a polymeric material, 30-70 mass% is preferable with respect to solid content of this layer, and 40-50 mass% is preferable.

-Other ingredients-
In addition to the above photopolymerization initiator, photopolymerizable compound, and polymer material, the photosensitive resin layer may further include a colorant, a surfactant, a solvent, a thermal polymerization inhibitor, an ultraviolet absorber, and the like as necessary. Additives can be used.

-Colorant-
Examples of the colorant include dyes and pigments. About the kind, size, etc. of a preferable pigment, it can select suitably from description of Unexamined-Japanese-Patent No. 11-149008, for example. 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 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 copolymers 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 represent a hydrogen atom or a methyl group, preferably R ¹ and 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%.

Of 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 obtained 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-
When forming the photosensitive resin layer, when adjusting the photosensitive resin composition for forming this layer, 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 layer 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 layer 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.

  The photosensitive resin layer can also contain “adhesion aid” described in JP-A No. 11-133600, other additives, and the like in addition to the additives.

  Next, a thermoplastic resin layer, an intermediate layer, a protective film, a temporary support, and the like provided as necessary when the structural material forming material for a liquid crystal display is configured as a transfer material will be described in detail.

-Thermoplastic resin layer-
In the transfer material, at least one thermoplastic resin layer can be provided between the photosensitive resin layer and the temporary support. The thermoplastic resin layer is preferably alkali-developable, and is preferably alkali-soluble from the viewpoint of preventing contamination of the transferred material by the thermoplastic resin layer itself protruding during transfer.

  This thermoplastic resin layer functions as a cushioning material that effectively prevents transfer defects caused by unevenness existing on the transfer material when the photosensitive resin layer is transferred to the transfer material. It can be deformed corresponding to the unevenness on the transfer material when the transfer material is heat-pressed to the transfer material, and the adhesion between the photosensitive resin layer and the transfer material can be improved.

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 at the time of transfer, and is effective in absorbing irregularities on the transfer material, and reticulation occurs in the photosensitive resin layer. In addition, no transfer failure is caused. Moreover, Preferably it is 1.5-16 micrometers, More preferably, it is 5-15.0 micrometers.
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 resin layer. It causes a defect.

  The thermoplastic resin layer can be configured using at least an alkali-soluble thermoplastic resin, and other components can be appropriately used as necessary. The alkali-soluble thermoplastic resin is not particularly limited and may 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 transfer material is preferably provided with an intermediate layer for the purpose of preventing mixing of components when applying a plurality of layers and during storage after application. In particular, it is preferably provided on the thermoplastic resin layer provided on the temporary support and between the thermoplastic resin layer and the photosensitive resin layer. An organic solvent is used to form the thermoplastic resin layer and the photosensitive resin layer. However, by providing an intermediate layer, the two layers can be prevented from being mixed with each other.

The intermediate layer is preferably one that is dispersed or dissolved in water or an aqueous alkali solution. 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 has such a conductive structure, when the temporary support is peeled off after the transfer material provided with the temporary support is brought into close contact with the transfer target, the temporary support or the target As a result, the transfer body 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 the unexposed dust remains in the subsequent exposure process. It is possible to effectively prevent the formation of pinholes accompanying the formation of the exposed portion. 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 material 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 transfer material can be further provided with a protective film as another layer.
The protective film has a function of protecting the photosensitive resin 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 resin layer, and examples thereof include silicon paper, polyolefin sheet, polytetrafluoroethylene sheet and the like. 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 transfer material is coated on a temporary support with a thermoplastic organic polymer (thermoplastic resin) and a dissolved solution (thermoplastic resin coating solution) in which the additive is dissolved, and dried to form a thermoplastic resin layer. After the coating, a prepared solution (a coating solution for an intermediate layer) prepared by adding a resin or an additive to a solvent that does not dissolve the thermoplastic resin layer is applied onto this thermoplastic resin layer, and dried to laminate the intermediate layer. In addition, the photosensitive resin composition prepared as described above is further applied onto the intermediate layer using a solvent that does not dissolve the intermediate layer, and the photosensitive resin layer is laminated by drying and is preferably produced. be able to.

  In addition to the above, prepare a first sheet provided with a thermoplastic resin layer and an intermediate layer in order from the temporary support side on the temporary support, and a second sheet provided with a photosensitive resin layer on the protective film, It can also produce by bonding together so that the intermediate | middle layer surface of a 1st sheet | seat and the surface of the photosensitive resin layer may contact | connect. Furthermore, a first sheet provided with a thermoplastic resin layer on a temporary support and a second sheet provided with a photosensitive resin layer and an intermediate layer in order from the protective film side 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 thermoplastic resin layer of the second sheet.

-Structural materials for liquid crystal displays-
The liquid crystal display structural material-forming material of the present invention is suitable for forming a liquid crystal display structural material, and can be suitably used for forming, for example, a photospacer, a rib material, a PDP partition wall material, and the like.
The structural material forming material for a liquid crystal display of the present invention may be configured as a transfer material capable of transferring a photosensitive resin layer when a temporary support is provided and a photosensitive resin is provided on the temporary support. When a substrate constituting a liquid crystal display is provided and a photosensitive resin layer is provided on the substrate, a liquid crystal display is manufactured as a liquid crystal display substrate on which a liquid crystal display structural material composed of the photosensitive resin layer is formed. Can be used.
Hereinafter, the photo spacer will be described as an example of the structural material for liquid crystal display.

  The photo spacer can be suitably produced using the above-described structural material forming material for liquid crystal display of the present invention. Since the structural material forming material for a liquid crystal display of the present invention is used, exposure can be performed satisfactorily as described above, and size variation due to profile collapse after development can be suppressed, so that display contrast and display unevenness can be eliminated. . In particular, it is effective in eliminating display unevenness of a VA display mode liquid crystal display element that is susceptible to cell thickness fluctuations.

  The photo spacer (a) when the structural material forming material for a liquid crystal display is configured as a transfer material, after the photosensitive resin layer is transferred and formed on the substrate for the liquid crystal display (at this time (before exposure) maskless) Transmission optical density OD at a single exposure wavelength of 405 nm ± 40 nm in pattern exposure is set to 0.1 to 1.5; layer formation step), (b) a liquid crystal display structural material forming material is used as a liquid crystal display substrate When configured, the photosensitive resin layer is exposed and alkali developed and patterned as it is (patterning step), and the patterned photosensitive resin layer is heat-treated (heat treatment step) if necessary. It can produce more suitably. Hereinafter, each process in the case of transfer will be briefly described.

In the layer forming step, the structural material forming material for a liquid crystal display of the present invention is laminated on the surface of the photosensitive resin layer, and the photosensitive resin layer is transferred and formed on the substrate.
In the case of transfer, a roller or flat plate in which a photosensitive resin layer formed in a film form on a temporary support is heated and / or pressurized on a substrate surface using a transfer material (hereinafter also referred to as a photosensitive transfer material). Then, the photosensitive resin layer is transferred onto the substrate by peeling off the temporary support. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From the viewpoint, it is preferable to use the method described in JP-A-7-110575.

  In the present invention, in particular, a single exposure wavelength of 405 nm ± 40 nm in maskless pattern exposure of at least a thermoplastic resin layer and a photosensitive resin layer (at this time (before exposure) on the temporary support in order from the temporary support side. In this embodiment, the photosensitive resin layer is transferred and formed on a substrate using a transfer material having a transmission optical density OD of 0.1 to 1.5).

  When the photosensitive resin layer is formed by coating, the layer thickness is preferably 0.5 to 10.0 μm, and more preferably 1 to 6 μm. When the layer thickness is in the above range, the generation of pinholes during the formation of coating during production is prevented, and development and removal of unexposed portions can be performed without requiring a long time.

  Specifically, after removing the protective film (cover film) from the photosensitive transfer material, the exposed surface of the photosensitive resin layer is overlaid on the substrate surface, which is the transfer material, and is applied by pressing and heating. Match (laminate). 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. Moreover, when using a board | substrate exceeding 1 m, a 2-cutter laminator, a 3-cutter laminator, etc. can be used.

Examples of the substrate on which the photosensitive resin layer is transferred and 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), and a substrate with a color filter (also referred to as a color filter substrate). And a driving substrate with a driving element (for example, a thin film transistor [TFT]). The thickness of the substrate is generally preferably 700 to 1200 μm.
Further, the substrate can be made to have good adhesion with the photosensitive resin layer by performing a coupling treatment in advance. As the coupling treatment, a method described in JP 2000-39033 A is preferably used.

  Further, an oxygen blocking film can be further provided on the photosensitive resin layer after the transfer formation. As a result, the exposure sensitivity can be increased, and the oxygen blocking film can have the same structure as that described in the section of the intermediate layer described later. The thickness of the oxygen blocking film is preferably 0.5 to 3.0 μm.

  When the structural material forming material for a liquid crystal display is configured as a substrate for a liquid crystal display as in (b), the photosensitive resin layer is exposed and alkali developed as it is and patterned (patterning step). The structural material forming material for a liquid crystal display here is a layer in which a photosensitive resin layer is provided on a substrate for a liquid crystal display, and the photosensitive resin layer includes the above-described photopolymerization initiator and the like. A photosensitive resin composition prepared so that the transmission optical density (OD) at a single exposure wavelength of 405 nm ± 40 nm in the maskless pattern exposure at the time of exposure is 0.1 to 1.5 is applied. It is done.

  Application of the photosensitive resin composition is a known coating method such as spin coating method, curtain coating method, slit coating method, dip coating method, air knife coating method, roller coating method, wire bar coating method, gravure coating method, Alternatively, it can be carried out by an extrusion coating method using a popper described in US Pat. No. 2,681,294. Among these methods, a method using a slit nozzle or a slit coater is preferable.

In the present invention, in particular, there is an embodiment in which a solution containing the above-described photopolymerization initiator, photopolymerizable compound and other components is applied onto a substrate with a slit nozzle and dried to form a photosensitive resin layer on the substrate. Is preferred. As the substrate here, a substrate with a transparent conductive film (for example, ITO film), a color filter substrate, a drive substrate with a drive element, or the like is preferable.
The layer thickness in the case of applying and forming is also the same as that in the case of transferring and forming the photosensitive resin layer.

  The slit-like nozzle is a slit-like nozzle having a slit-like hole at a portion where the liquid is discharged. As the slit nozzle or a slit coater having the slit nozzle, Japanese Patent Application Laid-Open Nos. 2004-89851 and 2004-2004. No. 17043, JP 2003-170098, JP 2003-164787, JP 2003-10767, JP 2002-79163, JP 2001-310147, etc. And a slit coater are preferably used.

  In the patterning step, the photosensitive resin layer formed on the substrate is exposed and alkali developed for patterning. Specifically, the photosensitive resin layer formed on the substrate is exposed by maskless pattern exposure according to the present invention, and after the exposure is completed, development processing using a developer is performed.

  Next, with respect to the method for forming a structural material for a liquid crystal display according to the present invention, an exposure method (maskless pattern exposure) in which a two-dimensional image is formed by performing relative scanning while exposing light while modulating light based on image data. The explanation will focus on the utilized exposure process.

  Maskless pattern exposure is an exposure method in which two-dimensional images are formed by using two-dimensional spatial light modulation devices and performing relative scanning while modulating light based on image data.

  An object called a “mask” in which an image (exposure pattern; hereinafter also referred to as a pattern) is formed with a material that does not transmit or weakly transmits exposure light is disposed in the optical path of the exposure light, and the photosensitive layer is the image. In contrast to the conventional mask exposure method (also referred to as mask exposure) in which exposure is performed in a pattern corresponding to the above, the photosensitive layer is exposed in a pattern without using the “mask”.

In maskless pattern exposure, an ultra-high 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 sealed in a quartz glass tube, etc., and has a higher vapor pressure by setting the vapor pressure of the mercury higher (the mercury vapor pressure when lighting is about 5 MPa) W. Elenbaas: Light Sources, Philips Technical Library 148-150). Of the bright line spectrum, a single exposure wavelength of 405 nm ± 40 nm is used, and h-line (405 nm) can be mainly used.

  Laser is an acronym for Light Amplification by Stimulated Emission of Radiation. 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 in the wavelength region.

  A semiconductor laser uses a light emitting diode that induces coherent light at a pn junction when electrons and holes flow out to the junction due to carrier injection, electron beam excitation, collision ionization, photoexcitation, etc. It is. The wavelength of the emitted coherent light is determined by the semiconductor compound. The laser wavelength is a single exposure wavelength of 405 nm ± 40 nm.

  In the present invention, the single exposure wavelength refers to the dominant wavelength in the case of using a laser, and in the case of using an ultra-high pressure mercury lamp, the emission wavelength other than 405 nm is cut with an ND filter to a wavelength larger than 365 nm or 405 nm. This means one wavelength only.

A method of performing relative scanning while modulating light will be described.
One typical method is a two-dimensional micromirror such as DMD (digital micromirror device, for example, an optical semiconductor developed by Dr. Larry Hornbeck et al. In 1987 in Texas Instruments). 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 and the like 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 such exposure heads having DMD, 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 type 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 of the present invention, for example, the following method can also be applied.
An example of drawing using a polygon mirror described in Japanese Patent Laid-Open No. 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 an exposure amount depending on a part of a 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 ultra high pressure mercury lamp and a method using a laser, but the latter is preferred. As the laser in the present invention, a laser having a single exposure wavelength of 405 nm ± 40 nm can be used, and specifically, a known laser such as a semiconductor laser (GaN-based) can be used.

In the patterning step, the light to be irradiated is not particularly limited and can be appropriately selected depending on the purpose. For example, the electromagnetic wave that activates the photopolymerization initiator and the sensitizer, ultraviolet to visible light, electrons X-rays, X-rays, laser light, and the like. Among these, laser light that can perform on / off control of light in a short time and easily control light interference is preferable.
The wavelength of the “ultraviolet to visible light” is not particularly limited and may be appropriately selected depending on the purpose. However, in order to shorten the exposure time of the photosensitive composition, 330 to 650 nm is preferable, 365 to 445 nm is more preferable, and 405 nm is particularly preferable.

  The light irradiation method is not particularly limited and can be appropriately selected depending on the purpose. For example, a high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, a halogen lamp, a cold cathode tube for a copying machine, an LED, a semiconductor laser, etc. The method of irradiating with the well-known light source of this is mentioned. Further, it is preferable to synthesize and irradiate two or more lights from these light sources, and to irradiate a laser beam (hereinafter sometimes referred to as a “combined laser beam”) composed of two or more lights. Is particularly preferred.

  There is no restriction | limiting in particular as the irradiation method of the said combined laser beam, Although it can select suitably according to the objective, A laser irradiated from a several laser light source, a multimode optical fiber, and this laser light source There is a method of forming and irradiating a combined laser beam with a collective optical system that collects light and couples it to the multimode optical fiber.

The beam diameter of the laser is not particularly limited, but among these, from the viewpoint of the resolution of the dark color separation barrier, the 1 / e ² value of the Gaussian beam is preferably 5 to 30 μm, and more preferably 7 to 20 μm.
Although it does not specifically limit as energy amount of a laser beam, From a viewpoint of exposure time and resolution, 1-100 mJ / cm < ² > is preferable especially and 5-20 mJ / cm < ² > is more preferable.
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.

  As the exposure apparatus, for example, the following apparatus can be used. Hereinafter, although an example of the three-dimensional exposure apparatus using a laser beam is shown, 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 the glass substrate 150 by adsorbing the glass substrate 150 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 modulator 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, the mirror device is configured by arranging 600 × 800 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 number of micromirror arrays in which a large number (for example, 800) of micromirrors are arranged in the longitudinal direction are arranged in a large number (for example, 600 sets) in the short direction. As shown, by tilting the DMD 50, the pitch P ₁ of the scanning trajectory (scan line) of the exposure beam 53 by each micromirror becomes narrower than the pitch P ₂ of the scanning line when the DMD 50 is not tilted, greatly increasing the resolution. Can be improved. On the other hand, since the tilt angle of the DMD 50 is very small, the scan width W ₂ when the DMD 50 is tilted and the scan width W ₁ when the DMD 50 is not tilted are substantially the same.

  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 405 nm in the wavelength range of 365 nm to 445 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 an emission width of 2 μm, and each of the laser beams B1 with a divergence angle in a direction parallel to or perpendicular to the active layer being, 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. 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. The 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, the 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 by about 80 times compared to 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 with 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, 600 sets of micromirror rows in which 800 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, 800 × 100 rows) is controlled to be 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, when only 300 sets are used in 600 micromirror rows, modulation can be performed twice as fast per line as compared to the case of using all 600 sets. Further, when only 200 sets of 600 micromirror arrays are used, modulation can be performed three times faster per line than when all 600 sets are used. That is, an area of 500 mm in the sub-scanning direction can be exposed in 17 seconds. Further, when only 100 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 a DMD in which 600 micromirror arrays in which 800 micromirrors are arranged in the main scanning direction are arranged in 600 sets 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.

  After the exposure as described above, if there is a thermoplastic resin layer and an intermediate layer by development processing, unnecessary portions of the thermoplastic resin layer, the intermediate layer, and the photosensitive resin layer are not present, and the thermoplastic resin layer and the intermediate layer are absent. In some cases, unnecessary portions of the photosensitive resin layer are removed to form a liquid crystal display structural material.

  Development after exposure can be carried out in accordance with a known alkali development method. For example, the photosensitive transfer material after exposure is developed using a solvent or an aqueous developer, particularly an alkaline aqueous solution (alkaline developer). It is immersed in a developing bath containing the liquid, or sprayed on the layer on the photosensitive transfer material with a spray or the like, and is further rubbed with a rotating brush, wet sponge, etc. or processed while being irradiated with ultrasonic waves. Etc. 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 resin layer by shower. Prior to development, it is preferable to spray an aqueous alkali solution having a low solubility of the photosensitive resin layer by a shower or the like in advance 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 resin layer, the thermoplastic resin layer and the intermediate layer is preferably, for example, a dilute aqueous solution of an alkaline substance, and further water miscible. What added the organic solvent with a small amount 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.

  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%.

  In addition, a heat treatment step can be provided after patterning, and in this step, the patterned photosensitive resin layer is heat-treated so as to obtain a desired crosslinking reaction rate. By this step, the resin part in the layer (polymeric monomer such as polymer substance, monomer, oligomer, etc.) is crosslinked to form a hard film.

  The crosslinking reaction rate is preferably 86 to 100%, more preferably 90 to 100%, and most preferably 95 to 100%. When the cross-linking reaction rate is within the above range, deformation recovery properties when plastically deformed can be obtained.

  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.

This will be further described with reference to an example in which a photospacer is produced by a transfer method.
The surface of the photosensitive resin layer exposed by removing the protective film of the liquid crystal display structural material forming material of the present invention is overlaid and laminated on the substrate surface, and the temporary support is bonded at the interface with the thermoplastic resin layer. The photosensitive resin layer is transferred onto the substrate by peeling and removing. After that, the photosensitive resin layer is exposed by maskless pattern exposure through the thermoplastic resin layer and the intermediate layer, and the unexposed portion of the photosensitive resin layer is developed and removed using an alkaline aqueous solution. Form. A photo spacer can be obtained by heat-treating the formed spacer pattern to cure the exposed portion.

<Liquid crystal display substrate>
The substrate for a liquid crystal display device of the present invention is constituted by using the above-described structural material forming material for a liquid crystal display of the present invention. When a photo spacer is formed as a structural material for a liquid crystal display, it is preferably formed on a display light-shielding portion such as a black matrix formed on a 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 display light-shielding portion such as TFT, 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 resin layer is laminated on the substrate surface, peeled and transferred to form a photosensitive resin layer, and then subjected to exposure, development, heat treatment, and the like to form a photo spacer, thereby forming the liquid crystal display of the present invention. A device substrate can be manufactured.
The substrate for a liquid crystal display device of the present invention may further be provided with colored pixels of three colors such as red (R), blue (B), and green (G) as necessary.

<Liquid crystal display element>
The liquid crystal display element of the present invention is constituted by providing the liquid crystal display device substrate of the present invention described above. As one of the liquid crystal display elements, a liquid crystal layer and a liquid crystal driving means (a simple matrix driving method and an active matrix driving method) are provided between a pair of substrates (including the substrate for a liquid crystal display device of the present invention) at least one of which is light transmissive. And the like) at least.

  In this case, the substrate for a liquid crystal display device of the present invention can be configured as a color filter substrate having a plurality of RGB pixel groups and each pixel constituting the pixel group being separated from each other by a black matrix. Since this color filter substrate is provided with a rectangular photo spacer, for example, having a good profile, the liquid crystal display element including the color filter substrate has a cell gap unevenness (cell thickness variation between the color filter substrate and the counter substrate). ) And the occurrence of display unevenness such as color unevenness can be effectively prevented. Thereby, the produced liquid crystal display element can display a vivid image.

  As another aspect of the liquid crystal display element, at least one of the liquid crystal display elements includes a liquid crystal layer and a liquid crystal driving means between a pair of transparent substrates (including the substrate for a liquid crystal display device of the present invention). The means has an active element (for example, TFT), and the pair of substrates is configured to be regulated to a predetermined width by a rectangular photo spacer having a good profile. Also in this case, the substrate for a liquid crystal display device of 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.
Further, the pixel group of the color filter substrate may be composed of two-color pixels exhibiting different colors, or may be composed of three-color pixels, four-color pixels or more. 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, stripe type, etc. is preferable, and when arranging pixel groups of four or more colors, any arrangement may be used. For producing the color filter, for example, after forming a pixel group of two or more colors, the black matrix may be formed as described above, or conversely, the pixel group may be formed after forming the black matrix. . Regarding the formation of RGB pixels, JP 2004-347831 A can be referred to.

<Liquid crystal display device>
The liquid crystal display device of the present invention is configured by providing the above-described liquid crystal display element of the present invention. For example, as described above, the gap between the pair of substrates arranged to face each other is regulated to a predetermined width by the photo spacer manufactured using the liquid crystal display structural material forming material of the present invention. The liquid crystal material is sealed (the sealed portion is referred to as a liquid crystal layer), and the thickness of the liquid crystal layer (cell thickness) is maintained at a desired uniform thickness. Since the liquid crystal display element of the present invention is provided, occurrence of display unevenness such as color unevenness is effectively prevented, and a vivid image can be displayed.

  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. Among them, in the liquid crystal display device of the present invention, from the viewpoint of exhibiting the effect of the present invention most effectively, a display mode that easily causes display unevenness due to fluctuations in the cell thickness of the liquid crystal cell is desirable, and the cell thickness is 2 to 4 μm. The VA display mode, the IPS display mode, and the OCB display mode are preferably configured.

  The basic configuration of the liquid crystal display device of the present invention 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). And (b) a driving substrate and a counter substrate provided with a counter electrode (conductive layer); and a counter substrate provided with a counter electrode (conductive layer). The liquid crystal display device of the present invention can be suitably applied to various liquid crystal display devices, and the like. .

  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 except that it includes the liquid crystal display element of the present invention. For example, the liquid crystal display device of the various types described in the “next-generation liquid crystal display technology” can be configured. . 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 of the present invention includes an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and the like, except that the liquid crystal display device of the present invention described above is provided. It can generally be configured using various members such as a viewing angle compensation film, an antireflection film, a light diffusion film, and an antiglare film. Regarding these members, 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 (Part 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.

  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
As shown below, an MVA mode liquid crystal display device configured as shown in FIG. 18 was produced.
-Fabrication of color filter substrate-
<Production of photosensitive resin 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 liquid having the following formulation P1 was applied onto the thermoplastic resin layer and dried to laminate an intermediate layer (oxygen barrier film). On this intermediate layer, a colored photosensitive resin composition K1 having the composition shown in Table 1 below was further applied and dried to laminate a photosensitive resin 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 resin 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 photosensitive resin layer.

  As described above, a temporary support, a thermoplastic resin layer, an intermediate layer (oxygen barrier film), and a black (K) photosensitive resin layer are laminated to produce a photosensitive resin transfer material configured as a laminate. (Hereinafter referred to as photosensitive resin 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 below: 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 Copolymer with (5 parts) (weight average molecular weight 30,000) ... 30 parts Methyl ethyl ketone ... 70 parts

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

  Next, the colored photosensitive resin composition K1 used in the production of the obtained photosensitive resin transfer material K1 was replaced with colored photosensitive resin compositions R1, G1, and B1 having the compositions described in Table 1 above. Except for this, photosensitive resin transfer materials R1, G1, and B1 were produced by the same method as described above.

<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 resin transfer material K1 is peeled off, the exposed photosensitive resin 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 Rubber Industries, Ltd.] was used for lamination under the conditions of 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, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra high pressure mercury lamp, the mask (quartz exposure mask having an image pattern) and the mask and the thermoplastic resin layer face each other. The distance between the mask surface and the surface of the photosensitive resin layer on the side in contact with the intermediate layer is set to 200 μm in a state where the arranged glass substrate stands upright substantially in parallel, and the thermoplastic resin layer is interposed through the mask. Pattern exposure was performed at an exposure amount of 70 mJ / cm ² from the side.

  Next, with a triethanolamine developer (containing 2.5% triethanolamine, nonionic surfactant, and polypropylene antifoaming agent; trade name: T-PD1, manufactured by Fuji Photo Film Co., Ltd.), 30 Shower development was performed at a flat nozzle pressure of 0.04 MPa at 50 ° C. for 50 seconds to remove the thermoplastic resin layer and the oxygen barrier film.

  Next, a sodium carbonate-based developer (containing 0.06 mol / liter sodium bicarbonate, sodium carbonate of the same concentration, 1% sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and a stabilizer; Using a trade name: T-CD1, manufactured by Fuji Photo Film Co., Ltd., shower development was performed at 29 ° C. for 30 seconds with a cone-type nozzle pressure of 0.15 MPa to obtain a pattern pixel.

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 rotary brush having a shower and nylon bristles at a cone type nozzle pressure of 0.02 MPa, thereby forming a black (K) image 16 on the glass substrate 11 as shown in FIG. Thereafter, the substrate was further post-exposed with 500 mJ / cm ² of 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.

  Thereafter, the glass substrate 11 on which the K image 16 is formed is again washed with a brush as described above and washed with a pure water shower, and then a silane coupling solution is not used, and the substrate preheating device is used for 2 minutes at 100 ° C. Heated.

-Formation of red (R) pixels-
Using the photosensitive resin transfer material R1 obtained above on the glass substrate 11 on which the K image 16 is formed, the same process as the formation of the K image 16 is performed to form the K image 16 on the glass substrate 11. A red pixel (R pixel) was formed on the side where it is present. However, the exposure amount in the exposure step was 40 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 amounts of 177 were 0.88 g / m ² and 0.22 g / m ² , respectively.
After that, the glass substrate 11 on which the R pixel is 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, a substrate preheating device is used. Heated at 100 ° C. for 2 minutes.

-Formation of green (G) pixels-
Next, using the photosensitive resin transfer material G1 obtained as described above, the same process as the formation of the K image 16 is performed, and a green pixel (on the side of the glass substrate 11 on which the K image 16 and the R pixel are formed). G pixel) was formed. However, the exposure amount in the exposure step was 40 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 11 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 solution. It heated at 100 degreeC with the heating apparatus for 2 minutes.

-Formation of blue (B) pixels-
Next, using the photosensitive resin transfer material B1 obtained above, the same process as the formation of the K image 16 is performed, and the glass substrate 11 on the side where the K image 16 and the R and G pixels are formed is blue. A pixel (B pixel) was formed. However, the exposure amount in the exposure step was 30 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 11 on which the R, G, and B pixels were formed was baked at 240 ° C. for 50 minutes to obtain a color filter 12.
Further, an ITO (Indium Tin Oxide) film 13 was formed thereon as a transparent electrode by sputtering, and a color filter substrate 10 was obtained.

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 is obtained by weighing out K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 and mixing at a temperature of 24 ° C. (± 2 ° C.) to 150 rpm. Then, methyl ethyl ketone, binder 1, hydroquinone monomethyl ether, DPHA solution, 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bis) in the amounts shown in Table 1 above were stirred. Ethoxycarbonylmethylamino) -3′-bromophenyl] -s-triazine and surfactant 1 are weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.), and a temperature of 40 ° C. (± 2 ° C.), 150 r. obtained by stirring at 30 pm 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-Carbon black ... 13.1 parts (Special Black 250, manufactured by Degussa)
5- [3-oxo-2- [4- [3,5-bis (3-diethylaminopropylaminocarbonyl) phenyl] aminocarbonyl] phenylazo] -butyroylaminobenzimidazolone ... 0.65 part Polymer [benzyl Random copolymer of methacrylate / methacrylic acid (= 72/28 [molar ratio]) (weight average molecular weight 37,000)] ... 6.72 parts ・ Propylene glycol monomethyl ether acetate ... 79.53 parts

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

<Preparation of colored photosensitive resin composition R1>
Colored photosensitive resin composition R1 measures R pigment dispersion 1, R pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 and mixes at a temperature of 24 ° C. (± 2 ° C.). The mixture was stirred at 150 rpm for 10 minutes, and then the amounts of methyl ethyl ketone, binder 2, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4 as shown in Table 1 above. -Oxadiazole, 2,4-bis (trichloromethyl) -6- [4 '-(N, N-bisethoxycarbonylmethylamino) -3'-bromophenyl] -s-triazine, and phenothiazine, Add in this order at a temperature of 24 ° C. (± 2 ° C.) and stir at 150 rpm for 10 minutes, then weigh out the amount of Additive 1 listed in Table 1 above, and temperature 24 ° C. (± 2 ° C.) so The mixture was stirred at 150 rpm for 20 minutes, and the surfactant 1 in the amount shown in Table 1 was weighed and added at a temperature of 24 ° C. (± 2 ° C.) and added at 30 rpm. And stirred 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 (trade name: Irgaphor Red B-CF, manufactured by Ciba Specialty Chemicals Co., Ltd.) 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 (trade name: Chromophthal Red A2B, manufactured by Ciba Specialty Chemicals) ... 18 parts-Random copolymer (weight) of polymer [benzyl methacrylate / methacrylic acid (= 72/28 [molar ratio]) Average molecular weight 37,000)] ... 12 parts Propylene glycol monomethyl ether acetate 70 parts * Binder 2 composition 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 measures the amount of G pigment dispersion 1, Y pigment dispersion 1, and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 and mixes at a temperature of 24 ° C. (± 2 ° C.). The mixture was stirred at 150 rpm for 10 minutes, and then the amounts of methyl ethyl ketone, cyclohexanone, binder 1, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3 shown in Table 1 above. , 4-oxadiazole, 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethylamino) -3′-bromophenyl] -s-triazine, and phenothiazine And added in this order at a temperature of 24 ° C. (± 2 ° C.), stirred at 150 rpm for 30 minutes, and weighed out the surfactant 1 in the amount shown in Table 1 above. It was added in degrees 24 ℃ (± 2 ℃) was stirred for 5 minutes at 30 rpm, was obtained by filtering with a 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 As the G pigment dispersion 1, “trade name: GT-2” manufactured by FUJIFILM Electronics Materials Co., Ltd. was used.
* Y pigment dispersion 1
Product name: CF Yellow EX3393 (manufactured by Gokoku Color Co., Ltd.)

<Preparation of colored photosensitive resin composition B1>
Colored photosensitive resin composition B1 measures the amount of B pigment dispersion 1, B pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 and mixes at a temperature of 24 ° C. (± 2 ° C.). The mixture was stirred at 150 rpm for 10 minutes, and then the amounts of methyl ethyl ketone, binder 3, DPHA solution, 2-trichloromethyl-5- (p-styrylstyryl) -1,3,4 as shown in Table 1 above. -Oxadiazole and phenothiazine were weighed out and added in this order at a temperature of 25 ° C. (± 2 ° C.) and stirred at a temperature of 40 ° C. (± 2 ° C.) at 150 rpm for 30 minutes. The amount of surfactant 1 listed in Table 1 was weighed out, added at a temperature of 24 ° C. (± 2 ° C.), stirred at 30 rpm 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 of benzyl methacrylate / methacrylic acid / methyl methacrylate (= 36/22/42 [molar ratio]) (weight average molecular weight 30,000) ... 27 parts-Propylene glycol monomethyl ether acetate ... 73 Part

-Production of photosensitive transfer sheet for spacers-
On a 75 μm thick polyethylene terephthalate film temporary support (PET temporary support), a thermoplastic resin layer coating solution having the following formulation A was applied and dried, and a dry layer thickness 6.0 μm thermoplastic resin layer (alkaline) A soluble layer) was formed.

[Prescription A for Coating Solution for Thermoplastic Resin Layer]
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer 25.0 parts (= 55 / 11.7 / 4.5 / 28.8 [molar ratio], mass average molecular weight 90,000)
-Styrene / acrylic acid copolymer: 58.4 parts (= 63/37 [molar ratio], weight average molecular weight 8,000)
2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane
39.0 parts · Surfactant 1 · 10.0 parts · Methanol · 90.0 · 1-methoxy-2-propanol · 51.0 parts · Methyl ethyl ketone · 700 parts

  Next, on the formed thermoplastic resin layer, an intermediate layer coating solution having the following formulation B was applied and dried to laminate an intermediate layer having a dry layer thickness of 1.5 μm.

[Prescription B of coating solution for intermediate layer]
Polyvinyl alcohol: 3.22 parts (PVA-205, saponification rate 80%, manufactured by Kuraray Co., Ltd.)
-Polyvinylpyrrolidone: 1.49 parts (PVP K-30, manufactured by IS Japan Co., Ltd.)
・ Methanol: 42.3 parts ・ Distilled water: 524 parts

  Next, a photosensitive resin layer coating solution having the formulation 1 shown in Table 2 below was further applied and dried on the formed intermediate layer, and a photosensitive resin layer having a dry layer thickness of 4.0 μm was laminated.

  As described above, after forming a laminated structure of PET temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer (the total layer thickness of the three layers is 11.5 μm), the surface of the photosensitive resin layer is formed. Further, a polypropylene film having a thickness of 12 μm was applied as a cover film by heating and pressing to obtain a photosensitive transfer sheet (1) for spacers.

-Production of photo spacer-
The cover film of the obtained photosensitive transfer sheet for spacer (1) is peeled off, and the surface of the exposed photosensitive resin layer is formed on the color filter substrate 10 [size 680 × 880 mm] on which the ITO film prepared above is sputtered. A laminator Lamic II type (manufactured by Hitachi Industries, Ltd.) was used, and the conveyance speed was 2.2 m / min under a linear pressure of 100 N / cm at 130 ° C. under heating and heating conditions. And pasted together. Thereafter, the PET temporary support was peeled and removed at the interface with the thermoplastic resin layer, and the photosensitive resin layer was transferred together with the thermoplastic resin layer and the intermediate layer.

Next, for the photosensitive resin layer, the thermoplastic resin layer, and the intermediate layer on the color filter substrate, using the following pattern forming apparatus in the air atmosphere, the photosensitive resin layer, the thermoplastic resin layer, and the intermediate layer The exposure pattern was exposed to light having a wavelength of 405 nm and an exposure amount of 80 mJ / cm ² while relatively moving the exposure head and the exposure head.

-Pattern forming device-
As the light irradiation means, a combined laser light source shown in FIGS. 9 to 14 and 600 sets of micromirror rows in which 800 micromirrors are arranged in the main scanning direction shown in FIG. Among the arrayed light modulation means, the DMD 50 controlled to drive only 800 × the number of columns in the use area, the microlens array 472 in which the microlenses shown in FIG. 19 are arrayed, and the microlens A pattern forming apparatus having optical systems 480 and 482 for forming an image of light passing through the array on the photosensitive resin layer was used. In addition, the aperture array 59 disposed in the vicinity of the condensing position of the microlens array 55 is disposed so that only light that has passed through the corresponding microlens 55a is incident on each aperture 59a.

Next, KOH developer CDK-1 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) is sprayed from a flat nozzle at 25 ° C. and a nozzle pressure of 0.15 MPa for 60 seconds to perform shower development, and unexposed portions are developed and removed. To obtain a pattern (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 10 provided with the spacer pattern was subjected to a heat treatment at 230 ° C. for 30 minutes to produce a photospacer 14.

-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 A 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 B 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 resin layer was coated. Further, an OSM-N film (manufactured by Tredegar Film Products, 23 μm) was attached to the surface of the photosensitive resin layer as a protective film. In this way, a photosensitive transfer material for protrusions is produced, in which a thermoplastic resin layer, an intermediate layer, a photosensitive resin layer for protrusions, and a protective film are laminated in this order from the PET temporary support side. did.

[Formulation C of projection forming coating liquid]
-Positive resist solution FH-2413F ... 53.3 parts (Fuji Film 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 resin layer for protrusions and the surface of the color filter substrate 10 on which the ITO film 13 is provided (on the color filter) are removed. Lamination was performed using a laminator type Lamic II [manufactured by Hitachi Industries, Ltd.] (lamination) under 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 resin layer, the intermediate layer, and the thermoplastic resin layer are sequentially laminated on the color filter substrate from the substrate side.

Next, the proximity exposure machine is set so that the distance between the mask surface of the photomask and the surface in contact with the intermediate layer of the photosensitive resin layer for projection is 100 μm above the thermoplastic resin layer which is the outermost layer. Then, a proximity exposure was performed with an irradiation energy of 70 mJ / cm ² using an ultrahigh pressure mercury lamp through a photomask.
Thereafter, a 1% triethanolamine aqueous solution was sprayed from above the thermoplastic resin at 30 ° C. for 30 seconds using a shower type developing device, and the thermoplastic resin layer and the intermediate layer were dissolved and removed. At this stage, the photosensitive resin 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 dibutylnaphthalenesulfonate is further sprayed at 33 ° C. for 30 seconds using a shower type developing device. Development was performed while developing and removing unnecessary portions (uncured portions) of the photosensitive resin layer for protrusions. Thereby, the protrusion 15 made of the photosensitive resin 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 15 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 pixels). The projection 15 was formed.

  Apart from the above, a TFT substrate 21 was prepared as a counter substrate. An ITO (Indium Tin Oxide) film 22 is formed on one surface of the TFT substrate by sputtering. Subsequently, an alignment film 24 made of polyimide was provided on the ITO film 22 of the TFT substrate and the ITO film 13 on the side of the color filter substrate 10 on which the photospacer 14 was provided.

  Thereafter, an epoxy resin sealant was printed at a position corresponding to the outer frame of the black matrix 16 provided around the pixel group of the color filter, and the color filter substrate 10 was bonded to the TFT substrate 21. . 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.) 15 and 23 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.

In addition, the detail of each composition in the composition of the said Table 2 is as follows.
* Pigment Silica sol 30% methyl isobutyl ketone dispersion (trade name: MIBK-ST, manufactured by Nissan Chemical Industries, Ltd.)
* Binder 1
Methacrylic acid / allyl methacrylate copolymer (= 20/80 [molar ratio], mass average molecular weight 36,000; polymer substance)
* The composition of the DPHA solution and the surfactant 1 is the same as that of the colored photosensitive resin composition described above.
* Coloring dye Victoria Pure Blue BOH-M (Hodogaya Chemical Co., Ltd.)
* Initiator 1
The following 9-phenylacridine (manufactured by Nippon Steel Chemical Co., Ltd .; acridine compound)
* Initiator 2
The following 2,4-bis (trichloromethyl) -6- [4 ′-(N, N-bisethoxycarbonylmethyl) -3′-bromophenyl] -s-triazine (Wako Pure Chemical Industries, Ltd.)

(Examples 2-5, Comparative Examples 1-5)
In Example 1, the photosensitive transfer sheet for spacer (2) was prepared in the same manner as in Example 1 except that Formula 1 of the coating solution for photosensitive resin layer was changed to Formulas 2 to 10 in Table 2 below. (10) and the MVA mode liquid crystal display device of the present invention were produced.

(Evaluation)
The following evaluation was performed using the photosensitive transfer sheet for spacers and the liquid crystal display device produced in each Example and Comparative Example. The evaluation results are shown in Table 3 below.
-1. Shape
The obtained color filter was cut vertically with the glass substrate to expose the cross section, and photographed with a scanning electron microscope (magnification 20000 times), the diameter, height and shape of the photo spacer were measured.

-2. Bubble failure
The obtained color filter was visually observed with a 200 × optical microscope, and the presence or absence of bubbles in the photospacer was examined. At this time, 1000 pixels were observed and evaluated according to the following ranks. The results are shown in Table 1 below. ○ Rank is acceptable.
〔Evaluation criteria〕
○ Rank: No bubbles at all △ Rank: One to two bubbles × Rank: Three to 10 bubbles

-3. Display contrast
For each of the obtained liquid crystal display devices, a ratio (= L ^a : L ^b ) between the luminance L ^a when displaying black and the luminance L ^b when displaying white is obtained, and this ratio is used as a contrast ratio as ^follows. Evaluation was performed according to the evaluation criteria. For measurement, a color luminance meter BM-5 (manufactured by Topcon Co., Ltd.) is installed at a distance of 50 cm in the vertical direction of the surface from the front side viewed by the observer, and under illumination of 300 lux (assuming a living environment in a general household) ).
〔Evaluation criteria〕
○: The contrast ratio was 200: 1 or more.
Δ: The contrast ratio was 150: 1 or more and less than 200: 1.
X: The contrast ratio was less than 150: 1.

  As shown in Table 3, in the example, a good spacer pattern profile was obtained after development, no gaps were formed between the patterns, the color density and the contrast were not lowered, and the contrast of the displayed image was high and bright. It was possible to display images with high display quality. On the other hand, in the comparative example, the pattern profile after development does not become a good rectangle, or the profile collapses due to the heat treatment after development, and the rectangularity is lost, resulting in gaps between patterns, color density and contrast Thus, an image with high display contrast could not be obtained.

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 sectional drawing which shows the structural example of the MVA mode liquid crystal display element of this invention. (A) is an example of a cross-sectional view along the optical axis showing the configuration of another exposure head having a different coupling optical system, and (B) is the light projected on the exposed surface when a microlens array or the like is not used. FIG. 2C is an example of a plan view showing an image, and FIG. 3C is an example of a plan view showing an optical image projected on an exposed surface when a microlens array or the like is used.

Explanation of symbols

50 ... Digital micromirror device (DMD)
54 ... Lens system 66 ... Fiber array light source 166 ... Exposure head (exposure unit according to the present invention)

Claims (6)

  A method for forming a structural material for a liquid crystal display, comprising: an exposure step of forming a two-dimensional image by exposing a photosensitive resin layer by relative scanning while modulating light based on image data; A method for forming a structural material for a liquid crystal display, wherein a transmission optical density (OD) of the photosensitive resin layer at a single exposure wavelength of 405 nm ± 40 nm is 0.1 to 1.5. Used in the method for forming a structural material for a liquid crystal display according to claim 1,
A structural material forming material for a liquid crystal display comprising a photosensitive resin layer having a transmission optical density (OD) of 0.1 to 1.5 at a single exposure wavelength of 405 nm ± 40 nm.   The structural material forming material for a liquid crystal display according to claim 2, wherein the photosensitive resin layer contains a photopolymerizable compound and a photopolymerization initiator.   A liquid crystal display substrate comprising a liquid crystal display structural material formed using the liquid crystal display structural material forming material according to claim 2.   A liquid crystal display element comprising the substrate for a liquid crystal display device according to claim 4.   A liquid crystal display device comprising the liquid crystal display element according to claim 5.

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