WO2007105381A1

WO2007105381A1 - Photosensitive resin composition for photospacer, method for producing photospacer, substrate for liquid crystal display, liquid crystal display element, and liquid crystal display

Info

Publication number: WO2007105381A1
Application number: PCT/JP2007/051459
Authority: WO
Inventors: Katsuya Takemasa
Original assignee: Fujifilm Corporation
Priority date: 2006-03-13
Filing date: 2007-01-30
Publication date: 2007-09-20
Also published as: TW200739216A

Abstract

Disclosed is a photosensitive resin composition for photospacers having high deformation recovery properties, which enables to eliminate display unevenness in a liquid crystal display having a cell thickness of 2-4 μm. Also disclosed are a method for producing a photospacer, a substrate for liquid crystal displays which enables a high image quality display by preventing display unevenness, a liquid crystal display element and a liquid crystal display. Specifically disclosed is a photosensitive resin composition for photospacers containing an alkali-soluble polymer material, a polymerizable monomer containing a urethane group and 5-15 acrylic groups, and a photopolymerization initiator. Also disclosed are a method for producing a photospacer by using such a photosensitive resin composition, a substrate for liquid crystal displays comprising such a photospacer, a liquid crystal display element and a liquid crystal display.

Description

Specification

Photospacer photosensitive resin composition, photospacer manufacturing method, liquid crystal display substrate, liquid crystal display element, and liquid crystal display device

Technical field

The present invention relates to a photosensitive resin composition for a photospacer suitable for the production of a spacer constituting a display device, and the production of the photospacer, in which variation in the cell thickness of the liquid crystal cell tends to cause display unevenness. The present invention relates to a method, and a substrate for a liquid crystal display device provided with a photospacer produced by this method, a liquid crystal display element, and a liquid crystal display device.

Background art

Conventionally, liquid crystal display devices have been widely used for display devices that display high-quality images. In general, a liquid crystal display device has a liquid crystal layer that can display an image with a predetermined orientation between a pair of substrates, and maintaining the distance between the substrates, that is, the thickness of the liquid crystal layer, determines the image quality. For this purpose, a spacer for keeping the thickness of the liquid crystal layer constant is provided. The thickness between the substrates is generally referred to as the “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 area. Is.

[0003] Spacers have been conventionally formed by bead dispersion, but in recent years, spacers with high positional accuracy have been formed by photolithography using a photosensitive resin composition. Come on! A spacer formed using such a photosensitive resin composition is called a photospacer.

[0004] For a photo spacer produced by patterning, alkali development, and beta using a photosensitive resin composition, plastic deformation does not occur when forming a panel in which the compressive strength of the spacer dot is weak. Has a tendency to grow. For high-quality image display, it is required that there is no problem that the uniformity of the liquid crystal layer cannot be maintained due to the thickness of the liquid crystal layer becoming smaller than the design value, or that there is no image unevenness. The In addition, it is important that the alkali development residue of the photosensitive resin composition is not generated in terms of improving the accuracy of the liquid crystal display device.

[0005] Conventionally, a TN mode has been adopted as a display mode of a liquid crystal display device (for example, Non-patent document 1), the problem of narrow viewing angle VA mode with a wide viewing angle has been proposed (for example, see non-patent document 2).

[0006] In the VA mode, a low dielectric constant protrusion called a rib is formed on one or both of a pair of upper and lower transparent electrodes, or both the pair of upper and lower transparent electrodes are patterned (for example, Non-Patent Document 3). By applying a partial tilt to the electric field generated between the electrodes, the orientation of the liquid crystal is multi-domained to realize a display device that can observe any angular force with the same brightness. is doing. Those using ribs are called MVA, ASV, CPA, etc., and those using both upper and lower transparent electrodes are called PVA.

This VA mode is one of the display modes in which fluctuations in the cell thickness of the liquid crystal cells tend to cause display unevenness, and other display modes such as the IPS mode and OCB mode also show the same tendency.

[0007] In relation to the above, as a spacer forming technique for keeping the thickness (cell thickness) of the liquid crystal layer constant, the use of a resin having an aryl group for forming the spacer is disclosed. (For example, see Patent Document 1).

Patent Document 1: Japanese Patent Application Laid-Open No. 2003-207787

Non-Patent Document 1: “Forefront of Liquid Crystal Business” by Yoshihiro Iwai, p. 41, published by Kogyo Kenkyukai (1993)

Non-patent document 2: “Nikkei Microdevices separate volume Flat Panel Display 2003”, practical edition, pages 82-85, Nikkei BP

Non-Patent Document 3: “Nikkei Microdevices separate volume Flat Panel Display 2003”, practical edition, page 103, Nikkei BP

Disclosure of the invention

Problems to be solved by the invention

[0008] Originally, a photo spacer used in a liquid crystal cell is required to have high deformation recovery properties. In order to achieve this, the crosslinking reaction rate of monomers and the like is increased, and the deformation recovery rate can be increased to some extent, but the improvement effect tends to reach its peak, and further improvement is required. It was. In particular, the VA mode described above employs a birefringence mode of liquid crystal, and thus the transmittance depends on the cell thickness (d), and the cell thickness unevenness is easily detected as the brightness unevenness. In other words, display unevenness is likely to occur due to variations in cell thickness. In addition, it is effective to further reduce the cell thickness from the conventional (TN mode) of 4.5 μm for faster response of the display. As a result, the proportion of the total cell thickness increases, and it becomes more susceptible to cell thickness irregularity (thickness nonuniformity). Furthermore, when a high-speed response is realized, it will be widely used for televisions, and the actual situation is that the demand for display unevenness, that is, cell thickness unevenness, is becoming stricter.

The present invention has been made in view of the above, and has a high degree of deformation recovery, and in particular for a photospacer that can eliminate display unevenness in a liquid crystal display device having a cell thickness of 2 to 4 μm. Photosensitive resin composition, method for producing photospacer using the same, liquid crystal display substrate, liquid crystal display element, and liquid crystal display capable of preventing display unevenness and displaying high-quality image An object is to provide an apparatus and to achieve the object. Means for solving the problem

[0011] In the present invention, when a polymerizable monomer containing a urethane group and 5 to 15 acrylic groups is used, the deformation recovery property is remarkably improved, and in particular, a thin structure having a cell thickness of 2 to 4 m. Obtained knowledge that it is particularly effective in improving display unevenness that tends to occur when

V has been achieved.

Specific means for achieving the above object are as follows.

[0012] A photosensitive resin composition for a photospacer, comprising <1> an alkali-soluble polymer substance, a polymerizable monomer containing a urethane group and 5 to 15 acrylic groups, and a photopolymerization initiator. It is a thing.

<2> The polymerizable monomer power is a compound represented by the following general formula (A) or (B)

<1> A photosensitive resin composition for a photospacer according to <1>.

[0014] [Chemical 1] OO

R _L 10 NHCOCH ₂ C (CH ₂ OCCH = CH ₂ ) ₃ J

(In the general formula (A) or (B), R represents the following formula (a), (b) or (c).)

1

[0016] [Chemical 2]

[0017] (In formula (a),! /, N represents an integer of 2 to 8.)

<3> At least two substrates, a liquid crystal provided between the substrates, two electrodes for applying an electric field to the liquid crystal, and a photospacer for regulating a cell thickness between the substrates. A method for producing the photospacer in a liquid crystal display device comprising: a photosensitive spacer for a photospacer according to <1> or <2> on one of the two substrates. A layer forming step of forming a photosensitive resin layer containing a fat composition, and the formed photosensitive resin And a patterning step of patterning the layer by exposing and alkali developing the layer.

[0019] <4> In the layer forming step, a photosensitive resin layer having a photosensitive resin layer composed of the photosensitive resin composition for a photospacer according to <1> or <2> on a temporary support. The method for producing a photospacer according to <3>, wherein the photosensitive resin layer is transferred so as to be in contact with one of the two substrates using a transfer material.

[0020] <5> In the layer forming step, a solution containing the photosensitive resin composition for a photospacer according to <1> or <2> is applied onto one of the two substrates and dried. Yes This is a method for manufacturing a photospacer as described in <3>.

<6> A substrate for a liquid crystal display device comprising a photospacer produced by the method for producing a photospacer according to any one of <3> to <5>.

[0022] <7> A liquid crystal display device comprising the liquid crystal display device substrate according to <6>.

<8> A liquid crystal display device comprising the liquid crystal display element according to <7>.

The invention's effect

[0024] According to the present invention, the photosensitive resin composition for a photospacer has a high degree of deformation recovery and can eliminate display unevenness particularly in a liquid crystal display device having a cell thickness of 2 to 4 µm. , A method of manufacturing a photospacer using the same, and a liquid crystal display device substrate, a liquid crystal display element, and a liquid crystal display device capable of preventing display unevenness and displaying a high-quality image can be provided. .

The present invention is particularly effective in improving display unevenness in a liquid crystal display device that easily causes display unevenness due to fluctuations in cell thickness even when the cell thickness is 2 to 4111.

Brief Description of Drawings

FIG. 1 is a schematic cross-sectional view showing a configuration example of an MVA mode liquid crystal display element of the present invention.

FIG. 2 is a schematic cross-sectional view showing a configuration example of a PVA mode liquid crystal display element of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the photosensitive resin composition for a photospacer of the present invention, the method for producing the photospacer, the substrate for a liquid crystal display device, the liquid crystal display element, and the liquid crystal display device will be described in detail. <Photosensitive spacer composition for photospacer and method for producing photospacer> The photosensitive resin composition for photospacer of the present invention comprises an alkali-soluble polymer substance and

And a polymerizable monomer containing a urethane group and 5 to 15 acrylic groups, and a photopolymerization initiator. Since the photospacer produced from the photosensitive resin composition for a photospacer of the present invention has a high degree of deformation recovery, display unevenness in the display element can be eliminated.

[0028] Further, the method for producing a photospacer of the present invention includes at least two substrates, a liquid crystal provided between the substrates, two electrodes for applying an electric field to the liquid crystal, and the space between the substrates. A photospacer for regulating the cell thickness of the liquid crystal display device, and the photospacer of the present invention is formed on one of the two substrates. A layer forming step of forming a photosensitive resin layer containing the photosensitive resin composition for spacers, and a patterning step of patterning the formed photosensitive resin layer by exposure and alkali development.

[0029] Specifically, the photospacer according to the present invention is formed from the photosensitive resin composition for photospacers of the present invention, and 5 to 15 urethane groups as polymerizable monomers in the composition. A compound containing an acrylic group is used.

According to the method for producing a photospacer of the present invention, a photospacer having a high degree of deformation recovery can be easily produced.

[0030] Hereinafter, a method for producing the photospacer of the present invention will be described, and details of the photosensitive resin composition for a photospacer of the present invention will be described through the description.

[Layer formation process]

In the layer forming step according to the present invention, a photosensitive resin layer containing the photosensitive resin composition for a photospacer of the present invention on a substrate (hereinafter, also simply referred to as “photosensitive resin composition layer”). This is a process of forming.

This photosensitive resin composition layer constitutes a photospacer that has good deformation recovery properties and can maintain a uniform cell thickness through the manufacturing process described later. By using the photospacer, display unevenness in an image in a display device, which tends to cause display unevenness due to a change in cell thickness, is effectively eliminated. [0031] As a method of forming a photosensitive resin composition layer on a substrate, (a) a method of applying a solution containing the photosensitive resin composition for a photospacer of the present invention by a known application method, and (b) A method of laminating by a transfer method using a photosensitive transfer material is preferable. Each is described below.

[0032] (a) Application method

The photosensitive resin composition can be applied by a known application method such as spin coating, curtain coating, slit coating, dip coating, air knife coating, roller coating, wire bar coating, gravure coating. Or an etha trusion coating method using a popper described in US Pat. No. 2,681,294. Among them, the method using a slit nozzle or a slit coater is preferable.

[0033] In the present invention, in particular, a mode in which a photosensitive resin composition is applied onto a substrate with a slit nozzle and dried to form a photosensitive resin composition layer on the substrate is preferable. is there.

[0034] When the photosensitive resin composition layer is formed by coating, the layer thickness is preferably 0.5 to 10.0 μm, more preferably 1 to 6 / ζ πι. When the layer thickness is within the above range, the generation of pinholes during the formation of coating during production can be prevented, and development and removal of unexposed areas can be performed without requiring a long time.

The slit-shaped nozzle is a slit-shaped nozzle having a slit-shaped hole at a portion from which the liquid is discharged. As the slit nozzle or a slit coater having the slit nozzle, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-79163, JP-A-2001-310147, etc. The slit-shaped nozzles and slit coaters described are preferably used.

[0036] (b) Transcription method

In the case of transfer, using a photosensitive transfer material, the photosensitive resin composition layer formed in a film shape on the temporary support is pressure-bonded or thermocompression-bonded with a roller or flat plate heated and Z or pressurized to the substrate surface. Then, the photosensitive resin composition layer is transferred onto the substrate by peeling off the temporary support. Specifically, the methods described in JP-A-7-110575, JP-A-11-77942, column 2000-334836, column 2002-148794 are disclosed. Examples include a minator and a laminating method. From the viewpoint of low foreign matter, it is preferable to use the method described in JP-A-7-110575.

[0037] In the present invention, in particular, a photosensitive transfer material for forming a spacer having a photosensitive resin composition layer on a temporary support is used, and a photosensitive resin is formed on a substrate. An embodiment in which the composition layer is transferred and formed is preferable. The layer thickness when the photosensitive resin composition layer is transferred and formed is also the same as when the coating is formed.

[0038] Specifically, after removing the protective film (cover film) from the photosensitive transfer material, the surface of the exposed photosensitive resin composition layer is superposed on the substrate surface as the transfer material, Apply pressure (heat) and bond (laminate). Bonding can be suitably performed using a known laminator (vacuum laminator or the like), and an auto cut laminator is preferable from the viewpoint of increasing productivity.

[0039] Examples of the substrate on which the photosensitive resin composition layer is formed include, for example, a transparent substrate (for example, a glass substrate or a plastic substrate), a substrate with a transparent conductive film (for example, an ITO film), and a substrate with a color filter (color). 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 / ζ πι.

In addition, the substrate can be subjected to a coupling treatment in advance to improve the adhesion between the photosensitive resin composition or the photosensitive resin composition layer of the photosensitive transfer material. As the coupling treatment, a method described in JP-A-2000-39033 is preferably used.

[0040] When forming the photosensitive resin composition layer, an oxygen-blocking film can be further provided on the photosensitive resin composition layer. As a result, the exposure sensitivity can be increased, and the oxygen blocking film can have the same structure as that described in the later section of the intermediate layer. The thickness of the oxygen blocking film is preferably 0.5 to 3.0 m.

Further, in order to improve transferability, a thermoplastic resin layer having cushioning properties may be provided.

[0041] -Photosensitive resin composition-

Next, the photosensitive resin composition will be described.

The photosensitive resin composition (photosensitive resin composition for photospacers of the present invention) is an alkali. It contains a soluble polymer substance, a polymerizable monomer containing a urethane group and 5 to 15 acrylic groups, and a photopolymerization initiator. Moreover, it can comprise using other components, such as a coloring agent and surfactant, as needed.

[0042] (A) Alkali-soluble polymer substance

The alkali-soluble polymer substance has a function as a binder component in forming a photospacer, and preferably has a crosslinking group itself. The alcoholic soluble polymer substance may be a monomer homopolymer or a copolymer composed of a plurality of monomers, which are appropriately selected according to the purpose, etc. A copolymer having at least a structural unit represented by the following general formula (1), and a structural unit composed of (meth) acrylate having at least one aromatic ring and at least one Z or aliphatic ring. It is mentioned as preferable.

[0043] [Chemical 3]

One »Formula

[0044] This copolymer includes, for example, a polymerizable monomer having a carboxyl group, a monomer represented by the following formula (2), an aromatic ring and (meth) acrylate having one or more Z or aliphatic rings, and If necessary, other monomers copolymerizable with these can be obtained by copolymerizing by a known method.

[0045] [Chemical 4]

Formula (2)

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 have a hydrogen atom or a substituent. Represents an alkyl group, an aryl group, a halogen atom, or a cyan group.

[0047] Examples of the polymerizable monomer having a carboxyl group include (meth) acrylic acid, belbenzoic acid, maleic acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. In addition, 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 and 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.

[0048] Examples of the monomer represented by the formula (2) include, for example, aryl (meth) acrylate, 3 chloro 2 probe (meth) acrylate, 3 phenol 2 probe (meta) ) Atrelate, 3— (Hydroxyphenol) 2 — Probe (Meth) acrylate, 3 — (2 — Hydroxyphenol) — 2 — Probe (Meth) acrylate, 3 — (3,4 dihydroxyphenyl) —2—probe (meth) acrylate, 3- (2,4-dihydroxyphenol) 2—probe (meth) acrylate, 3— ( 3, 4, 5 Trihydroxyphenyl) 1-2-probe (meth) acrylate, 3- (3-methoxy-4-hydroxyphenol) 2-probe (meth) acrylate, 3— (3,4 dihydroxy mono-5-methoxyphenol) 2—probe (meth) acrylate, 3— (3,5 dimethoxy monohydroxyl ester) 2 Probe (meth) atarylate, 3— (2 Hydroxy 4-methylphenol) 2—Probe (meth) acrylate, 3— (4 —Methoxyphenol) —2—Probe (Meth) atallylate, 3— (4-Ethoxyphenol) 2-Probe (meth) acrylate, 3- (2-Methoxyphenol)-2-Probe (meth) acrylate, 3- (3,4 Dimethoxyphenol) 2-Pro Base (meth) acrylate, 3— (3-methoxy 4-propyloxy) 2-Probe (meth) acrylate, 3- (2, 4, 6 trimethoxy) 1 —Probe (meth) acrylate, 3— (3-methoxy —4 benzyloxyphenyl) —2—Probe (meth) acrylate, 3— (3— (3′— Methoxyphenol— 4) Benzyloxyphenyl) 2-Probe (meth) acrylate, 3— (3, 4, 5 Trimethoxyphenol) 1 2-Probe (meth) acrylate, 3 — (4-Methylphenol) 2-Probe (meth) acrylate;

[0049] 3 Phenol— 3— (2, 4, 6 Trimethyl Phenol) —2-Probe (Meth) Atylate, 3, 3— [Di- (2, 4, 6 Trimethyl Phenol— )] — 2—Probe (Meth) Atalylate, 3 ferrules 3— (4 Methylphenol) —2—Probe (Meth) acrylate, 3, 3 diferrules 2— Probe (meth) acrylate, 3— (2 chlorophenol) — 2 — Probe (meth) acrylate, 3 — (3 chlorophenol) — 2 — Probe (meth) acrylate 3-(4 chlorophenol) 2-probe (meth) acrylate, 3-(2, 4 dichlorophenol) 2-probe (meth) acrylate, 3-(2 bromophenol -Le) -2—Probe (meth) attalylate, 3 Bromo—3 Felulu 2—Probe (meth) atalylate, 3 Chlorone 3—Fuel-Lou 2—Probe ( (Meta) attalylate, 3— (4-Trophele) -2—Probe (Meta) Atarylate, 3 -— (2-Trophele) —2-Probe (Meta) Atarylate, 3-— (3-Tropheel ) 2-Probe (meth) acrylate, 2-Methyl 1 3-Ferule 2—Probe (meth) acrylate, 2-Methyl 3— (4-Chlor) 2—Pro Bale (meta) atelate,

[0050] 2—Methyl 3— (4—-Trophenyl) 2—Probe (Meth) Atalylate, 2 Methyl —3— (4 Aminophenol) One 2-Probe (Meth) Atari 2-methyl-3, 3-diphenyl 2-propyl (meth) ate, 2-ethyl 1,3-diphenyl 2-propyl (meth) ate, 2-ethoxymethylene -Phenol-2-Probe (Meth) Atalylate, 2-Methyl 3- (4-Methoxy Phenol) 2-Probe (Meth) Alkyl Relay, 2, 3 Diphenyl- 2—Probe (Meta) Atrelay®, 1, 2, 3 卜 Referrer 2—Probe (Meta) Attalylate, 2, 3, 3 Triferre 2—Probe (Meta) Atalylate, 1, 3 Diphenol- 2 -Probe (meth) acrylate, 1— (4-Methylphenol) 3-Fueru 2—Probe (meth) acrylate, 1— Ferrule 3— (4-Methylphenol) 2-Probe (meth) acrylate, 1—Fuel leu 3-— (4-methoxyphenol) 2-Probe (meth) attaly 1- (4-methoxyphenol) 3 phenol 2-probe (meth) acrylate, 1, 3 di (4 chlorophenol) — 2-probe (meth) acrylate, 1 (4 brom fuel) 3 Ferro 2-Probe (meta) attalylate;

1 Ferrule 3— (4-Trophele) 1—Probe (Meth) Attalate, 1, 3—Di (2—Trophe) —2—Probe (Meth) Atari 1- (4-Dimethylaminophenol) 3 Ferrule 2—Probe (meth) acrylate, 1—Fuel 3— (4-Dimethylaminophenol) 1— Probe (meth) acrylate, 1, 1-di (4 dimethylaminophenol) 1 3-Fuel loop 2—Probe (meth) acrylate, 1, 1, 3 Triphenyl 1 —Probe (meth) acrylate, 1, 1, 3, 3—Tetraferrule 2—Probe (meth) acrylate, 1 (4 methylphenol) 3 Ferrule 2—Probe -Metal Atalylate, 1—Fuel 2—Probe (Meta) Atalylate, 1, 2—Di-Fuel 2—Probe (Meta) Atalylate, 1—Fuel 2 —Methyl 2-probe Meth) Atari rate, hexyl 1-cyclopropyl 2-Purobe - Le (meth) Atari rate, 2-benzyl-one

2 Probe (meta) acrylate, 1, 1-ge (4 chlorophenol) 2—Probe (meta) acrylate, 1—Cyano 2—Probe (meth) acrylate, 3 Carlino 2 Propell (meth) acrylate, 3— (2—Methylphenol) —2—Probe (meth) acrylate, 3— (2, 4 Dimethylphenol) —2 —Probe (meth) atalylate, 1— (2—carbethoxyisopropyl) —3—Methyl—2—Probe (meth) atalylate, 1— (1—carbethoxyisopropyl) —2 —Probe (meth) atallylate, 1— (1—carbethoxychyl) 3—Methyl-2 probe (meth) acrylate, 1 carboxylate 3 chlor

3 Methyl-2-probe (meth) acrylate, 1 carbethoxymethylene 3 Methyl — 2 probe (meth) acrylate, 1-cyan 3-methyl-2- probe (meth) acrylate 1-cyclohexyl 3- (2-hydroxycyclohexyl) 2-probe (meth) acrylate, 3 cyclopentyl 2-probe (meth) acrylate; [0052] 3 furyl—2—probe (meth) acrylate, 3 chloro—2—probe (meth) acrylate, 3 bromo 1—probe (meth) acrylate, 2 —Methyl 3-chloro 1—Probe (meth) acrylate, 2-Methyl—3 Bromine— 2-Probe (meth) acrylate, 2 Chlor 3—Ferule 2—Pro- (Meth) attalylate, 2 bromide 3—Ferrolu 2—probe (meth) attalylate, 2 bromide 3— (4-trofehl) 2 -probe (meth) attalylate , 2 -Fluoro 3 phenol-2 -Probes (meth) acrylate, 2 Fluoro 3— (4-Methoxyphenol) 2 -Probes (meth) acrylate, 2 Siano 3 -Fe 2—Probe (meth) acrylate, 2 chloro 1—Probe (meth) acrylate, 2—Brom— 2—Probe (me ) Atarylate, 2-chloro-1,3,3 difluoro-2—probe (meth) atalylate, 2 fluoro-3 cucumber route 2—probe (meth) atalylate, 2,3 dibromo—2—pro Base (meth) acrylate, 2 Chloro 3-methyl 2-probe (meth) acrylate, 1,1-dimethyl 2-probe (meth) acrylate, 2-pentale ( (Meth) acrylate, 2-hexyl (meth) acrylate, 2-heptyl (meth) acrylate, and the like.

Among these, aryl (meth) acrylate is particularly preferred in terms of curability and raw material price.

[0053] Examples of the "(meth) acrylate having at least one aromatic ring and Z or aliphatic ring" include, for example, (meth) acrylic acid cycloalkyl ester [for example, (meth) acrylic acid cyclohexyl, (Meth) acrylic acid norbornyl, (meth) acrylic acid adamantyl, etc.], (meth) acrylic acid aryl ester [e.g., (meth) acrylic acid fur, (meth) acrylic acid black mouth foul, (Meth) acrylic acid methoxy file, (meth) acrylic acid naphthyl, etc.], aralkyl esters [eg, (meth) acrylic acid benzyl, (meth) acrylic acid phenethyl etc.], and the like.

Of these, benzyl (meth) acrylate and cyclohexyl (meth) acrylate are preferred in terms of raw material price, solubility, pigment dispersibility, and the like.

[0054] Further, as "other monomers" copolymerizable with these structural units, for example, (meth) acrylic acid alkyl ester [for example, methyl (meth) acrylate, ethyl (meth) acrylate, Propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic acid n— Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate , (Meth) acrylic acid such as stearyl (meth) acrylate ( ¹ to ¹⁸ ) alkyl ester, etc.];

[0055] (Meth) acrylic acid aralkyl esters [for example, (meth) acrylic acid benzyl, etc.], substituted (meth) acrylic acid alkyl esters [for example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl ( (Meth) acrylate, dimethylaminopropyl (meth) acrylate, etc.], (meth) acrylamides [eg (meth) acrylamide, dimethyl (meth) acrylamide, isopropyl (Meth) acrylamide, t-butyl (meth) acrylamide, etc.], substituted (meth) acrylamides [for example, (meth) atalyloylmorpholine, dimethylaminopropyl (meth) acrylamide, etc.], aromatic bullets [for example, scan styrene, Bulle toluene, _alpha - methyl styrene, etc.], heterocyclic Bulle [E.g., berylimidazole, vinyl pyridine, etc.], butyl esters [e.g., vinyl acetate, propionate butyl, versatic acid butyl, etc.], Ν-buramides [e.g. Formamide, Ν-buluacetoamide, etc.], aryl esters [eg, allylic acetate, etc.], halogen-containing monomers [eg, salt vinylidene, vinyl chloride, etc.], cyanobyl [eg, (meth) acrylonitrile, etc. ], Olefins [for example, ethylene, propylene, etc.], and the like.

[0056] Among these, (meth) acrylic acid alkyl ester [for example, (meth) methacrylic acid methyl ester, 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. , (Meth) acrylate ethyl, propyl (meth) acrylate, isopropyl (meth) acrylate, η-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, ( Hexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl, etc.] are particularly preferred.

These other copolymerizable components may be used alone or in combination of two or more.

[0057] wherein the copolymerization ratio of each component is "structural unit having a carboxyl group" 1 0-40 Monore ^_0/0 force S Preferably, 15-35 Monore ^_0/0 force S More preferably, 20 to 35 Monore ^_0/0 force S especially good Masui. When the structural unit having a carboxyl group is within the above range, good developability is obtained. As well as being obtained, the developer resistance of the image area is also good. Also, it or 20-80 Monore ^_0/0 force S preferably "Concrete unit structure represented by the general formula (I)", 20-75 Monore ^_0/0 force S, and particularly preferably 25 to 75 Monore%. When the structural unit represented by the general formula (I) is within the above range, good curability and developability can be obtained. Also, "having one or more aromatic rings and Ζ or aliphatic ring (meth) structural unit comprising Atari rate" 10 to 70 mole ^_0/0 preferably fixture 10 to 60 mole ^_0/0 further preferred instrument 10 to 50 mol% is particularly preferred. When the structural unit composed of (meth) acrylate having at least one aromatic ring and one or more aliphatic rings is within the above range, the pigment dispersibility is excellent and the developability and curability are also good.

[0058] The weight average molecular weight of the copolymer suitable as the alkali-soluble polymer substance is preferably 5,000 to 200,000 S, more preferably 10,000 to 100,000, more preferably 20,000 to 80,000. Particularly preferred. If the weight average molecular weight is within the above range, it is desirable from the viewpoint of the suitability for production of the copolymer and developability.

[0059] Hereinafter, specific examples of the copolymer suitable as an alkali-soluble polymer substance include alkali-soluble binders described in paragraph numbers [0031] to [0054] of JP 2003-131379 A, JP 2005 — Alkali-soluble binder described in paragraph Nos. [0035] to [0036] of No. 3861, and a resin having an aryl group and a hydroxyl group described in paragraph Nos. [0035] to [0037] of No. 2003-207787 , Can be referred to.

[0060] The copolymer suitable as the alkali-soluble polymer substance can be obtained by copolymerizing a corresponding monomer according to a conventional method by a known method. For example, it can be obtained by dissolving these monomers in a suitable solvent and adding a radical polymerization initiator to polymerize them in a solution.

[0061] Examples of suitable solvents for copolymerization include forces that can be arbitrarily selected according to the solubility of the monomer and the copolymer to be produced. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol , Acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethylformamide, formaldehyde, toluene, and mixtures thereof. In addition, a polymerization initiator can be used, and examples of the polymerization initiator include 2, 2′-azobis (isobuty-mouth-tolyl) (ΑΙΒΝ), 2, 2′-azobis mono (2 , 4'-dimethylvale-tolyl), peroxides such as benzoyl peroxide, and persulfates.

[0062] In addition, a known chain transfer agent may be appropriately used for the purpose of adjusting the molecular weight. In addition, it may be necessary to appropriately adjust the polymerization concentration, initiator amount, chain transfer agent, polymerization temperature, and the like. For example, the polymerization concentration is preferably 5 to 50% by mass, more preferably 10 to 40% by mass.

[0063] The content of the alkali-soluble polymer substance in the photosensitive resin composition (or photosensitive resin composition layer) is 30 to 70 masses relative to the solid content of the composition or the layer. 40% to 50% by mass is preferred.

[0064] (i) Polymerizable monomer

The polymerizable monomer according to the present invention contains a urethane group and 5 to 15 acrylic groups. If the number of acryl groups is less than 4, the deformation recovery rate of the photospacer may be insufficient, and if it exceeds 15, the development time increases, which is not preferable in production.

The number of acrylic groups is more preferably 5-9, and most preferably 5-6.

Examples of the monomer having 5 to 6 acrylic groups include compounds represented by the following general formula (Α) or (Β).

[0065] [Chemical 5]

[0066] In the general formula (A) or (B), R represents the following formula (a) (b) or (c).

1

[0067] [Chemical 6]

[0068] In the formula (a), n represents an integer of 28.

[0069] Commercially available monomers may be used as the polymerizable monomer according to the present invention. As monomers having 6 talyl groups, UA-306H, UA-306T, and UA-306I manufactured by Kyoeisha Chemical Co., Ltd. are used. The As a monomer having 9 acrylic groups, there is UA-32P manufactured by Shin-Nakamura Igaku.

As a monomer having 10 acrylic groups, UA-510H manufactured by Kyoeisha Co., Ltd. is available. As a monomer having 15 acrylic groups, there is UA-32P manufactured by Shin-Nakamura Igaku.

[0070] Further, the polymerizable monomers may be used in combination of two or more, in addition to being used alone. Examples of monomers that may be used in combination include ester compounds, amide compounds, and other compounds.

[0071] Examples of the ester compound include monofunctional (meth) acrylic acid ester, polyfunctional (meth) acrylic acid ester, itaconic acid ester, crotonic acid ester, isocrotonic acid ester, maleic acid ester, and other ester compounds. , Etc. These may be used alone or in combination of two or more. Of these, monofunctional (meth) acrylic acid esters and polyfunctional (meth) acrylic acid esters are preferred.

[0072] Examples of the monofunctional (meth) acrylic acid ester include polyethylene glycol mono

(Meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxychetyl mono (meth) acrylate, and the like.

[0073] Examples of the polyfunctional (meth) acrylic acid ester include polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1, 3-Butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, penta erythritol tetra (meth) acrylate, di Pentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hex (meth) acrylate, dipenta erythritol poly (meth) acrylate Sorbito Tri (meth) Atari rate, sorbitol tetra (meth) Atari rate, trimethylol E Tan tri (meth) Atari rate, neopentyl Legris Koruji (meth) Atari rate, such as hexanediol di (meth) Atari rate and the like to. Of these, dipentaerythritol poly (meth) acrylate is particularly preferable.

[0074] Other examples of the polyfunctional (meth) acrylic acid ester include those obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane, JP-B 48-41708, JP-B 50-6034 Polyurethane acrylates described in JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, and JP-B-52-30490 Epoxy acrylate which is a reaction product of epoxy resin and (meth) acrylic acid, and (meth) acrylate ester urethane urethane (meth) acrylate and the like described in JP-A-60-258539 And bull esters.

[0075] Examples of the "other ester compound" include trimethylolpropane tri (atallyloyloxypropyl) ether, tri (atariloy mouth kichetil) isocyanurate, Japan Adhesion Association Vol. 20, No. 7, No. 300. Photocurable monomers and oligomers described on page 308.

[0076] Further, examples of the amide compound include amides (monomers) of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and specific examples include methylene bis (meth) acrylamide, 1, 6-hexamethylene bis- (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, xylylene bis (meth) acrylamide, and the like described in JP-A-60-258539. And (meth) acrylic acid amide.

Examples of the “other compounds” include aryl compounds described in JP-A-60-258539.

[0077] The content of the polymerizable monomer in the photosensitive resin composition (or photosensitive resin composition layer) is 10 to 60% by mass with respect to the total solid content of the composition or the layer. 20 to 50% by mass is more preferable.

In the present invention, the ratio (MZB) of the content B (mass%) of the alkali-soluble polymer substance to the content M (mass%) of the polymerizable monomer in the photosensitive resin composition. ) Is preferably 0.6 to 1.5. A more preferable range of the ratio M / B is 0.7 to 1.0.

[0079] (C) Photopolymerization initiator

The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of about 50 or more in a wavelength region of about 300 to 500 nm. For example, as disclosed in JP-A-2-48664, JP-A-1-152449, and JP-A-2-153353, aromatic ketones, oral fin dimers, benzoin, benzoin ethers, polyhalo And halogens, hydrocarbon derivatives, ketone compounds, ketoxime compounds, organic peroxides, thio compounds, hexaarylbiimidazoles, aromatic onium salts, ketoxime ethers, and the like.

[0080] Among the above, a combination of 4,4'-bis (jetylamino) benzophenone and 2- (o black-mouthed) 4,5 diphenylimidazole dimer, 4- [ρ-Ν, Ν '—Di (ethoxycarboromethyl) 2,6 di (trichloromethyl) s triazine], 2, 4 Bis (trichloromethyl) — 6— [4— (Ν, Ν'-bisethoxycarboromethylmethylamino) — 3-Bromophenol] s triazine and the like are preferable.

[0081] Two or more photopolymerization initiators may be used in combination in addition to the single photoinitiator.

The content of the photopolymerization initiator in the photosensitive resin composition (or photosensitive resin composition layer) is from 0.6 to 0.6 with respect to the amount of the thread and the cross-linking group in the composition. 2.82 mol Ζmol is preferred 1.0 to 2.0 mol Ζmol is more preferred. When the content is within the above range, the crosslinked structure is stabilized, and the height of the produced photospacer can be kept uniform.

[0082] (D) Other ingredients

The photosensitive resin composition (or photosensitive resin composition layer) may further comprise a colorant, a surface active agent, if necessary, in addition to the alkali-soluble polymer substance, the polymerizable monomer, and the photopolymerization initiator. Additives such as an agent, a solvent, a thermal polymerization inhibitor, and an ultraviolet absorber can be used.

[0083] One colorant

Examples of the colorant include dyes and pigments. As for the preferred pigment type, size, etc., for example, the description in JP-A-11-149008 can be selected as appropriate. 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. The extender pigment is not particularly limited and may be appropriately selected depending on the intended purpose. For example, extender pigments described in paragraphs [0035] to [0041] of JP-A No. 2003-302639 are preferable. Preferable examples of the color pigment include the pigments described in paragraph No. [0043] of JP-A-2003-302639.

[0084] Surfactant

As surfactant, constituent of photosensitive resin composition (or photosensitive resin composition layer) Anything that mixes with can be used. As preferable surfactants, paragraph numbers [0015 to [0024] of JP-A-2003-337424, paragraph numbers [0012 to [0017] of JP-A-2003-177522, and paragraphs of JP-A-2003-177523 are disclosed. No. [0012 To [0 015], Paragraph No. [0010 To [0013] of JP 2003-177521, Paragraph No. [0010 TO [0013], JP 2003-177520, JP 2003-177520] The surfactants described in paragraph numbers [0012] to [0015] of JP-A-11-133, paragraph numbers [0034] to [0035] of JP-A-11 133600, and JP-A-6-16684 are preferably exemplified.

From the viewpoint of obtaining higher effects, fluorosurfactants and Z or silicon surfactants (fluorine surfactants or silicon surfactants, surfactants containing both fluorine and silicon atoms) The most preferable is a fluorosurfactant in which it is preferable to select one or more of the above.

[0085] When a fluorosurfactant is used, the fluorine atom number of the fluorine-containing substituent in the surfactant molecule is preferably 1 to 38, more preferably 5 to 25, and most preferably 7 to 20. . When the number of fluorine atoms is within the above range, it is desirable from the viewpoint of good solubility and an effect of improving unevenness.

[0086] Particularly preferably, the surfactant contains a monomer A represented by the following general formula (a) and a monomer B represented by the following general formula (b) as a copolymerization component, Examples thereof include copolymers having a copolymerization ratio (AZB [mass ratio]) with the monomer B of 20Z80 to 60Z40 (hereinafter also referred to as “surfactant suitable for the present invention”).

[0087] [Chemical 7]

In the general formula:

And R ³ are each independently a hydrogen atom or a methyl group. Represents, preferably

R ² is a hydrogen atom, and R ³ 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, and among them, an alkyl group having 1 to 2 carbon atoms is preferable. R ⁴ is particularly preferably a hydrogen atom.

In the general formula (a), n represents an integer of 1 to 18, preferably an integer of 2 to 10. m represents an integer of 2 to 14, and preferably an integer of 4 to 12. C F in the general formula (a) is m 2m + l The ratio of C F to monomer A, which may be linear or branched, is preferably 20 to 70% by mass. M 2m + l

Particularly preferred is 40 to 60% by mass.

In the general formula (b), p and q each independently represent an integer of 0 to 18, preferably 2

~ 8. p and q may 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.

[0092] Suitable surfactants in the present invention (copolymer), based on the total weight of the copolymer, wherein 20 to 60 mass Monomer A ^_0/0, the monomer B and 80 to 40 mass ⁰ / _0, and the monomers a and another is preferred instrument further being copolymerized in copolymerization ratio as its remaining mass% of any monomer other than B is a monomer a 25 to 60 weight ^_0/0 the monomer B 60 to 40 mass ^_0/0, and the monomer a and other optional monomers and the remaining mass percent was copolymerization ratio in copolymerized preferably that are members monomers a and non-B 25-60 mass ^_0/0, the monomer B 75 to 40 weight ^_0/0, and any other monomer other than said monomers a and B are copolymerized in copolymerization ratio as its remaining mass%, Rukoto Is more preferred.

[0093] Among the surfactants suitable for the present invention (a copolymer obtained by copolymerizing at least monomer A and monomer B), a preferred form is that R ¹ in the general formula (a) is a hydrogen atom. N = 2, m = 6, R ² in the general formula (b) is a hydrogen atom, R ³ force S methyl group, R ⁴ is a hydrogen atom, P = 7, q = 0, monomer B, or R ² in the general formula (b),

And R ⁴ is a hydrogen atom, and a monomer B in which p = 0 and q = 7 is copolymerized at a copolymerization ratio (Α / Β) of 20Z80 to 60Z40. Particularly preferred is a copolymerization ratio of 25-60 to 40-40. 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 a copolymerization component are described in paragraph No. 2003-337424. As described in Table 1 of No. [0068].

[0094] Solvent

In addition to the above components, an organic solvent can be used for preparing the photosensitive resin composition. Examples of organic solvents include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol methanol monomethyl ether ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactyl lactate, methyl lactate, strength prolatatum, etc. I can list them.

[0095] Thermal polymerization inhibitor

The photosensitive resin composition can further contain a thermal polymerization inhibitor. Examples of thermal polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, tert-butinole strength, tectonole, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol) ), 2, 2'-methylenebis (4-methyl 6t-butylphenol), 2 mercaptobenzimidazole, phenothiazine and the like.

[0096] UV absorber

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

[0097] Specifically, phenyl salicylate, 4 t-butyl phenol salicylate, 2,4-di-t-butyl phenol 3 ', 5'-di-t- 4'-hydroxybenzoate, 4 t-butyl Phenylsalicylate, 2,4-Dihydroxybenzophenone, 2 Hydroxy-4-methoxy benzophenone, 2 Hydroxy 4-n-Otoxybenzophenone, 2— (2′-Hydroxy-5 ′ methylphenyl) benzotriazole, 2 — (2 ′ Hydroxy 3′— t-Butyl — 5′—Methylphenol) 1-5 Chlorobenzozoazole, Ethyl 2 Cyan 3, 3—Diphenyl Atarylate, 2, 2 ′ Hydroxy-4-methoxybenzophenone , Nickel jib Tildithiocarbamate, bis (2, 2, 6, 6-tetramethyl-4-pyridine) -sebacate, 4 t-butylphenol salicylate, phenyl salicylate, 4-hydroxy 2, 2, 6, 6-tetramethylpiperidine condensate Bis (2,2,6,6-tetramethyl-4-piperiduryl) -ester, 2- [2hydroxy-3,5bis (α, a-dimethylbenzyl) phenol] — 2H benzotriazole, 7- {[4 Black mouth 6- (Jetylamino) -5-triazine-2 yl] amino} 3 phenol coumarin and the like.

In addition to the additives, the photosensitive resin composition can also contain “adhesion aid” described in JP-A-11-133600, other additives, and the like.

[0099] As described above, the photosensitive resin composition layer according to the present invention can be formed by a transfer method using a photosensitive transfer material as well as by a coating method in which the photosensitive resin composition is applied. The photosensitive transfer material can be suitably formed using an integral transfer film such as a resin transfer material described in JP-A-5-72724, and is an integral transfer film. As an example of the structure, a structure having a laminated structure of the temporary support Z, the thermoplastic resin layer Z, the intermediate layer Z, the photosensitive resin composition layer Z, and the protective film is suitable.

[0100] -Photosensitive transfer material-

Next, the photosensitive transfer material will be described.

The photosensitive transfer material according to the present invention has a photospace comprising a temporary support and a thermoplastic resin layer and a photosensitive resin composition layer that are at least alkali-soluble in order from the temporary support side. A photosensitive transfer material for forming a substrate may be used. In addition, if necessary, it may have other layers such as an intermediate layer and a protective film.

[0101] Photosensitive resin composition layer

The photosensitive resin composition layer is a layer constituting the photospacer when the photospacer is formed. The photosensitive resin composition layer can be suitably formed by applying and drying the photosensitive resin composition for a photospacer of the present invention by a known application method.

[0102] The photosensitive resin composition is preferably applied with a slit-like nozzle having a slit-like hole in the portion from which the liquid is discharged. The specific details of the slit nozzle and slit coater are as described above. The layer thickness of the photosensitive resin composition layer is 0.5-10. 1 to 6 / ζ πι is more preferable. When the layer thickness is within the above range, the generation of pinholes during coating formation during production can be prevented, and development and removal of unexposed portions can be performed without requiring a long time.

[0103] Thermoplastic resin layer

In the photosensitive transfer material, at least one thermoplastic resin layer can be provided between the photosensitive resin composition layer and the temporary support. The thermoplastic resin layer is preferably alkali-soluble from the viewpoint that alkali development is possible, and that the thermoplastic resin layer protruding during transfer can prevent contamination of the transferred material.

[0104] This thermoplastic resin layer effectively prevents transfer defects caused by unevenness on the transfer material when the photosensitive resin composition layer is transferred to the transfer material. The photosensitive resin composition layer and the transferred material can be deformed corresponding to the irregularities on the transferred material when the photosensitive transfer material is heat-pressed to the transferred material. Adhesion with the material can be improved.

[0105] The thickness of the thermoplastic resin layer is preferably 0.1 to 20 m. When the layer thickness is within the above range, the peelability of the temporary support force at the time of transfer is excellent, and it is effective for absorbing irregularities on the transfer material, and the photosensitive resin composition layer is reticulated. Chillons are generated and transfer defects do not occur. Further, it is preferably 1.5 to 16 / ζ πι, more preferably 5 to 15.0 μm.

Reticulation means that when the intermediate layer is stretched due to moisture absorption or the like, the flexible thermoplastic resin layer buckles and fine wrinkles are formed on the surface of the photosensitive resin composition layer. This is a cause of transfer failure.

[0106] The thermoplastic resin layer can be composed of at least a thermoplastic resin, and other components can be appropriately used as necessary. The thermoplastic resin is not particularly limited and can be appropriately selected, but those having a substantial softening point of 80 ° C. or less are preferable.

[0107] Examples of the thermoplastic resin having a substantial softening point of 80 ° C or lower include, for example, a kenne of ethylene and acrylate copolymer, styrene and (meth) acrylate. Saponified product with copolymer, saponified product with butyltoluene and (meth) acrylic acid ester copolymer, poly (meth) acrylic acid ester, (meth) atariate with (meth) acrylic acid butyl and vinyl acetate, etc. Examples of suitable materials such as sulfonic acid ester copolymers are “Plastic Performance Handbook” (edited by the Japan Plastics Industry Federation, All-Japan Plastics Molding Industry Association, published by the Industrial Research Council, 1968 10). Among those organic polymers whose soft spot is about 80 ° C or less as described in the 25th of May), those that are alkali-soluble are also included. These may be used alone or in combination of two or more.

[0108] Further, even if the substantial soft softening point is 80 ° C or lower, and even if it is an organic polymeric material itself having a softening point of 80 ° C or higher, Examples thereof include those having a substantial softening point of 80 ° C or less by adding various compatible plasticizers. The plasticizer can be appropriately selected according to the purpose without any particular limitation. For example, polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptino phthalate, dibutino phthalate, tricresyl. Phosphate, Cresino resifeninore phosphate, biphenyl diphosphate phosphate, and the like.

[0109] In addition to the thermoplastic resin, the thermoplastic resin layer has a soft softness point substantially not exceeding 80 ° C for the purpose of adjusting the adhesion force with the temporary support as another component. Within the range, various polymers, supercooling substances, adhesion improvers, surfactants, mold release agents and the like can be added.

[0110] Middle layer

The photosensitive transfer material is preferably provided with an intermediate layer for the purpose of preventing mixing of components during the application of a plurality of layers and during storage after 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 composition layer. An organic solvent is used to form the thermoplastic resin layer and the photosensitive resin composition layer, but by providing an intermediate layer, it is possible to prevent the two layers from being mixed with each other.

[0111] The intermediate layer is preferably dispersed or dissolved in water or an aqueous alkali solution. Known materials can be used for the intermediate layer. For example, polyvinyl ether Z maleic anhydride polymer and carboxyalkyl cellulose described in JP-A No. 46-2121 and JP-B No. 56-40824 can be used. Water-soluble salts, water-soluble cellulose ethers, water-soluble salts of carboxyalkyl starch, polybulualcohol, polybulupyrrolidone, polyacrylamides, water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide And water-soluble salts of the group consisting of various types of starch, various starches, and the like, copolymers of styrene and maleic acid, maleate resin, and the like.

These may be used alone or in combination of two or more.

[0112] Among the above, it is preferable to use a water-soluble resin, that is, a water-soluble polymer material. Among these, it is preferable to use at least polyvinyl alcohol, and the combination of polyvinyl alcohol and polyvinylpyrrolidone is preferable. Especially preferred.

The polyvinyl alcohol can be appropriately selected according to the purpose without any restriction, and preferably has an acidity of 80 mol% or more.

[0113] When polyvinylpyrrolidone is used, the content thereof is preferably 1 to 75% by volume, more preferably 1 to 60% by volume, particularly 10 to 50% by volume, based on the solid content of the intermediate layer. I like it. When the content is within the above range, sufficient adhesion to the thermoplastic resin layer can be obtained, and the oxygen blocking ability is also good.

[0114] The intermediate layer preferably has a low oxygen permeability. In other words, it is preferable to be composed of an oxygen-blocking film having an oxygen-blocking function. The sensitivity during exposure is improved, the time load of the exposure machine can be reduced, the productivity can be improved, and the resolution can also be improved. .

[0115] The thickness of the intermediate layer is preferably about 0.1 to 5 / ζ πι, more preferably 0.5 to 2 m.

When the thickness of the intermediate layer is within the above range, the oxygen barrier property is not lowered, and an increase in the intermediate layer removal time during development can be prevented.

[0116] Temporary support

The temporary support is preferably a chemically / thermally stable and flexible material that does not interfere with the transfer and preferably has a peelability to the thermoplastic resin layer.

[0117] The material of the temporary support can be appropriately selected according to the purpose without any particular restriction. Examples thereof include polytetrafluoroethylene, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyethylene, and polypropylene. It is done.

[0118] The structure of the temporary support can be appropriately selected depending on the purpose without particular limitation, and may be either a single layer structure or a laminated structure. In addition, the temporary support is subjected to surface treatment such as glow discharge from the viewpoint of ensuring good releasability with the thermoplastic resin layer. Don't have an undercoating layer like gelatin that you like! /. The thickness of the temporary support is about 5 to 300 m, preferably 20 to 150 m.

[0119] 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, the temporary support is removed when the temporary support is peeled off after the photosensitive transfer material provided with the temporary support is brought into close contact with the transfer target. As a result, the transferred object and the like are not charged and attract the surrounding dust and the like. As a result, after the temporary support is peeled off, no dust or the like adheres to the thermoplastic resin layer, and the subsequent exposure process. Thus, pinhole formation due to the formation of an extra unexposed portion can be effectively prevented. 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.

[0120] The temporary support having conductivity can be obtained by containing a conductive substance in the temporary support. The conductive substance is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include metal oxides and antistatic agents.

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. Examples of the form of the metal oxide include crystal fine particles and composite fine particles.

[0121] Examples of the antistatic agent include alkyl phosphate-based surfactants such as Electro Stripper Sakai (manufactured by Kao Corporation), Elenon No. 19 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Betaine amphoteric surfactants such as Amo Igen K (Daiichi Kogyo Seiyaku Co., Ltd.), polyoxyethylene fatty acid ester nonionic surfactants such as Nissan Noon L (Nippon Yushi Co., Ltd.) Emulgen 106, 120, 147, 420, 220, 905, 910 (manufactured by Kao Corporation) and Nissan-Non E (manufactured by NOF Corporation) Non-ionic Other nonionic surfactants such as surfactants, polyoxyethylene alkylphenol ethers, polyhydric alcohol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, etc. The These may be used alone or in combination of two or more. [0122] The conductive layer can be formed by appropriately selecting a configuration using a known conductive material, and the conductive material has a stable conductive effect without being affected by the humidity environment. For example, ZnO, TiO, SnO, AlO, InO, SiO, MgO, BaO, MoO

2 2 2 3 2 3 2 3 and the like are preferable. These may be used in combination of two or more, in addition to being used alone.

[0123] The volume resistivity of the metal oxide or the conductive substance is preferably 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω′cm or less. The particle diameter of the metal oxide or the conductive material is preferably 0.01 to 0.7 111 m, more preferably 0.02 to 0.5 m force! /,

[0124] In the conductive layer, as a binder, for example, gelatin, cellulose nitrate, cenololose triacetate, cenololose diacetate, cenololose acetate butyrate, cellulose esters such as cellulose acetate propionate, vinylidene chloride Further, homopolymers or copolymers including butyl chloride, styrene, acrylonitrile, butyl acetate, alkyl acrylates having 1 to 4 carbon atoms, butyl pyrrolidone, etc., soluble polyesters, polycarbonates, soluble polyamides, and the like can be used.

In addition to the above, the photosensitive transfer material can be further provided with a protective film as another layer.

The protective film has a function of protecting the photosensitive resin composition layer from dirt and damage during storage and the like, and can be composed of the same or similar material as the temporary support. As the protective film, any material that can be easily peeled off from the photosensitive resin composition layer may be used. For example, a silicon paper, a polyolefin sheet, a polytetrafluoroethylene sheet, and the like are preferably used. Among these, a polyethylene sheet or film, or a polypropylene sheet or film is preferable. The thickness of the protective film is preferably 5 to about L 00 m, force S, and more preferably 10 to 30 m.

[0126] For the photosensitive transfer material, a solution (thermoplastic resin coating solution) in which an additive is dissolved together with a thermoplastic organic polymer (thermoplastic resin) is applied onto a temporary support. After preparing a thermoplastic resin layer by drying, a prepared solution (intermediate solution) was prepared by adding a resin additive to the solvent without dissolving the thermoplastic resin layer on this thermoplastic resin layer. The intermediate coating layer is applied and dried, and an intermediate layer is laminated.On the intermediate layer, a solvent that does not dissolve the intermediate layer is used. The photosensitive resin composition prepared as described above is applied, dried, and laminated with a photosensitive resin composition layer, which can be suitably produced.

[0127] In addition to the above, a first sheet in which a thermoplastic resin layer and an intermediate layer were provided in order from the temporary support side on the temporary support, and a photosensitive resin composition layer on the protective film were provided. The second sheet may be prepared and bonded so that the surface of the intermediate layer of the first sheet is in contact with the surface of the photosensitive resin composition layer. Furthermore, a first sheet provided with a thermoplastic resin layer on a temporary support, and a second sheet provided with a photosensitive resin composition layer and an intermediate layer in that order on the protective film side cover, This is prepared by adhering so that the surface of the intermediate layer of the first sheet is in contact with the surface of the thermoplastic resin layer of the second sheet.

[0128] [Patterning process]

In the patterning step according to the present invention, the photosensitive resin composition layer formed on the substrate is subjected to patterning by exposure and alkali development. Specifically, a predetermined mask is disposed above the photosensitive resin composition layer formed on the substrate, and further above the mask (mask) via the mask and, optionally, the thermoplastic resin layer and the intermediate layer. The photosensitive resin composition layer is exposed from the side not facing the photosensitive resin composition layer, and after the exposure is completed, development processing using a developer is performed.

[0129] The light source used for the exposure may be appropriately selected and used as long as it can irradiate light in a wavelength region capable of curing the photosensitive resin composition layer (for example, 365 nm, 405 nm, etc.). wear. Specifically, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp and the like can be mentioned. The exposure amount is usually about 5 to 200 miZcm ² , preferably about 10 to 100 miZcm ² .

[0130] The development can be performed according to a known alkali development method. For example, the photosensitive transfer after exposure using a solvent or an aqueous developer, particularly an alkaline aqueous solution (alkaline developer) or the like. The material is immersed in a developer bath containing a developer or sprayed onto the layer on the photosensitive transfer material by spraying, etc., and further rubbed with a rotating brush, wet sponge, etc., or irradiated with ultrasonic waves. It is possible to carry out the process while processing. The developer temperature is preferably 20 ° C to 40 ° C. After development, it is preferable to wash with water. [0131] As a development method, a known method such as paddle development, shower development, shower & spin development, dip development or the like can be used.

Here, the shower development will be described. The uncured portion can be removed by spraying a developer on the photosensitive resin composition layer after exposure. Prior to development, it is preferable to spray a low-solubility alkaline solution having a low solubility in the photosensitive resin composition layer by shower or the like to remove the thermoplastic resin layer, intermediate layer, and the like. Further, it is preferable to remove the development residue while spraying a cleaning agent or the like after showering with a shower and rubbing with a brush or the like.

[0132] The alkaline aqueous solution used for dissolving the photosensitive resin composition layer, the thermoplastic resin layer, and the intermediate layer in the process of development after exposure and removal of unnecessary parts includes, for example, alkaline substances. A dilute aqueous solution is preferred, and a water-miscible organic solvent added in a small amount is also preferred. The alkaline substance is not particularly limited and may be appropriately selected according to the purpose. Examples thereof include 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 hydrogen carbonate and potassium hydrogen carbonate, alkali metal silicates such as sodium silicate and potassium silicate, alkali metal metasilicates such as sodium metasilicate and potassium metasilicate, triethanol And tetraalkylammonum hydroxides such as amine, diethanolamine, monoethanolamine, morpholine, tetramethylammonium hydroxide, and trisodium phosphate. These may be used alone or in combination of two or more.

[0133] The alkaline aqueous solution preferably has an alkaline substance concentration of 0.01 to 30% by mass, and preferably has a pH of 8 to 14.

[0134] The water-miscible organic solvent can be appropriately selected according to the purpose. For example, methanol, ethanol, 2-propanol, 1 propanol, butanol, diacetone anolenoure, ethyleneglycolole monomethinoatenore. , Ethyleneglycolenoethylenole etherol, ethyleneglycololemono n-butinoleethenole, benzenoreanolenoconole, acetone, methylethylketone, cyclohexanone, _ε -force prolataton, γ-butyrolataton, dimethylformamide, Dimethylacetamide, hexamethylphosphoramide, ethyl lactate , Methyl lactate, ε-force prolatatam, Ν-methylpyrrolidone and the like. The amount of the water-miscible organic solvent added is preferably 0.1 to 30% by mass.

[0135] Various known surfactants can be added to the alkaline aqueous solution, and the addition amount in the case of adding the surfactant is preferably 0.01 to L0 mass%. . The developer temperature is preferably 20 ° C to 40 ° C, and the developer pH is preferably 8 to 13. A roller conveyor or the like is installed in the developing tank, and the substrate moves horizontally. The photosensitive resin is preferably formed on the upper surface of the substrate in order to prevent damage to the single conveyor. When the substrate size exceeds 1 meter, when the substrate is transported horizontally, the developer stays near the center of the substrate, and the difference in development between the center of the substrate and the peripheral part becomes a problem. To avoid this, it is desirable to tilt the substrate diagonally. The inclination angle is preferably 5 ° force 30 °.

In addition, it is preferable to spray pure water before development to moisten the photosensitive resin composition layer so that a uniform development result is obtained.

[0136] Further, after development, if air is blown lightly on the substrate to remove excess liquid substantially and then shower water washing is performed, a more uniform development result is obtained. Moreover, if the residue is removed by spraying ultrapure water at a pressure of 3 to lOMPa with an ultra-high pressure washing nozzle before washing with water, a high-quality image without residue can be obtained. If the substrate is transported to a subsequent process with water droplets attached to the substrate, the process may be soiled or stains may remain on the substrate. Therefore, it is preferable to remove excess water or water droplets by draining with an air knife.

[0137] (Post exposure)

Post exposure is preferably performed between the development and the heat treatment described below from the viewpoints of controlling the cross-sectional shape of the image, controlling the hardness of the image, controlling the surface roughness of the image, and controlling the film thickness reduction of the image. Examples of the light source used for the post-exposure include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp described in paragraph No. 0074 of JP-A-2005-3861. In the post-exposure, it is preferable to directly irradiate the substrate with light of a light source such as an ultra-high pressure mercury lamp or a metal halide without using an exposure mask or the like from the viewpoint of simplification of equipment and power saving. Implement from both sides as needed. In addition, the exposure amount is also 2000 mjZ square centimeters for the top surface: 100 forces, bottom surface: 100 to 2000 mjZ square centimeters Within the range of the above, adjust appropriately according to the above control purpose.

[0138] (Heat treatment)

The hardness of the image can be ensured by reacting the monomer and the crosslinking agent contained in the photosensitive resin composition layer of the present invention by heat treatment. The heat treatment temperature is preferably in the range of 150 ° C to 250 ° C. Hardness is insufficient at temperatures below 150 ° C, and adhesion to the substrate tends to deteriorate at temperatures above 250 ° C. The heat treatment time is preferably 10 minutes to 150 minutes. If it is less than 10 minutes, the hardness is insufficient, and if it is 150 minutes or more, the adhesion tends to be poor.

[0139] Since the photospacer produced by the method for producing a photospacer of the present invention is formed using the photosensitive resin composition layer of the present invention, the photospacer is high when plastically deformed. It exhibits a deformation recovery rate (preferably 70% or more) and has sufficient mechanical properties, so it is effective to keep the cell thickness of the liquid crystal cell uniform. Therefore, the photo spacer can be suitably used for a display device that easily causes display unevenness due to a variation in the cell thickness of the liquid crystal cell.

[0140] The deformation recovery rate of the photospacer produced by the method for producing a photospacer of the present invention is as follows. The photospacer of mφ is a frustum indenter of 50 μΐηφ and the load speed is 0. Deformation recovery rate when performing a load-unloading test under the conditions of 145 gfZ seconds, maximum load 50 mN or 130 mN, holding time 5 seconds, and measurement temperature 23 ° C.

When the maximum load is 50 mN, 75% or more is preferable, 85% or more is more preferable, and 90% or more is more preferable.

When the deformation recovery rate is within the above range, the liquid crystal layer having a desired thickness can be obtained by withstanding the compressive strength of external force and preventing plastic deformation during panel formation. As a result, display unevenness that may occur due to thickness changes is eliminated, and high-quality images can be displayed.

[0141] When the maximum load is 130 mN, 70% or more is preferable, 80% or more is more preferable, and 85% or more is more preferable.

When the deformation recovery rate is within the above range, it can withstand the compressive strength of the external force after forming the panel. As a result, display unevenness (unevenness such as ripples) that can occur due to the compressive strength of the external force is eliminated, and high-quality images can be displayed.

[0142] <Liquid crystal display substrate>

The substrate for a liquid crystal display device of the present invention is obtained by the method for producing a photospacer of the present invention. It is equipped with a photospacer obtained. The photo spacer 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, or the like. There may be a transparent conductive layer (transparent electrode) such as ITO or a liquid crystal alignment film such as polyimide between the driving element such as TFT and the photo spacer.

[0143] For example, when the photospacer is provided on the display light-shielding portion or the drive element, the display spacer is covered with the display light-shielding portion (black matrix or the like) or the drive element previously disposed on the substrate. For example, a photosensitive resin composition layer of a photosensitive transfer material is laminated on a substrate surface, peeled and transferred to form a photosensitive resin composition layer, and then subjected to exposure, development, heat treatment, and the like. By forming a photospacer, the substrate for a liquid crystal display device of the present invention can be produced.

The liquid crystal display substrate 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.

[0144] <LCD device>

The liquid crystal display element of the present invention is configured by providing the liquid crystal display device substrate of the present invention. As one of the liquid crystal display elements, at least one of the pair of optically transparent substrates (including the substrate for a liquid crystal display device of the present invention) and a liquid crystal layer and liquid crystal driving means (simple matrix driving method and active matrix driving method) Including at least).

[0145] 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 photospacer having a uniform height and excellent deformation recovery property, a liquid crystal display device equipped with the color filter substrate has a cell gap between the color filter substrate and the counter substrate. Occurrence of unevenness (cell thickness fluctuation) is suppressed, and display unevenness such as color unevenness can be effectively prevented. Thereby, the produced liquid crystal display element can display a clear image.

[0146] Further, as another aspect of the liquid crystal display element, at least one of the liquid crystal layer and the liquid crystal driving means is provided between a pair of light transmissive substrates (including the liquid crystal display device substrate of the present invention). The liquid crystal driving means has an active element (e.g., TFT) and is configured to be regulated to a predetermined width by a photo spacer having a uniform height between a pair of substrates and excellent deformation recovery. is there. 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.

[0147] Examples of the liquid crystal that can be used in the present invention include nematic liquid crystal, cholesteric liquid crystal, smectic liquid crystal, and ferroelectric liquid crystal.

In addition, 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 and four or more pixel forces. For example, in the case of three colors, it consists of three hues of red (R), green (G), and blue (B). When arranging pixel groups of three RGB colors, any arrangement may be used when arranging pixel groups of four or more colors that are preferred to be mosaic type or triangle type. For the production of the color filter, for example, a black matrix may be formed as described above after forming a pixel group of two or more colors, or conversely, a pixel group may be formed after forming a black matrix. Good. Regarding the formation of RGB pixels, JP 2004-347831 A can be referred to.

[0148] <Liquid crystal display device>

The liquid crystal display device of the present invention is configured by providing the liquid crystal display element of the present invention. In other words, as described above, a space between a pair of substrates disposed so as to face each other is regulated to a predetermined width by a photospacer produced by the method for producing a photospacer of the present invention, and a regulated gap is formed. The liquid crystal material is encapsulated (the encapsulated portion is referred to as a liquid crystal layer), and the thickness (cell thickness) of the liquid crystal layer is maintained at a desired uniform thickness.

[0149] As the liquid crystal display mode in the liquid crystal display device, STN type, TN type, GH type, ECB type, ferroelectric liquid crystal, antiferroelectric liquid crystal, VA type, IPS type, OCB type, ASM type, and other various types Are preferably mentioned. In particular, 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 in which a display mode that easily causes display unevenness due to the variation of the cell thickness of the liquid crystal cell is desired is 2 to 4. VA type display mode that is μm, IPS type It is preferable to be configured to display mode, OCB type display mode.

[0150] 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 ( (B) A drive substrate and a counter electrode (conducting layer). The liquid crystal display device of the present invention can be applied to various liquid crystal display devices, such as a device in which a counter substrate provided is opposed to each other with a photospacer interposed, and a liquid crystal material is sealed in the gap portion. It can be suitably applied.

[0151] The liquid crystal display device is described, for example, in "Next-generation liquid crystal display technology (edited by Tatsuo Uchida, side industry research committee, 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 for 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)”.

[0152] The liquid crystal display device of the present invention includes an electrode substrate, a polarizing film, a retardation film, a knocklight, a spacer, a viewing angle compensation film, and an antireflection film, except that the liquid crystal display device of the present invention described above is provided. It can be generally constructed using various members such as a film, a light diffusion film, and an antiglare film. As for these materials, for example, “'94 Liquid Crystal Display Peripheral Materials” Chemicals' Kayaba (Kentaro Shima, CMC Co., Ltd., published in 1994), “2003 Current Status and Future Prospects for Liquid Crystal-related Yakuhin (Volume 2) ( Ryoyoshi Omotesaki, Fuji Chimera Research Institute, Inc., 2003, etc.) ”.

[0153] The disclosure of Japanese application 2006—068237 is incorporated herein by reference to its overall strength. In addition, all documents, patent applications, and technical standards described in this specification are the same as when individual documents, patent applications, and technical standards are specifically and individually described to be incorporated by reference. Which is incorporated herein by reference.

[0154] 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 of the present invention. Unless otherwise noted, “Part "Is based on mass.

[0155] In this example, 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. It can be configured with a tube.

[Example 1]: Transfer method

As shown below, an MVA mode liquid crystal display device configured as shown in FIG. 1 was produced.

Making a first-rate filter substrate

Using a slit-like nozzle on a 75 μm thick polyethylene terephthalate film temporary support (PET temporary support), apply a thermoplastic resin coating solution consisting of the following formulation HI, and dry it to make the thermoplastic A resin layer was formed. Next, the intermediate layer (oxygen barrier film) was laminated on the thermoplastic resin layer by applying and drying an intermediate layer coating solution having the following formulation P1. On this intermediate layer, a colored photosensitive resin composition K1 having the composition described in the following Table 1 (transfer method) was applied and dried to laminate a photosensitive resin composition layer. In this way, a thermoplastic resin layer with a dry film thickness of 15 m, an intermediate layer with a dry film thickness of 1.6 m, and a photosensitive film with a dry film thickness of 2.4 m on the PET temporary support. A fat composition layer was provided, and a protective film (12 μm thick polypropylene film) was pressure-bonded onto the photosensitive resin composition layer.

[0157] [Table 1]

As described above, the temporary support, the thermoplastic resin layer, the intermediate layer (oxygen barrier film), and the photosensitive resin composition layer of black (K) are laminated to form a photosensitive body. A photosensitive transfer material was prepared (hereinafter referred to as photosensitive resin transfer material K1).

[0159] [Prescription Hl of coating solution for thermoplastic resin layer]

• Metanore 1M

'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) = 55Zll. 7/4. 5/28. 8, Mass average molecular weight = 100,000, Tg

70 ° C] 'Styrene Z acrylic acid copolymer ••• 13.6

[Copolymerization ratio (molar ratio) = 63/37, mass average molecular weight = 10,000, Tg = 100 ° C]

• 2, 2 Bis [4 (Methacryloxypolyethoxy) phenol] propane (manufactured by Shin-Nakamura Engineering Co., Ltd.)… 9. 1 part

• Surfactant 1… 0.54 parts

[0160] * Surfactant 1:

Mega Fuck F 780 F (Dainippon Ink Chemical Co., Ltd.)

Shizuru

• C F CH CH OCOCH = CH (40 parts) and H (OCH (CH) CH) OCOCH = C

6 13 2 2 2 3 2 7

Copolymer of H (55 parts) and H (OCH CH) OCOCH = CH (5 parts) (mass average molecular weight

2 2 2 7 2

30,000) ... 30 copies

• Methyl ethyl ketone… 70 parts

[0161] [Prescription Pl of intermediate layer coating solution]

'Polybulol alcohol… 2. 1 part

(PVA-205 (Niety rate = 88%), manufactured by Kuraray Co., Ltd.)

• Polybulol pyrrolidone… 0.95 parts

(PVP, K-30; made by IPS Japan Ltd.)

Methanore---44¾

• 53 parts distilled water

[0162] Next, the colored photosensitive resin composition K1 used for the production of the obtained photosensitive resin transfer material K1 was colored photosensitive resin comprising the composition described in Table 1 (transfer method). Photosensitive resin transfer materials Rl, G1, and B1 were prepared in the same manner as described above except that the photosensitive resin compositions R1, G1, and B1 were replaced.

[0163] <Production of color filter substrate>

-Black (K) image formation-

A non-alkali glass substrate of 680 X 880 mm size was washed with a rotating brush with nylon bristles while spraying a glass detergent solution adjusted to 25 ° C by shower for 20 seconds, washed with pure water, and then washed with a silane cup. Ring solution (N— β-(aminoethyl) -γ-Aminopropyltrimethoxysilane 0.3 mass% aqueous solution; trade name: ΚΒΜ603, manufactured by Shin-Etsu Chemical Co., Ltd.) was sprayed for 20 seconds and washed with pure water. After cleaning, the glass substrate was heated at 100 ° C. for 2 minutes with a substrate preheating device.

[0164] Next, after peeling off the protective film of the photosensitive resin transfer material K1, the exposed photosensitive resin composition layer is overlaid so as to contact the surface of the glass substrate heated at 100 ° C for 2 minutes. Laminator Lamic II (manufactured by Hitachi Industries, Ltd.) was used for lamination under conditions of a rubber roller temperature of 130 ° C., a linear pressure of 100 NZcm, and a conveying speed of 2.2 mZ. Next, the PET temporary support was peeled off and transferred onto a glass substrate.

[0165] Next, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, a mask (quartz exposure mask having an image pattern), the mask and thermoplastic resin The distance between the mask surface and the surface on the side of the photosensitive resin composition layer that is in contact with the intermediate layer of the photosensitive resin composition layer is set to 200 m, with the glass substrate placed so that the layers face each other in a vertical state. Then, pattern exposure was performed with the exposure of the thermoplastic resin layer side force of 70 mjZcm ² through the mask.

[0166] Next, triethanol amine developing solution (triethanolamine § Min 30 mass ^_0/0 containing, trade name: T - PD2, manufactured by Fuji Photo Film Co., 12 times with pure water (T-PD2 1 The solution obtained by diluting 11 parts by mass of pure water with 11 parts by mass) was developed with shower at 30 ° C. for 50 seconds and a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer. Subsequently, air was blown onto the upper surface of the substrate to drain the liquid, and then pure water was sprayed for 10 seconds in a shower to clean the pure water, and air was blown to reduce the liquid pool on the substrate.

Continuing carbonate Na based developer (0.38 mol Z l sodium bicarbonate, sodium carbonate 0.47 mol Z l, dibutyl sodium naphthalene sulfonate 5 wt ^{_0/0, Ύ} two on surfactants, defoamers , Containing stabilizer, trade name: T CD1, manufactured by Fuji Photo Film Co., Ltd. diluted 5 times with pure water), shower developed at 29 ° C for 30 seconds, cone type nozzle pressure 0.15 MPa The resin composition layer was developed to obtain a patterning image.

Bow I Continued Detergent (Phosphate · Silicate · Nonionic Surfactant · Antifoam · Stabilizer Contains, Product Name: T—SD1 manufactured by Fuji Photo Film Co., Ltd.) diluted 10 times with pure water Used at 33 ° C for 20 seconds, sprayed with a cone-type nozzle pressure of 0.02 MPa, showered with nylon hair The residue formed by rubbing the image formed by the rotating brush was removed to obtain a black (K) image 16 (K image may be referred to as a black matrix).

Thereafter, the substrate was post-exposed with an exposure amount of 500 miZcm ^{2 with} an ultra-high pressure mercury lamp and then heat-treated at 220 ° C. for 15 minutes.

[0167] After that, the glass substrate 11 on which the K image 16 was formed was again cleaned with a brush as described above, washed with pure water, and then washed with a substrate preheating device without using a silane coupling solution. Heated at ° C for 2 minutes.

[0168] Formation of red (R) pixels

Using the photosensitive resin transfer material R 1 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, and the K image 16 on the glass substrate 11 is formed. A red pixel (R pixel) was formed on the side where it was formed. However, the exposure amount in the exposure process was 4 OmjZcm ^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. O / zm, and the amount of CI pigment 'Red (CIPR) 254 and CIPR 177 applied respectively. .

0. 22gZm was ^2.

After that, the glass substrate 11 on which the R pixel is formed is brush-washed again using the cleaning agent as described above, shower-washed with pure water, and then pre-heated without using a silane coupling solution. The apparatus was heated at 100 ° C for 2 minutes.

[0169] —Formation of Green (G) Pixel—

Next, using the photosensitive resin transfer material G1 obtained above, the same process as the formation of the K image 16 is performed, and the K image 16 and the R pixel of the glass substrate 11 are formed. A dark pixel (G pixel) was formed on the substrate. However, the exposure amount in the exposure process was 40 mjZcm ² , and shower development with a sodium carbonate-based developer was 34 ° C. for 45 seconds.

The thickness of the G pixel is 2. O / zm. The application amount of CI pigment 'Green (CIPG) 36 and CI pigment' Yellow (CIPY) 150 is 1.

It was 0.48 gZm ² .

After that, the glass substrate 11 on which the R pixel and the G pixel are formed is again brush-cleaned with the cleaning agent as described above, shower-washed with pure water, and without using a silane coupling liquid, Heated at 100 ° C for 2 minutes with a heating device. [0170] Formation of blue (B) pixel

Next, using the photosensitive resin transfer material B1 obtained above, the same process as the formation of K image 16 is performed! On the other hand, blue pixels (B pixels) were formed on the side of the glass substrate 11 where the K image 16 and R and G pixels were formed. However, the amount of exposure in the exposure process was set at 40 ° C for 36 seconds at 36 ° C for shower development with 30miZcm Na carbonate developer.

The thickness of the B pixel is 2. O / zm. The application amount of CI pigment 'Blue (CIPB) 15: 6 and CI pigment' Violet (CIPV) 23 is 0.63 g / m ² and 0.07 g / respectively. It was m ^2.

[0171] Thereafter, the glass substrate 11 on which the R, G, and B pixels were formed was beta-treated 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.

[0172] Here, the preparation of the colored photosensitive resin compositions Kl, Rl, Gl, and B1 shown in Table 1 will be described.

Colored photosensitive resin composition K1 is prepared by removing K pigment dispersion 1 and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 above and mixing at a temperature of 24 ° C (± 2 ° C). Stir at .pm for 10 minutes, then the amount of methyl ethyl ketone, binder 1, hydroquinone monomethyl ether, DPHA solution, 2, 4 bis (trichloromethyl) — 6— [4'— (N, N bisethoxycarboromethyl) amino-3'-bromophenol] —s Triazine, Surfactant 1 is removed and added in this order at a temperature of 25 ° C (± 2 ° C). It was obtained by stirring at 40 ° C. (± 2 ° C.) and 150 rpm for 30 minutes.

[0173] Details of each composition in the composition described in Table 1 are as follows. Surfactant 1! / Is as described above.

* Composition of K pigment dispersion 1

'Carbon black… 13. 1 copy

(Special Black 250, manufactured by Degussa)

• 5— [3-Oxo 2— [4— [3, 5 Bis (3 Jetylaminopropylaminocarbo- Le) Huel] Amino Carbo] Fueru Lazo] -Butylo Lamino Bennes Imidazolone--

0. 65 咅

• Polymer [Random copolymer of benzyl metatalylate Z methacrylic acid (= 72Z28 [molar ratio]) (mass average molecular weight 37,000)]-6.72 parts

'Propylene glycol monomethyl ether acetate 79.53 parts

[0174] * Binder 1 composition

• Random copolymer (mass average molecular weight 40,000) of polymer (benzyl metatalylate Z methacrylic acid (= 78Z22 [molar ratio])) 27 parts

'Propylene glycol monomethyl ether acetate ··· 73 parts

* Composition of DPHA solution

'Dipentaerythritol hexaatalylate (containing 500ppm polymerization inhibitor MEHQ, trade name: KAYARAD DPHA, Nippon Kayaku Co., Ltd.) ... 76 parts

Propylene glycol monomethyl ether acetate · · · 24 parts

The colored photosensitive resin composition R1 is made up of R pigment dispersion 1, R pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts described in Table 1 (transfer method), at a temperature of 24 ° C. (± 2 ° C) and stirred at 150 rpm for 10 minutes, then the amount of methyl ethyl ketone, binder 2, DPHA solution, 2 trichloromethyl-5- (p-styryl) listed in Table 1 above. Styryl) -1,3,4 oxadiazole, 2,4 bis (trichloromethyl) -6— [4 '— (N, N bisethoxycarboromethyl) amino-3′-bromophenol] —s triazine, and phenothiazine Then, the mixture is added in this order at a temperature of 24 ° C (± 2 ° C), stirred at 15 Or.pm for 10 minutes, and the surfactant 1 in the amount shown in Table 1 is further removed. Depressurize and add at a temperature of 24 ° C (2 ° C) and stir at 30 rpm for 30 minutes. It was obtained by the over to.

[0176] The details of each composition in the composition R1 described in Table 1 are as follows. The compositions of the DPHA solution and the surfactant 1 are the same as those of the colored photosensitive resin composition K1.

* R Composition of Pigment Dispersion 1 • CI Pigment Red 254 · “8.0

• 5— [3-Oxo 2— [4- [3,5-Bis (3 Jetylaminopropylaminocarbole) phenol] Aminocarbol] Fuelazo] -Butyloylaminobenzimidazolone -0. 8 咅

• Polymer [Random copolymer of benzyl metatalate Z methacrylic acid (= 72Z28 [molar ratio]) (mass average molecular weight 37, 000)]-6.4 parts

• Propylene glycol monomethyl ether acetate · · · 84. 8 parts

[0177] * R Composition of Pigment Dispersion 2

• C. I. Pigment · Red 177 · · · 18 copies

• 1 part of polymer (benzyl metatalylate Ζ methacrylic acid (= 72Ζ28 [molar ratio]) random copolymer (mass average molecular weight 37, 000))

• Propylene glycol monomethyl ether acetate '· · 70 parts

* Binder 2 composition

'Random copolymer of benzyl metatalylate Ζ methacrylic acid Ζ methyl metatalylate (= 38 Ζ 25 Ζ 37 [molar ratio]) (mass average molecular weight 30, 000) · · · 27 parts

'Propylene glycol monomethyl ether acetate ··· 73 parts

Colored photosensitive resin composition G1 is obtained by weighing G pigment dispersion 1, cocoon pigment dispersion 1, and propylene glycol monomethyl ether acetate in the amounts described in Table 1 (Transfer method), at a temperature of 24 ° C ( ± 2 ° C) and 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, 4 oxadiazole, 2, 4 bis (trichloromethyl) 6— [4 '— (N, N-bisethoxycarboromethyl) amino 1 3′-bromophenol] —s -Triazine and phenothiazine were removed by force, added in this order at a temperature of 24 ° C (± 2 ° C), stirred at 150 rpm for 30 minutes, and then the surface activity in the amount shown in Table 1 above. Remove agent 1 and add it at a temperature of 24 ° C (± 2 ° C) and stir at 30 rpm for 5 minutes. It was obtained by filtration Mesh # 200.

[0179] The details of each composition in the composition G1 described in Table 1 are as follows. Also, The composition of the binder 1, the DPHA liquid, and the surfactant 1 is the same as that of the colored photosensitive resin composition K1.

* Composition of G pigment dispersion 1

• C. I. Pigment Green 36

• Random copolymer (mass average molecular weight 37,000) of polymer [benzyl metatalylate Z methacrylic acid (= 72Z28 [molar ratio])] 1 part

'Cyclohexanone ... 35 parts

Propylene glycol monomethyl ether acetate 35 parts

* Y pigment dispersion 1

Product Name: CF Yellow ΕΧ3393 (Mikuni Color Co., Ltd.)

Colored photosensitive resin composition B1 is obtained by removing the amount of Pigment Dispersion 1, Pigment Dispersion 2, and Propylene Glycol Monomethyl Ether Acetate in the amounts described in Table 1 (Transfer Method) at a temperature of 24 ° C. (± 2 ° C) and stirred at 150 rpm for 10 minutes, then the amount of methyl ethyl ketone, binder 3, DPHA solution, 2 trichloromethyl-5- (p-styryl) listed in Table 1 above. Stylyl) 1, 3, 4 Oxadiazole and phenothiazine are removed, and the temperature is 25. C (± 2. C) is added in this order, and the temperature is 40. The mixture was stirred at 150 rpm for 30 minutes at C (± 2. C), and then the surfactant 1 in the amount shown in Table 1 above was scraped off and added at a temperature of 24 ° C (± 2 ° C). Then, it was stirred for 5 minutes at 30 rpm and obtained by filtering through nylon mesh # 200.

[0181] The details of each composition in the composition B1 described in Table 1 are as follows. The composition of DPHA solution and surfactant 1 is the same as that of the colored photosensitive resin composition K1.

* B pigment dispersion 1

Product Name: CF Blue EX3357 (Mikuni Color Co., Ltd.)

* B Pigment dispersion 2

Product Name: CF Blue EX3383 (Mikuni Color Co., Ltd.)

* Binder 3 composition 'Random copolymer of benzyl metatalylate Z methacrylic acid Z methyl metatalylate (= 36Z22Z42 [molar ratio]) (mass average molecular weight 30, 000) · · · 27 parts

'Propylene glycol monomethyl ether acetate ··· 73 parts

[0182] Fabrication of photosensitive transfer sheet for spacers

On a polyethylene terephthalate film temporary support (PET temporary support) with a thickness of 75 μm, apply a coating solution for a thermoplastic resin layer consisting of the following formulation A, dry it, and dry layer thickness 6. O ^ m A thermoplastic resin layer (an alkali-soluble thermoplastic resin layer) was formed.

[0183] [Formulation A of coating liquid for thermoplastic resin layer]

• Methyl methacrylate / 2-ethyl hexyl acrylate / benzyl methacrylate / methacrylic acid copolymer… 25.0 parts

(= 55/11. 7/4. 5/28. 8 [molar ratio], weight average molecular weight 90, 000) • Styrene Z acrylic acid copolymer… 58. 4 parts

(= 63Z37 [molar ratio], weight average molecular weight 8,000)

• 2, 2 Bis [4- (methacryloxypolyethoxy) phenol] propane

… 39. 0 copies

• Surfactant 1… 10.0 parts

• Methanore… 90. 0

• 1—Methoxy-2-propanol… 51.0 parts

• Methyl ethyl ketone: 700 parts

[0184] Next, an intermediate layer coating solution consisting of the following formulation B was applied onto the formed thermoplastic resin layer.

Then, an intermediate layer having a dry layer thickness of 1.5 / z m was laminated.

[Formulation B of coating solution for intermediate layer]

'Polybulol alcohol… 3. 22 parts

(PVA-205, hatching rate 80%, manufactured by Kuraray Co., Ltd.)

• Polybylpyrrolidone… 1. 49 parts

(PVP K 30, manufactured by ISP Japan Co., Ltd.)

• Methanore… 42. 3 咅

'Distilled water… 524 parts [0186] Next, a photosensitive resin composition layer coating solution having the formulation 1 shown in Table 2 below was further applied onto the formed intermediate layer and dried to obtain a dry layer thickness of 4 .: L m. A layer of the active resin composition layer was laminated.

[0187] After forming the laminated structure of the PET temporary support Z thermoplastic resin layer Z intermediate layer Z photosensitive resin composition layer (total thickness of the three layers is 11.6 m) as described above Further, a 12 μm-thick polypropylene film as a cover film was applied to the surface of the photosensitive resin composition layer by applying heat and pressure to obtain a photosensitive transfer sheet (1) for spacers.

[0188] Fabrication of a photospacer

The cover film of the resulting photosensitive transfer sheet for spacer (1) was peeled off, and the exposed surface of the photosensitive resin composition layer was formed on the color filter substrate 10 on which the ITO film prepared above was sputtered. The film was laminated on the ITO film 13 and bonded using a laminator Lamic II type (manufactured by Hitachi Industries, Ltd.) under a heating condition of a linear pressure of 100 NZcm and 130 ° C. at a conveyance speed of 2 mZ. Thereafter, the PET temporary support was peeled off at the interface with the thermoplastic resin layer, and the photosensitive resin composition layer was transferred together with the thermoplastic resin layer and the intermediate layer (layer forming step).

[0189] Next, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, a mask (quartz exposure mask having an image pattern), the mask and a thermoplastic film. The distance between the mask surface and the surface of the photosensitive resin composition layer that is in contact with the intermediate layer of the photosensitive resin composition layer in a state where the color filter substrate 10 disposed so as to face the oil layer is substantially parallel and vertical. Proximity exposure was performed at 40 m and a thermoplastic resin layer side force through the mask with an exposure amount of 60 miZ cm ² . Next, KOH developer CDK-1 (Fuji Film Select Kokusu Materials Co., Ltd., 100-fold diluted solution) was sprayed from a flat nozzle at 23 ° C and a nozzle pressure of 0.04 MPa for 80 seconds. The pattern was developed by shower development and unexposed areas were removed to obtain a pattern (spacer pattern) (patterning process).

The resulting spacer pattern is a transparent column with a diameter of 20 m and an average height of 3.7 m.

[0190] Next, the color filter substrate 10 provided with the spacer pattern was subjected to a heat treatment at 230 ° C for 30 minutes (heat treatment step) to produce a photospacer 14. [0191] Production of photosensitive transfer material for protrusions

A polyethylene terephthalate film temporary support (PET temporary support) with a thickness of 75 μm was coated with a coating solution for a thermoplastic resin layer having the same formulation as Formula A, dried, and the dry film thickness was 15 / A zm thermoplastic resin layer was provided. Next, an intermediate layer coating solution having the same prescription power as the formulation B was applied on the formed thermoplastic resin layer and dried to provide an intermediate layer having a dry film thickness of 1.6 m. Next, a projection forming coating solution having the following prescription C force is prepared, and this projection forming coating solution is applied onto the intermediate layer and dried to control the liquid crystal alignment with a dry film thickness of 2.O ^ m. A photosensitive resin composition layer for protrusions was applied. Further, a 12 μm-thick polypropylene film was attached to the surface of the photosensitive resin composition layer as a protective film. In this way, the protrusion photosensitive film is formed by laminating the thermoplastic resin layer, the intermediate layer, the protrusion photosensitive resin composition layer, and the protective film in this order from the PET temporary support side. A transferable material was prepared.

[0192] [Prescription C of coating liquid for protrusion formation]

'Positive resist solution FH— 2413F---53. 3 parts

(Fuji Film Elect Mouth-Cux Materials Co., Ltd.)

• Methyl ethyl ketone ".46. 7 parts

• Surfactant 1… 0.04 parts

[0193] Protrusion formation

The photosensitive transfer material force for protrusions obtained from the above is peeled off the protective film, the exposed surface of the exposed photosensitive resin composition layer for protrusions and the side of the color filter substrate 10 on which the ITO film 13 is provided (on the color filter) The surfaces were superposed and laminated using a laminator type Lamic II (manufactured by Hitachi Industries Ltd.) under conditions of a linear pressure of 100 NZcm, a temperature of 130 ° C, and a conveying speed of 2.2 mZ (laminate). Thereafter, only the PET temporary support of the photosensitive transfer material for protrusions was peeled off at the interface with the thermoplastic resin layer. At this time, the photosensitive resin composition layer, the intermediate layer, and the thermoplastic resin layer are laminated on the color filter substrate in this order from the substrate side.

[0194] Next, a distance between the mask surface of the photomask and the surface on the side in contact with the intermediate layer of the light-sensitive resin composition layer for protrusions is 100 above the outermost thermoplastic resin layer. μm A proximity exposure machine was installed, and a proximity exposure was performed with an irradiation energy of 70 miZcm ² using an ultrahigh pressure mercury lamp through a photomask.

After that, triethanolamine developer (containing 30% by mass of triethanolamine, trade name: T-PD2, manufactured by Fuji Photo Film Co., Ltd.) 12 times with pure water (T-PD2 1 part by weight and 11 parts by weight of pure water (diluted in a ratio of 11 parts by weight) are sprayed at 30 ° C for 30 seconds, and the thermoplastic resin layer and intermediate layer are dissolved and removed. did. At this stage, the photosensitive resin composition layer for protrusions was substantially undeveloped. Subsequently, an aqueous solution containing 0.085 mol ZL of sodium carbonate, 0.085 mol ZL of sodium hydrogen carbonate and 1% sodium dibutyl naphthalenesulfonate was further sprayed at 33 ° C. for 30 seconds in a shower type developing device. Then, unnecessary portions (uncured portions) of the photosensitive resin composition layer for protrusions were developed and removed. As a result, protrusions 15 made of a photosensitive resin composition layer for protrusions that were patterned in a desired shape were formed on the color filter (RGB pixels). Next, the color filter substrate on which the protrusions 15 are formed is beta-treated at 240 ° C for 50 minutes, so that the vertical cross-sectional shape is 1.5 m high on the color filter (RGB pixels). Protrusions for controlling the liquid crystal orientation were formed.

[0195] 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 of the color filter substrate 10 on the side where the photospacer 14 was provided.

[0196] Thereafter, an epoxy resin sealant is 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 is attached to the TFT. Bonded to substrate 21. Next, the two bonded substrates were heat-treated to cure the sealing agent, and a laminate of two substrates was obtained. 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 the completion of the injection, a liquid crystal cell was obtained by applying an adhesive to the injection port portion and sealing it with ultraviolet irradiation.

[0197] Polarizing plates (HLC2-2518, manufactured by Sanritz Co., Ltd.) 25 and 23 were attached to both surfaces of the liquid crystal cell thus obtained. Next, although not shown, the red (R) LED is FR1112H, green A sidelight type backlight is constructed using (G) LED DGl 112H and blue (B) LED DBl 112H (a chip type LED manufactured by Stanley Ichi Electric Co., Ltd.). The MVA mode liquid crystal display device of the present invention was fabricated by arranging it on the back side of the liquid crystal cell.

[0198] (Examples 2 to 14)

In Example 1, the photosensitive resin for spacers was prepared in the same manner as in Example 1, except that the formulation 1 of the coating solution for the photosensitive resin composition layer was changed to the formulations 2 to 14 in Table 2 below. The transfer sheets (2) to (14) were produced, and the MVA mode liquid crystal display device of the present invention was produced. The units in Table 2 are parts by mass.

[0199] (Comparative Examples 1 to 3)

In Example 1, except that the formulation 1 of the coating solution for the photosensitive resin composition layer was replaced with the formulation 15 to 17 in Table 2 below, the same as in Example 1, for the spacer Photosensitive transfer sheets (15) to (17) were produced, and a comparative MVA mode liquid crystal display device was produced.

[0200] [Table 2]

Here, Structural Formulas 1 to 17 in Table 2 are as shown in Table 3. R ¹ and n in Table 3 corresponds to R ¹ and n each in the general formula (A) or (B). In Table 3, the general formula (C) is as follows.

[0202] [Table 3] Acrylic base R ¹ n

Structural formula 1 6 General formula (A) (a) 4

Structural formula 2 6 General formula (A) (a) 6

Structural formula 3 6 General formula (A) (a) 8

Structural formula 4 6 General formula (A) (b)-Structural formula 5 6 General formula (A) (c)-Structural formula 6 5 General formula (B) (a) 4

Structural formula 7 5 General formula (B) (a) 6

Structural formula 8 5 General formula (B) (b) ―

Structural formula 9 6 General formula (A) (a) 6

Structural formula 1 C 5 General formula (B) (a) 6

Structural formula 1 1 15 U-15HA ^¾ '

Structural formula 1 2 15 U-15HA *,

Construction type 1 2 9 UA32P "' ¹

Structural formula 1 4 9 UA32P

Formula 1 5 0 DPHA · ²

Structural formula 1 6 4 U-4HA

Structural formula 1F 16 General formula (C) I--Urethane alkylate monomer by Shin-Nakamura Chemical Co., Ltd.

Dipentaerythritol hexaacrylate (polymerization inhibitor)

MEHQ500pprri contained; trade name: KAYARAD DPHA, Nippon Kayaku Co., Ltd.)

The details of each composition in the formulation described in Table 2 are as follows.

Water noider 1

'Zaryl methacrylate methacrylate copolymer

(= 20/80 [molar ratio], mass average molecular weight 36000; polymer substance)

Water binder 2

• Polymer [Random copolymer of benzylmetatalate / methacrylic acid (= 72Z28 [molar ratio]) (mass average molecular weight 37,000)] 27 parts

• Propylene glycol monomethyl ether acetate .73 parts

* Decolorizing dye

• Victoria Pure Blue BOH— M (Hodogaya Chemical Co., Ltd.) [0204] [Chemical 8]

(C)

[Example 15]

In Example 1, the glass substrate is replaced with a glass substrate of 2400 mm X 2400 mm size, and a photosensitive transfer sheet for spacer (1) of size 9 cm X 9 cm is 1400 mm wide, 16 Om long and 900 mm wide, 160 m long. Instead of the photosensitive transfer sheet for spacers (1) configured in two sizes of rolls (1), two roll-type photosensitive transfer sheets for spacers are placed side by side and laminated at the same time. A 2300 mm × 2300 mm size color filter substrate was obtained in the same manner as in Example 1 except that the laminate was laminated in the same manner as in Example 1, and the MVA mode liquid crystal display device of the present invention (see FIG. 1) was produced. In this example, a two-clad laminator described in Japanese Patent Application No. 2004-199886 was used for the laminating apparatus.

Although the obtained MVA mode liquid crystal display device was large-sized, the image had no unevenness and was of high quality to the same extent as in Example 1.

[0206] (Evaluation)

The following evaluations were carried out using the photospacers and liquid crystal display devices prepared in the examples and comparative examples. The results are shown in Tables 4 and 5 below.

[0207]: L deformation recovery rate (Condition 1)

Each of the photo spacers was measured by a micro hardness tester (DUH-W201, manufactured by Shimadzu Corporation) as follows and evaluated. The measurement was performed by a load-unloading test method using a frustum frustum indenter with a maximum load of 50 mN and a holding time of 5 seconds. This measured force is also calculated as the deformation recovery rate [%] by the following formula and evaluated according to the following criteria: did.

Deformation recovery rate (%) = (Deformation amount by weight m] Recovery amount after Z load release m]) X IOO

[0208] <Evaluation criteria>

A: Deformation recovery rate was 90% or more.

◯: Deformation recovery rate was 85% or more and less than 90%.

Δ: Deformation recovery rate was 75% or more and less than 85%.

X: Deformation recovery rate was less than 75%.

[0209] 2-node deformation recovery rate (Condition 2) —

Each of the photo spacers was measured by a micro hardness tester (DUH-W201, manufactured by Shimadzu Corporation) as follows and evaluated. The measurement was carried out by the load-unloading test method using a frustum frustum indenter with a maximum load of 130 mN and a holding time of 60 seconds. For this measured force, the deformation recovery rate [%] was calculated according to the following formula, and evaluated according to the following criteria.

[0210] <Evaluation criteria>

A: Deformation recovery rate was 85% or more.

A: Deformation recovery rate was 80% or more and less than 85%.

Δ: Deformation recovery rate was 70% or more and less than 80%.

X: Deformation recovery rate was less than 70%.

[0211] 3. Display unevenness

For each liquid crystal display device, the gray display when a gray test signal was input was observed visually and with a loupe, and the presence or absence of display unevenness was evaluated according to the following evaluation criteria.

◯: Display unevenness was not recognized at all.

Δ: Display unevenness was slightly recognized. X: Display unevenness was noticeable.

[0212] 4. Finger press test

For each of the liquid crystal display devices, the surface of the display panel device was lightly pressed with one finger, and the finger was released instantly. Ripples were observed as soon as the panel was released. This is shown in Table 4.

[0213] 5.Developability

In the above-mentioned “-protrusion formation”, after the proximity exposure, a 1% triethanolamine aqueous solution is sprayed from above the thermoplastic resin at 30 ° C. for 30 seconds in a shower type developing device, and the thermoplastic resin layer. Then, the intermediate layer is dissolved and removed, and subsequently, an aqueous solution containing 0.085 mol ZL sodium carbonate, 0.085 mol ZL sodium hydrogen carbonate and 1% sodium dibutylnaphthalene sulfonate at 33 ° C in a shower type developing device. Development was carried out while spraying for a second. SEM observation was performed on the periphery of the protrusions that were formed, and it was confirmed whether residues were left around. When a residue was found after 30 seconds of development, the development time was lengthened and the time for no residue was confirmed. The results are shown in Table 5 below.

[0214] [Table 4]

Deformation recovery rate

Example Display unevenness Finger press test

Condition 1 /% Condition 2 /%

Example 1 92 (©) 85 (©) 〇 The spreading ripples were small and recovered instantly. Example 2 93 (©) 88 (©) 〇 The spreading ripples were small and recovered instantly. Example 3 9U®) 86 (©) 〇 The spreading ripples were small and recovered instantly. Example 4 91 (@) 85 (©) 〇 The spreading ripples were small and recovered instantly. Example 5 90 (©) 86 (©) 〇 The spreading ripples were small and recovered instantly.

Recovered.

Turned.

Yes

Recovered.

"did.

Example 11 93 (©) 86 (©) O The ripples of the wide force were small and recovered instantly. Example 12 93 (©) 84 (0) O The spreading ripple was slightly large but recovered instantly.

Comparative Example 1 82 (厶) 65 (x) X 1

It took about a second.

1 comparative example 2 74 (x) 66 (x) X ripples spreading

It took about a second.

Comparative Example 3 A photo spacer could not be formed during development. Cannot be evaluated. ] Banquet developability (including SEM photo observation results)

Example 1 Remaining--No review. The column shape without any problem was shown.

Example 2 Same as above

Example 3 Same as above

Example 4 Same as above

Example 5 Same as above

Example 6 Same as above

Example 7 Same as above

Example 8 Same as above

In 30 seconds, there is a slight residue around the pillar. Example 9 shows a column shape with no problem at development time of 45 seconds

It was. 45 seconds is a time that does not matter in terms of productivity.

Example 1 0 No residue. The column shape without any problem was shown.

At 30 seconds, there is a slight residue around the pillar. Demonstrates a column shape with a development time of 80 seconds. Example 1 1

It was. 80 seconds is a good time for productivity.

At 30 seconds, a little left around the pillar; Development time 90 seconds shows no problem ί shape showing Example 1 2

It was. 90 seconds is a good time for productivity.

At 30 seconds, there is a slight remaining on the pillar side. Development time 60 seconds shows no problem ½ shape Example 1 3

It was. 60 seconds is a good time for productivity.

In 30 seconds, there is a slight residue around the pillar; Example 1 4 Shows a column shape with a development time of 65 seconds.

It was. 65 seconds is a good time for productivity.

Comparative Example 1 Remaining-; no wrinkle. The column shape without any problem was shown.

Comparative Example 2 Same as above

At 30 seconds, there is a slight residue around the pillar. Comparative Example 3 in which residual residue was confirmed even after 200 seconds of development

. There is a problem with productivity when developing over 200 seconds.

[0216] As shown in Table 4, in the examples, a photospacer with good deformation recovery was obtained, and the image displayed by the liquid crystal display device was suppressed in display unevenness and had high image quality. On the other hand, in the comparative example, the deformation recovery property of the photospacer is inferior, and the liquid crystal display device manufactured using the photospacer has noticeably uneven display due to the variation in cell thickness.

[Example 16]

A PVA mode liquid crystal display device configured as shown in FIG. 2 was fabricated as follows. The same components as those in the first embodiment are denoted by the same reference numerals, and detailed description thereof is omitted.

First, a color filter substrate was produced in the same manner as in Example 1, and a photospacer was produced using the same photosensitive transfer sheet for spacers as in Example 1. Photos No protrusion was formed after the production of the spacer.

[0219] Next, a TFT substrate 21 was separately prepared as a counter substrate. An ITO (Indium Tin Oxide) film 22 is formed on one surface of the TFT substrate by sputtering. Subsequently, the ITO film (transparent electrode) 13 of the force filter substrate 10 and the ITO film 22 of the TFT substrate 21 were patterned for the PVA mode, respectively, and an alignment film 24 made of polyimide was further provided thereon.

[0220] After that, a sealant of UV-curing resin is applied to the seal portion having a width of 0.5 mm and a height of 40 m corresponding to the outer frame of the black matrix 16 provided around the pixel group of the color filter. Was applied by the dispenser method, the liquid crystal for PVA mode was dropped, and the color filter substrate and the TFT substrate were bonded together. Thereafter, the pressure was returned to normal pressure, and a load was applied to control the cell thickness to m. In this state, a metal halide lamp is used to filter out UV light of less than 340 nm, and the sealant is exposed in a nitrogen atmosphere so that the integrated light intensity from 340 to 390 nm is equivalent to 3,000 nj / cm ^2. After photocuring, the sealing agent was cured by heat treatment to obtain a liquid crystal cell. Polarizing plates (HLC2-2518, manufactured by Sanritz Co., Ltd.) 25 and 23 were attached to both surfaces of the liquid crystal cell thus obtained. Next, a CCF L knocklight was constructed and installed on the back side of the liquid crystal cell to which the polarizing plate was attached, and the PVA mode liquid crystal display device of the present invention was fabricated.

[0221] For the PVA mode liquid crystal display device obtained in this example, display unevenness was evaluated in the same manner as in Example 1. Also in this example, a photospacer with good deformation recovery properties was obtained in the same manner as in Example 1, and no display unevenness was observed in the image displayed by the liquid crystal display device (evaluation ◯). was gotten.

[0222] (Example 17): Coating (liquid registration) method

—Preparation of color filter (application by slit nozzle)--Black (K) image formation-

A non-alkali glass substrate of size 680 X 880 mm (hereinafter simply referred to as a glass substrate) was cleaned with an 11 V cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. This glass substrate was heat-treated at 120 ° C for 3 minutes to stabilize the surface state. Then, after cooling the glass substrate and adjusting the temperature to 23 ° C, the coater for glass substrate having a slit nozzle The colored photosensitive resin composition K1 having the composition shown in Table 1 was applied with MH-1600 (manufactured by F'AS Asia). Subsequently, using a vacuum dryer VCD (manufactured by Tokyo Ohka Kogyo Co., Ltd.), part of the solvent was dried for 30 seconds to eliminate the fluidity of the coating film, and then pre-betated at 120 ° C for 3 minutes. 2. A 4 m photosensitive resin composition layer K1 was formed.

[0223] Next, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) equipped with an ultra-high pressure mercury lamp, a mask (quartz exposure mask having an image pattern) and a photosensitive resin composition layer K1 are provided. With the obtained alkali-free glass substrate standing upright, the distance between the mask surface and the surface of the photosensitive resin composition layer K1 was set to 200 m, and the entire surface was exposed at an exposure dose of 300 miZ cm.

Next, after spraying pure from a shower nozzle and uniformly moistening the surface of the photosensitive resin composition layer K1, KOH developer CDK-1 (manufactured by Fuji Film Elect Kokusu Materials Co., Ltd .; A 100-fold diluted alkaline developer containing KOH and a nonionic surfactant was sprayed from a flat nozzle at 23 ° C and a nozzle pressure of 0.04 MPa for 80 seconds to perform shower development, and a black pattern was obtained. (Development process). Subsequently, ultrapure water is sprayed at a pressure of 9.8 MPa with an ultrahigh pressure cleaning nozzle onto the side of the glass substrate where the black pattern is formed to remove the residue, and a black (K) image is formed on the alkali-free glass substrate. did. Thereafter, heat treatment (beta) was performed at 220 ° C for 30 minutes.

[0224] Formation of red (R) pixels

Using the colored photosensitive resin composition R2 having the composition shown in Table 1 above on the glass substrate on which the K image was formed, coating, exposure, development, and beta were performed in the same manner as the formation of the K image. A K image of the glass substrate was formed, and red pixels (R pixels) were formed on the other side. However, the exposure amount in the exposure process was 150 mjZcm ² and the shower development in the development process was 60 ° C. at 23 ° C.

The thickness of the R pixel is 1. CI pigment 'Red (CIPR) 254 and CIPR 177 are applied respectively. .

0. 22gZm was ^2.

[0225] Green (G) image formation

Next, a colored photosensitive resin composition G2 having the composition shown in Table 1 above is applied to the glass substrate on which the K image and R pixel are formed, and is applied and exposed in the same manner as in the formation of the K image. Then, development and beta were performed, and a green pixel (G pixel) was formed on the side of the glass substrate on which the K image and R pixel were formed. However, the exposure amount in the exposure process was 150 mjZcm ² and the shower development in the development process was 60 ° C. at 23 ° C.

The thickness of the G pixel is 1.6 m. The application amount of CI pigment 'Green (CIPG) 36 and CI pigment' Yellow (CIPY) 150 is 1.

It was 0.48 gZm ² .

[0226] Blue (B) Image formation

Next, a colored photosensitive resin composition B2 having the composition shown in Table 1 above is used on the glass substrate on which the K image, R pixel, and G pixel are formed, in the same manner as in the formation of the K image. Coating, exposure, development, and beta were performed, and blue pixels (B pixels) were formed on the side of the glass substrate where the K image, R pixels, and G pixels were formed. However, the exposure dose in the exposure process was 150 miZcm ² and the shower development in the development process was 60 ° C. at 23 ° C.

The thickness of the B pixel is 1.6 m, and the application amounts of CI pigment 'Blue (CIPB) 15: 6 and CI pigment' Violet (CIPV) 23 are 0.63 g / m ² and 0.07 g / m, respectively. ² .

[0227] The colored photosensitive resin composition G2, B2 is prepared according to the preparation of the colored photosensitive resin composition G1, B1, and the preparation of the colored photosensitive resin composition R2. This is explained below.

Colored photosensitive resin composition R2 is obtained by weighing R pigment dispersion 1, R pigment dispersion 2, and propylene glycol monomethyl ether acetate in the amounts shown in Table 1 above, at a temperature of 24 ° C (2 ° C). Mix and stir at 150 rpm for 10 minutes, then methyl ketyl ketone, binder 2, DPHA solution, 2 trichloromethyl mono-5- (ρ-styrylstyryl) — 1, 3, 4— Oxadiazole, 2, 4 Bis (trichloromethyl) -6- [4— (N, N-bisethoxycarboromethyl) amino-3-bromophenol] s Triazine and phenothiazine are used at a temperature of 24 ° C (± 2 ° C) and added in this order and stirred at 150 rpm for 30 minutes, and then the additive 1 in the amount shown in Table 1 above is stripped off to a temperature of 24 ° C (± 2 ° C ) And stirred at 150 rpm for 20 minutes, and the surfactant 1 in the amount shown in Table 1 above. Was removed by force, added at a temperature of 24 ° C. (± 2 ° C.), stirred at 30 rpm for 30 minutes, and filtered through nylon mesh # 200.

[0228] Details of each composition in the composition R2 described in Table 1 are as follows. Further, R pigment dispersion 1, R pigment dispersion 2, binder 2, DPHA solution, and surfactant 1 in the colored photosensitive resin composition R2 are as described above.

* Additive 1: Phosphate ester special activator (HIPLAAD ED152, manufactured by Enomoto Kasei Co., Ltd.)

[0229] On the color filter produced as described above, an ITO film was formed as a transparent electrode by sputtering to obtain a color filter substrate.

[0230] Fabrication of a photospacer (liquid cash register method)

A glass substrate coater MH-1600 (manufactured by F.S. Japan Co., Ltd.) having a slit-like nozzle is formed on the ITO film of the color filter substrate on which the ITO film produced above is formed by sputtering. A coating solution for a photosensitive resin composition layer having the formulation 1 shown in Table 2 was applied. Then, using a vacuum dryer VCD (manufactured by Tokyo Ohka Kogyo Co., Ltd.), part of the solvent was dried for 30 seconds to eliminate the fluidity of the coating film. The coating solution was removed and pre-betaged at 120 ° C. for 3 minutes to form a photosensitive resin composition layer having a film thickness of 2.4 / zm (layer forming step).

Subsequently, a photospacer was produced on the color filter substrate by the same patterning process and heat treatment process as in Example 1. However, the exposure was 300miZcm ² and development with Na carbonate-based image solution was 23 ° C for 60 seconds.

[0231] After the fabrication of the photospacer, the MVA mode liquid crystal display device of the present invention (see Fig. 1) was fabricated in the same manner as in Example 1 using this color filter substrate. With respect to the MVA mode liquid crystal display device obtained in this example, display unevenness was evaluated in the same manner as in Example 1. In this example, too, a photomask with good deformation recovery properties was obtained as in Example 1. A spacer was obtained, and no display unevenness was observed in the image displayed by the liquid crystal display device (evaluation ◯), and a high-quality image was obtained.

Explanation of symbols

[0232] 10 ... Color filter substrate

12 ··· Colored pixels .... Black matrix ... Photo spacer

TFT substrate (counter substrate)

Claims

Claims [1] A photosensitive resin composition for a photospacer, comprising an alkali-soluble polymer substance, a polymerizable monomer containing a urethane group and 5 to 15 acrylic groups, and a photopolymerization initiator. object. [2] The photosensitive resin composition for a photospacer according to claim 1, wherein the polymerizable monomer is a compound represented by the following general formula (A) or (B).

[Chemical 1]

1

[Chemical 2]

(In formula (a), n represents an integer of 2 to 8.)

[3] 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, A method of manufacturing the photospacer in a liquid crystal display device comprising:

A layer forming step for forming a photosensitive resin layer containing the photosensitive resin composition for a photospacer according to claim 1 or 2 on one of the two substrates,

A patterning step of exposing and alkali-developing and patterning the formed photosensitive resin layer;

A method for manufacturing a photospacer.

[4] The layer forming step uses a photosensitive transfer material having a photosensitive resin layer composed of the photosensitive resin composition for photospacers according to claim 1 or 2 on a temporary support. The method for producing a photospacer according to claim 3, wherein the photosensitive resin layer is transferred so as to be in contact with one of the two substrates.

[5] In the layer forming step, the solution containing the photosensitive resin composition for photospacers according to claim 1 or 2 is applied onto one of the two substrates and dried. A manufacturing method of the described photospacer.

[6] A substrate for a liquid crystal display device comprising a photospacer produced by the method for producing a photospacer according to any one of claims 3 to 5.

[7] A liquid crystal display device comprising the liquid crystal display device substrate according to claim 6.

8. A liquid crystal display device comprising the liquid crystal display element according to claim 7.