JP2003245993A - Transfer material for forming reflecting plate and its manufacturing method, reflecting plate and liquid crystal display device and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal display device having a reflecting electrode which includes good reflecting characteristics in a simple step and a method for manufacturing the same and to provided a transfer material for forming the reflecting plate and a method for manufacturing the same. <P>SOLUTION: The transfer material for forming the reflecting plate comprises at least one deformed layer and at least one resin layer, sequentially provided on a temporary support so that a rugged part is provided by embossing on the surface of the deformed layer at the resin layer side. The method for manufacturing the same is provided. The liquid crystal display device comprises a first substrate having a first electrode having a light reflecting function and partly formed on the surface opposed to a second substrate, the second substrate disposed oppositely to the first substrate, and a liquid crystal layer sealed between the first substrate and the second substrate. The method for manufacturing the liquid crystal display device having the resin layer which includes the rugged part on the surface comprises the steps of transferring the transfer material for forming the reflecting plate between the first substrate and the second substrate. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transfer material for forming a reflection plate, a method for manufacturing the same, a reflection plate, a liquid crystal display device and a method for manufacturing the same, and particularly to OA equipment, personal computers, portable information terminals and the like. The present invention relates to a reflective liquid crystal display device that utilizes outside light such as room lighting and sunlight, and a manufacturing method thereof, a reflection plate, a transfer material for forming a reflection plate used therefor, and a manufacturing method thereof.

[0002]

2. Description of the Related Art In recent years, a liquid crystal display device (LCD) has been most widely used or expected as a flat panel type display device replacing a CRT. Among them, thin film transistors (TFTs)
The LCD of the (stor) system (TFT-LCD) is expected to further expand the market by application to personal computers, word processors, OA devices, portable televisions and the like. Especially in the field of notebook type personal computers and portable information terminals as portable information tools with the progress of the multimedia society, power consumption is intended to be thinner and lighter and to prolong the usable time of the device. There is a demand for a liquid crystal display device with less power consumption. Since the reflective liquid crystal display device uses outside light such as indoor lighting and sunlight, it consumes less or less power due to the backlight and front light, and consumes less power than conventional transmissive liquid crystal display devices. It is possible to reduce electric power, and it is possible to reduce the thickness and weight.

In such a reflection type liquid crystal display device, a TN (twisted nematic) system, an STN has been conventionally used.
A (super twisted nematic) system and a phase transition type guest-host system as described in JP-A-5-173158 are used.

In order to obtain a brighter display in these reflection type liquid crystal display devices, it is necessary to increase the intensity of light scattered in a direction perpendicular to the display screen with respect to incident light from all angles. . For this reason, JP-A-6-
In Japanese Patent No. 75237, it is described that the uneven shape is controlled and formed on an insulating glass substrate, and a reflecting plate having a metal film such as Al or Ag formed thereon is formed thereon. The reflection plate of the above proposal, after forming a columnar convex portion using a polymer material on the glass substrate surface by photolithography or the like, and thermally deforming the corner of the upper edge portion of the columnar structure by heat treatment, A shape having a rounded upper edge is formed, and a polymer resin film is further laminated to fill the gaps in the columnar structure to form a continuous wavy surface shape. Al, Ag, etc. are formed on the wavy resin surface. By forming the metal film of 1), a reflector having a continuous wavy surface is manufactured.

However, in the production of the reflecting plate according to the above proposal, it is necessary to form a film structure of at least three layers, and three film forming steps and processing steps are required. There are drawbacks. Furthermore, a heating step of at least 200 ° C. or higher is required in order to make the upper edge of the columnar portion into a rounded shape with no corners. For this reason,
When a polymer resin substrate is used as the substrate for the purpose of further thinning and weight reduction of the liquid crystal display device, the substrate may be deformed or contracted during heating, so that the process cannot be performed and the usable material is high. There was a problem that it was limited to heat-resistant resins and the like.

In order to solve such a problem, Japanese Patent Laid-Open No. 11-
Japanese Patent No. 153804 proposes a reflective liquid crystal display device which has a convex shape formed by self-formation by multiple exposure of a photocurable resin and does not require heat treatment, and a manufacturing method thereof.

The control of the convex shape formed by this self-formation depends on the irradiated light energy, and the height of the convex portion can be controlled up to about 2 μm by controlling the light irradiation time or the light irradiation energy. Can be controlled.

However, the irradiation energy of the light is, for example, about 1.2 J / cm ^{2 to} 1.5 J / cm ² , and the irradiation time requires about 200 seconds. For this reason, the above method has a problem that the takt time of the production line is as long as 3 minutes or more and the productivity is poor.

On the other hand, a transflective liquid crystal display device (semitransmissive L
CD) has begun to spread as an optimal system for mobile applications. This cell structure is complicated, and a transmissive LCD part and a reflective LCD part are provided side by side within one pixel.
If these two parts are designed with the same liquid crystal thickness, each switching can be adjusted only halfway.
A system has been proposed in which the liquid crystal thickness of the CD portion is twice that of the reflective LCD portion (Japanese Patent Laid-Open No. 11-2422).
26, JP 2000-187220 A).

That is, in the double structure transflective LCD, the cell gap formed by bonding the substrate glass is basically adjusted to the gap d1 of the transmissive LCD, but the reflective LC is used.
Since the cell gap is halved in the D portion, it is approximately 1 / 2d1.
An insulating film having a thickness of 1 is formed by photolithography. In order to form a reflector that diffusely reflects on the insulating film, the insulating film may be a coating film having a two-layer structure.
No. 20, for example.

However, this method requires a multi-step process, resulting in a high cost of the LCD.

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to solve the above problems in the prior art and to solve the following problems. That is, the present invention provides a transfer material for forming a reflection plate and a manufacturing method thereof, a reflection plate manufactured from the transfer material, and a liquid crystal display device having a reflection electrode having good reflection characteristics by a simple process and a manufacturing method thereof. The purpose is to provide.

[0013]

Means for solving the problems Means for solving the above problems are as follows. That is, <1> At least one deformation layer and at least one resin layer are provided in this order on a temporary support, and (1) the resin layer is provided on the surface of the deformation layer on the resin layer side. An irregularly arranged uneven portion having a depth or a protrusion height of 2% or more and 200% or less of the thickness, a size in the plane direction of 1 to 15 μm, and (2) the thickness of the resin layer Has a depth or protrusion height of 2% or more and 200% or less, and a size in the plane direction of 1
It is a transfer material for forming a reflection plate, characterized in that any one of the concavo-convex portions having a size of 5 μm is provided by embossing. <2> At least one resin layer is provided on the temporary support, and (1) a depth of 2% or more and 200% or less of the resin layer thickness on the surface of the temporary support on the resin layer side, or Irregularly arranged irregularities having a protrusion height and a size in the plane direction of 1 to 15 μm, and (2) 2 of the resin layer thickness.
% Or more and 200% or less in depth or protrusion height, and any one of the concavo-convex portions having a size in the surface direction of 1 to 5 μm is provided by embossing, and the reflection plate forming transfer. It is a material. <3> At least one resin layer is provided on the temporary support, and as the temporary support, at least the surface on the resin layer side of the temporary support is 2% or more and 200% or less of the thickness of the resin layer. The transfer material for forming a reflection plate is characterized by using a material having an uneven portion having a depth or a protruding height. <4> The temporary support material is the reflection plate-forming transfer material according to <3>, which is a single-gloss aluminum foil. <5> The transfer material for forming a reflection plate according to any one of <1> to <4>, wherein the resin layer is an alkali-soluble photosensitive resin layer. <6> The transfer material for forming a reflection plate according to any one of <1> to <4>, wherein the resin layer is a photosensitive resin layer containing no alkali-soluble colorant. <7> At least one deformation layer and at least one resin layer are provided in this order on the temporary support, and (1) the thickness of the resin layer is provided on the surface of the deformation layer on the resin layer side. 2% or more and 200% or less of depth or protrusion height, the size in the plane direction is 1 to 15 μm, and irregularly arranged irregular portions, and (2) 2% of the resin layer thickness. Has a depth or protrusion height of 200% or more and has a size in the plane direction of 1
It is a method for producing a transfer material for forming a reflection plate, characterized in that any one of the concavo-convex portions having a thickness of 5 μm is provided by embossing. <8> At least one resin layer is provided on the temporary support, and (1) a depth of 2% or more and 200% or less of the resin layer thickness on the surface of the temporary support on the resin layer side, or Irregularly arranged irregularities having a protrusion height and a size in the plane direction of 1 to 15 μm, and (2) 2 of the resin layer thickness.
% Or more and 200% or less in depth or protruding height, and the size of 1-5 μm in the surface direction is provided by embossing any one of the uneven portions, and a reflection plate forming transfer material characterized by the above-mentioned. It is a manufacturing method. <9> The reflective plate-forming transfer material according to any one of <1> to <6> is transferred to a substrate, exposed, and developed.
It is a reflector having a light-reflecting functional material layer formed on a resin layer having a concavo-convex surface formed by baking. <10> A liquid crystal display device using the reflection plate according to <9> as one reflection electrode. <11> A first substrate on which at least a part of a first electrode having a light reflecting function is formed on a surface facing the second substrate, and a second substrate arranged to face the first substrate. And a liquid crystal layer encapsulated between the first and second substrates, the first substrate and the first substrate
And a resin layer having irregularities on the surface formed in a step including transfer using the transfer material for forming a reflection plate described in any one of the above items <1> to <6>. A characteristic liquid crystal display device. <12> The liquid crystal display device is the liquid crystal display device according to <11>, which has a color filter on array (COA) structure. <13> The liquid crystal display device is the liquid crystal display device according to <11>, which has a semi-transmissive structure. <14> The liquid crystal display device according to <11>, which has a color filter on array (COA) structure and a transflective structure. <15> A first substrate on which at least a part of a first electrode having a light reflecting function is formed on a surface facing the second substrate, and a second substrate arranged to face the first substrate. And a liquid crystal layer enclosed between a first substrate and a second substrate, the method <1> through <1> between the first substrate and the first electrode. 6> The method for manufacturing a liquid crystal display device, characterized in that a resin layer having irregularities on the surface is formed in a step including transfer using the transfer material for forming a reflection plate according to any one of 6>.

The reflection plate-forming transfer material described in the above item <1> or <2> is formed on the surface of the deformation layer or the temporary support on the resin layer side.
(1) An irregularly arranged uneven portion having a depth or a protruding height of 2% or more and 200% or less of the resin layer thickness, a size in the plane direction of 1 to 15 μm, and (2) ) Efficiently forming by embossing any one of the concavo-convex portions having a depth or a protrusion height of 2% or more and 200% or less of the resin layer thickness and a size in the plane direction of 1 to 5 μm. Therefore, it is possible to obtain a reflective electrode having good reflection characteristics.

The reflection plate-forming transfer material described in the above <3> comprises at least one resin layer provided on a temporary support, and as the temporary support, at least the resin layer side of the temporary support is provided. By using a material whose surface has unevenness having a depth or a protruding height of 2% or more and 200% or less of the thickness of the resin layer, it is possible to efficiently manufacture it in a simple process, so that good reflection can be obtained. A reflective electrode having characteristics can be obtained.

Therefore, according to the present invention, by a simple process, a reflective electrode having a good reflective property,
Among the liquid crystal display devices used for office automation equipment, personal computers, portable information terminals, etc., a reflective liquid crystal display device utilizing outside light such as room lighting or sunlight can be efficiently manufactured at low cost.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. <First Reflective Plate-Forming Transfer Material> The reflective plate-forming transfer material of the present invention comprises, as a first aspect, at least one deformation layer and at least one resin layer on a temporary support. Are provided in order, on the resin layer side surface of the deformation layer,
(1) By embossing irregularly arranged uneven portions having a depth or a protruding height of 2% or more and 200% or less of the resin layer thickness, and a size in the plane direction of 1 to 15 μm. It will be provided. Further, the transfer material for forming a reflection plate of the present invention,
In the first aspect, the surface of the deformable layer on the resin layer side has (2) a depth or a protrusion height of 2% or more and 200% or less of the resin layer thickness, and a size in the plane direction. Is 1-5
An uneven portion of μm is provided by embossing.

The resin layer is preferably a photosensitive resin layer, and the photosensitive resin layer is preferably alkali-soluble from the viewpoint of improving the developing solubility. Further, the photosensitive resin layer does not contain a colorant, the base of the reflector,
It is preferable for use as a reflective electrode in a liquid crystal cell. However, the resin layer may be colored for the purpose of removing stray light.

In the reflection plate forming transfer material after the reflection plate forming transfer material is transferred to the substrate so that the resin layer (photosensitive resin layer) is in contact with the substrate, a portion having convex and concave portions corresponding to the concave and convex portions is formed. That is, the thickness of the resin layer is 2% or more and 200% or less of the thickness of the other resin layer portion having no uneven portion.

-Shape, size, and number of uneven portions-
Although not particularly limited, square, rectangle, circle, ellipse and the like are preferable. When the shape (shape in the surface direction) viewed from above the uneven portion is square or circular, one side (or diameter) is 1
˜15 μm, preferably about 2 to 10 μm. When the shape (shape in the surface direction) viewed from above the uneven portion is rectangular or elliptical, the short side (or short diameter) is 1 to 15 μm.
m, preferably about 2 to 10 μm. In addition,
The short side (short diameter) is 1 μm and the long side (long diameter) is 15
Although a rectangle or an ellipse having a size of μm is closer to a line than a figure, the present invention includes all the uneven portions having such a shape. In this case, it is preferable to prevent the occurrence of coloring or stripes due to diffraction by randomly arranging the size and shape of the irregularities and arranging them. When the uneven portions are not randomly arranged (when regularly arranged), the shape as viewed from above the uneven portion (the shape in the surface direction)
If is square or circular, one side (or diameter) is 1 to 5
μm.

It is necessary that the depth or the protrusion height of the uneven portion is 2% or more and 200% or less of the thickness of the resin layer,
Preferably 5% or more and 100% or less, more preferably 10
% To 80%, more preferably 15% to 60%. The depth or the protruding height of the uneven portion indicates the maximum depth or the maximum protruding height when the depth or the protruding height varies. If the depth or protrusion height of the uneven portion is less than 5% of the thickness of the resin layer, good reflection characteristics cannot be obtained, while if it exceeds 300%, the alignment of the liquid crystal is disturbed and the contrast deteriorates. Further, the number of the concavo-convex portions varies depending on the application of the liquid crystal display device, etc., but is 1 to 3000 pieces, and preferably 10 to 30 pieces per 1 color pixel.
It is 0. It should be noted that one single-color pixel is one for black and white.
Pixel means a pixel corresponding to one color in the case of color, and the concavo-convex portion preferably has at least two sizes. Furthermore, it is more desirable that the irregularities are arranged irregularly and have a continuous wave shape from the viewpoint of obtaining good reflection characteristics.

-Method of Forming Concavo-convex Part-Employing the layer adjacent to the photosensitive resin layer of the reflection plate-forming transfer material according to the first embodiment, for example, the concavo-convex part formed on the deformable layer, by efficiently performing embossing. Can be formed.

Here, the embossing is a technique for forming an uneven portion on a material by rolling or embossing using an embossing roll or an embossing plate in which etching or an uneven pattern is engraved. The embossing roll used in the present invention is
Between a metal roll or a lithographic plate with a diameter of 100 to 900 mm in which irregularities of irregular size corresponding to irregularities are irregularly carved on the surface, and a pair of rolls (preferably an elastic roll with a flat surface) An uneven portion is formed on the surface of the material by passing the material through and pressing it with a lithographic plate. Rolling temperature is 50 ~ 200 ℃, speed is 3 ~ 150
It is preferable that the m / min and the linear pressure are about 0.3 to 20 t / m. As for the embossing, for example, “Surface Technology Handbook (edited by the Surface Technology Association of Japan, published by Nikkan Kogyo Shimbun (1998))”, “New Paper Processing Handbook (edited by Business Paper Times, published by Business Paper Times) (1980)) "and the like.

In the reflection plate-forming transfer material of the present invention, the deformed layer adjacent to the resin layer is embossed to form irregularities on the layer, and the resin layer (photosensitive resin layer) is formed thereon. Except for forming, it can be manufactured by a usual method.

The reflection plate-forming transfer material according to the first aspect comprises a temporary support provided with at least one deformation layer and at least one resin layer. A deformation layer and a photosensitive resin layer are provided in this order on a support,
Further, it has other layers appropriately selected as necessary. Hereinafter, each constituent layer of the transfer material for forming a reflection plate and constituent components contained therein will be described.

-Temporary support-The temporary support preferably has a releasability to the deformable layer to such an extent that transfer is not hindered, and it is chemically and
It is preferably thermally stable and flexible. Specifically, a thin film sheet of Teflon ^(R) , polyethylene terephthalate, polycarbonate, polyethylene, polypropylene or the like, or a laminate thereof is preferable.

In order to ensure good releasability between the temporary support and the deformable layer, it is preferable that no surface treatment such as glow discharge is applied and no undercoat layer such as gelatin is provided.

The thickness of the temporary support is 5 to 300.
μm is suitable, and 20 to 150 μm is preferable.

-Deformation Layer- The deformation layer is provided on the temporary support and mainly contains an alkali-soluble thermoplastic resin, and may contain other components as necessary. In addition, the transfer material for forming a reflection plate is formed by sequentially laminating a deformation layer and a resin layer on the temporary support, and particularly, the adhesion strength between the deformation layer and the temporary support is different from that of other layers. It is preferable that the adhesive strength is larger than the adhesive strength in 1., which is advantageous in that only the resin layer can be transferred by peeling the temporary support and the deformable layer at the time of transfer.

The thermoplastic resin is appropriately selected depending on the intended purpose without any restriction, but it is preferable to use a resin having a substantial softening point of 80 ° C or lower. Softening point is 80
As the thermoplastic resin having a temperature of ℃ or less, for example, a saponified product of ethylene and an acrylic acid ester copolymer, a saponified product of styrene and a (meth) acrylic acid ester copolymer, a vinyltoluene and a (meth) acrylic acid ester copolymer Examples include saponified products with polymers, saponified products with poly (meth) acrylic acid esters, and (meth) acrylic acid ester copolymers with butyl (meth) acrylate and vinyl acetate, etc. Alternatively, two or more kinds may be used in combination.

Further, organic materials having a softening point of about 80 ° C. or less, as described in "Plastic Performance Handbook" (edited by Japan Plastics Industry Federation, All Japan Plastics Molding Federation, published by Industrial Research Board, issued October 25, 1968) Among the polymers, those soluble in an aqueous alkaline solution can also be used.

Further, even if an organic polymer substance having a softening point of 80 ° C. or higher is added, various plasticizers compatible with the organic polymer substance are added to the organic polymer substance to substantially soften it. The point can be lowered to 80 ° C. or lower for use. Examples of the plasticizer include the same plasticizers that can be used in the photocurable composition described above.

When the above-mentioned organic polymer substance is used, various polymers, supercooling substances and adhesion-improving substances are used in order to adjust the adhesive force with a temporary support, which will be described later, within a range where the substantial softening point does not exceed 80 ° C. Agents, surfactants, release agents and the like can also be added.

The deformation layer is prepared by dissolving the thermoplastic resin and, if necessary, other components in an organic solvent to prepare a coating solution (deformation layer coating solution). For example, a known method such as spin coating is used. It can be formed by coating on a temporary support by a coating method.

Examples of the organic solvent include alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol methyl ethyl ether and ethylene glycol monoethyl ether. Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether; Glycol methyl ether acetate, propylene glycol alkyl ether acetates such as propylene glycol ethyl ether acetate: toluene, xylene and the like aromatic hydrocarbons; methyl ethyl ketone, cyclohexanone, 4-hydroxy -
Ketones such as 4-methyl-2-pentanone; ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2 -Methyl hydroxy-2-methylbutanoate,
Methyl 3-methoxypropionate, ethyl 3-methoquinopropionate, methyl 3-ethoxypropionate, 3-
Esters such as ethyl ethoxypropionate, ethyl acetate and butyl acetate; and the like. These organic solvents may be used alone or in combination of two or more.

Among these, in view of solubility of each component and film forming property, glycol esters such as ethylene glycol dimethyl ether, ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate, ethyl 2-hydroxypropionate, and 3 Particularly preferred are esters such as methyl methoxypropionate and ethyl 3-ethoxypropionate, and diethylene glycols such as diethylene glycol dimethyl ether.

Furthermore, N-methylformamide, N, N-
Dimethylformamide, N-methylformanilide, N
-Methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1
It is also possible to add a high boiling point solvent such as -octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate.

Further, a polymerizable monomer and a polymerization initiator for the photosensitive resin layer, which will be described later, are included, and at the same time as embossing,
Alternatively, after the embossing, before applying the photosensitive resin layer, light irradiation may be performed to initiate polymerization to form the deformable layer.

The layer thickness of the thermoplastic resin is 0.5.
-100 μm is preferable, and 3-50 μm is more preferable. If the layer thickness is less than 0.5 μm, sufficient unevenness may not be obtained during embossing, while 100
If it exceeds μm, the manufacturability may decrease.

-Photosensitive Resin Layer- The photosensitive resin layer can be preferably formed by the photosensitive resin composition described in detail below.

((Photosensitive resin composition)) The photosensitive resin composition of the present invention contains a polymerizable monomer, a (meth) acrylic acid-containing polymer and a polymerization initiator, and contains a negative type photopolymerization system or a positive type. Any type of photopolymerization system can be used. This resin composition is a thermoplastic resin composition having a softening property or an adhesive property at a temperature of 150 ° C. or lower, and is easily soluble in an alkaline solution in an unirradiated portion and contains a colorant. If necessary, it also contains other components such as a thermoplastic binder and a compatible plasticizer.

-Polymerizable Monomer- The polymerizable monomer is an addition-polymerizable compound having at least two ethylenically unsaturated bonds, and does not impair the alkali solubility of the (meth) acrylic acid-containing polymer described later, It is polymerized upon irradiation with light and reduces the solubility in an aqueous alkaline solution together with the (meth) acrylic acid-containing polymer.

The polymerizable monomer can be appropriately selected from compounds having two or more terminal ethylenically unsaturated bonds in one molecule, and examples thereof include a monomer, a prepolymer and
That is, those having a chemical structure such as a dimer, a trimer and an oligomer, a mixture thereof, or a copolymer thereof are included.

Specifically, for example, an ester of an unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) with an aliphatic polyhydric alcohol compound, an unsaturated carboxylic acid Examples thereof include amides of acids and aliphatic polyvalent amine compounds.

Examples of the ester (monomer) of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound include acrylic acid ester, methacrylic acid ester, itaconic acid ester, crotonic acid ester, isocrotonic acid ester,
Examples include maleic acid esters.

Examples of the acrylic acid ester include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentel glycol diacrylate, and tripentene glycol diacrylate. Methylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate,
Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (Acryloyloxyethyl) isocyanurate, polyester acrylate oligomer and the like can be mentioned.

Examples of the methacrylic acid ester include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3
-Butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p-
(3-methacryloxy-2-hydroxypropoxy)
Examples thereof include phenyl] dimethylmethane and bis [p- (methacryloxyethoxy) phenyl] dimethylmethane.

Examples of the itaconic acid ester include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate,
Examples thereof include tetramethylene glycol diitaconate, pentaerythritol diitaconate, and sorbitol tetriconate.

Examples of the crotonic acid ester include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate and sorbitol tetradicrotonate.

Examples of the isocrotonic acid ester include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate and sorbitol tetraisocrotonate.

As the maleic acid ester, for example,
Examples thereof include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramale. Furthermore, a mixture of the above-mentioned various esters can also be mentioned.

As the amide (monomer) of the unsaturated carboxylic acid and the aliphatic polyvalent amine compound, for example, methylenebis-acrylamide, methylebisbis-methacrylamide, 1,6-hexamethylenebis-acrylamide, 1,6-hexa Methylenebis-methacrylamide,
Diethylenetriamine tris acrylamide, xylylene bis acrylamide, xylylene bis methacrylamide, etc. are mentioned.

Other examples include Japanese Examined Patent Publication No. 48-417.
No. 08, the polyisocyanate compound having two or more isocyanate groups in one molecule is added with a hydroxyl group-containing vinyl monomer represented by the following general formula (I) to obtain two or more molecules in one molecule. Examples thereof include vinyl urethane compounds containing a polymerizable vinyl group. _{CH 2 = C (R) COOCH} 2 CH (R 1) OH (I) [wherein, R and ^{R 1} represents H or CH _3. ]

Further, urethane acrylates described in JP-A-51-37193, JP-A-48-64183,
No. 4, Japanese Patent Publication No. 49-43191, Japanese Patent Publication No. 52-3049
Polyfunctional acrylates and methacrylates such as polyester acrylates, epoxy acrylates obtained by reacting an epoxy resin with (meth) acrylic acid, and the like described in each publication such as No. 0 can be mentioned. Furthermore, the Japan Adhesive Association magazine (vo1.20, No.7, p.300-308 (19
Those introduced as photo-curable monomers and oligomers in 1984)) can also be used.

The above polymerizable monomers may be used alone or in combination of two or more. The content of the polymerizable monomer is preferably 10 to 60% by mass of the total solid content of the photosensitive resin composition, more preferably 20 to 50% by mass.

The mass ratio of the total amount of the polymerizable monomer to the total amount of the (meth) acrylic acid-containing polymer described later is 0.5 to 0.9. If the mass ratio is less than 0.5, curing by photopolymerization is insufficient and hardness is insufficient. On the other hand, if it exceeds 0.9, a preferable shape cannot be obtained.

-(Meth) acrylic acid-containing polymer- The (meth) acrylic acid-containing polymer is contained mainly as a binder component and can be developed with an alkaline solution. The (meth) acrylic acid-containing polymer is generally a polymer having a carboxylic acid group in its side chain, for example, JP-A-59-44615 and JP-B-54-3.
4327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-71048, and a methacrylic acid copolymer and acrylic acid. Copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer,
Examples thereof include partially esterified maleic acid copolymers.
Moreover, the cellulose derivative which has a carboxylic acid group in a side chain is also mentioned.

In addition to the above, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are also preferred. In particular,
The copolymer of benzyl (meth) acrylate and (meth) acrylic acid and the multi-component copolymer of benzyl (meth) acrylate, (meth) acrylic acid and other monomers described in US Pat. No. 4,139,391 are listed. be able to. Furthermore, alcohol-soluble nylon can also be mentioned. Further, a plurality of (meth) acrylic acid-containing polymers may be used in combination.

The (meth) acrylic acid-containing polymer usually has an acid value in the range of 50 to 300 mg KOH / 1 g and 1
It is used by appropriately selecting from those having a mass average molecular weight in the range of 000 to 300,000. The acid value is 5
If it is less than 0 mgKOH / 1 g, the alkali developability may be significantly reduced, while on the other hand, 300 mgKOH / 1
If it exceeds g, the target structure may not be obtained.

The mass average molecular weight of the (meth) acrylic acid-containing polymer is 1,000 to 3,000 as described above.
00 is preferred, and particularly 10,000 to 250,000
Is preferred. If the mass average molecular weight is less than 1000, the target structure may not be obtained,
On the other hand, when it exceeds 300,000, the developability may be extremely lowered. The mass average molecular weight is a polystyrene equivalent average molecular weight measured by GPC (gel permeation chromatography).

The content of the (meth) acrylic acid-containing polymer is 20 to 60 of the total solid content of the photosensitive resin composition.
Mass% is preferable, and 30 to 55 mass% is more preferable.
The content of the (meth) acrylic acid-containing polymer is 20% by mass.
If the amount is less than 60% by weight, it may be difficult to form a film when the photosensitive resin composition is applied onto a support, while if it exceeds 60% by mass, the content ratio of the polymerizable monomer decreases.
Polymerization may be poor.

-Polymerization Initiator- The polymerization initiator is capable of substantially initiating the photopolymerization of the polymerizable monomer, and all compounds having the ability to initiate the polymerization reaction of the polymerizable monomer are used. It is possible. Among them, it is particularly preferable to contain at least one component having a molecular extinction coefficient of at least about 50 in the wavelength region of about 300 to 500 nm and have photosensitivity to light rays in the ultraviolet region.

Examples of the polymerization initiator include halogenated hydrocarbon derivatives, ketone compounds, ketoxime compounds, organic peroxides, thio compounds, hexaarylbiimidazoles, aromatic onium salts, ketoxime ethers,
JP-A-2-48664, JP-A-1-152449
Aromatic ketones, lophine dimers, benzoins, benzoin ethers, polyhalogens, and combinations of two or more of these, and the like described in JP-A No. 2-153353.

Among these, halogenated hydrocarbon compounds having a triazine skeleton, ketoxime compounds, hexaarylbiimidazole, 4,4′-bis (diethylamino), in terms of excellent photosensitivity, storability, adhesion to substrates, etc. ) Benzophenone and 2- (o-chlorophenyl)-
A combination of 4,5-diphenylimidazole dimers,
2,4-bis (trichloromethyl) -6- [4- (N, N
-Diethoxycarbonylmethylamino) -3-bromophenyl] -s-triazine, 4- [p-N, N-di (ethoxycarbonylmethyl) -2,6-di (trichloromethyl) -s-triazine] Preferred systems are preferred.

Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Bull. Chem.
Soc. Japan, 42, 2924 (Wakabayashi et al., 19
69) [e.g., 2-phenyl-4,6]
-Bis (trichloromethyl) -s-triazine, 2-
(P-Chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-
(P-Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ', 4'-dichlorophenyl) -4,6-bis (trichloromethyl) -s-
Triazine, 2,4,6-tris (trichloromethyl)
-S-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2-n-nonyl-4,
6-bis (trichloromethyl) -s-triazine, 2-
(Α, α, β-Trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine and the like]; British Patent No. 1
Compounds described in Japanese Patent No. 388492 [for example, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylstyryl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl)
-S-triazine, 2- (p-methoxystyryl) -4
-Amino-6-trichloromethyl-s-triazine, etc.]; Compounds described in JP-A-53-133428 [for example, 2- (4-methoxy-naphth-1-yl)-
4,6-bis-trichloromethyl-s-triazine, 2
-(4-Ethoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- [4-
(2-Ethoxyethyl) -naphth-1-yl] -4,6
-Bis (trichloromethyl) -s-triazine, 2-
(4,7-Dimethoxy-naphth-1-yl) -4,6-
Bis (trichloromethyl) -s-triazine, 2- (acenaphtho-5-yl) -4,6-bis (trichloromethyl) -s-triazine, etc.]; German Patent No. 3337024
Described in the specification of the present invention [for example, 2- (4-styrylphenyl) -4,6-bis (trichloromethyl) -s-
Triazine, 2- (4-p-methoxystyrylphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (1-naphthylvinylenephenyl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-chlorostyrylphenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (4-thiophen-2-vinylenephenyl) -4,6-bis ( Trichloromethyl)
-S-triazine, 2- (4-thiophen-3-vinylenephenyl) -4,6-bis (trichloromethyl) -s
-Triazine, 2- (4-furan-2-vinylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-benzofuran-2-vinylenephenyl) -4,6-bis (trichloro) Methyl) -s-triazine, etc.]; Org. Chem. (FC Scha
efer et al., 29, 1527 (1964)) [eg, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s. -Triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2-amino-4
-Methyl-6-tribromomethyl-s-triazine, 2
-Methoxy-4-methyl-6-trichloromethyl-s-
Triazine and the like]; Compounds described in JP-A-62-58241 [eg, 2- (4-phenylacetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-naphthyl- 1-acetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-p-tolylacetylenephenyl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (4-p-methoxyphenylacetylenephenyl)
-4,6-bis (trichloromethyl) -s-triazine, 2- (4-p-isopropylphenylacetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-p-ethyl) Phenylacetylenephenyl) -4,6-bis (trichloromethyl) -s-triazine etc.]; Compounds described in JP-A-5-281728 [for example, 2- (4-trifluoromethylphenyl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (2,6-difluorophenyl) -4,6-
Bis (trichloromethyl) -s-triazine, 2-
(2,6-Dichlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,6-dibromophenyl) -4,6-bis (trichloromethyl) -s
-Triazine and the like], and the like.

Examples of the ketoxime compound include compounds represented by the following general formula (II).

[0067]

[Chemical 1]

In the general formula (II), R ² and R ³ are
Each independently, may have a substituent, represents a hydrocarbon group optionally having an unsaturated bond, a heterocyclic group,
They may be the same or different from each other. R ⁴ and R ⁵ are
Each may independently have a hydrogen atom or a substituent,
It represents a hydrocarbon group which may have an unsaturated bond, a heterocyclic group, a hydroxyl group, a substituted oxy group, a mercapto group or a substituted thio group, which may be the same or different from each other.
In addition, R ⁴ and R ⁵ may be bonded to each other to form a ring, and in this case, the ring is —O—, —NR ⁶ —, —O—.
CO -, - NH-CO - , - represents at least one divalent group connecting backbone as which may contain an alkylene group having a carbon number of 2-8 ring selected from _- S- and -SO 2 . R ⁶ and R ⁷ each independently represent a hydrogen atom, a hydrocarbon group which may have a substituent, and may contain an unsaturated bond, or a substituted carbonyl group.

Specific examples of the compound represented by the general formula (II) are shown below. However, the present invention is not limited to these. For example, p-methoxyphenyl-2-N, N-dimethylaminopropyl ketone oxime-O-allyl ether, p-methylthiophenyl-2
-Morpholinopropyl ketone oxime-O-allyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O-benzyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O-n-butyl ether, p -Morpholinophenyl-2-morpholinopropyl ketone oxime-O
-Allyl ether, p-methoxyphenyl-2-morpholinopropyl ketone oxime-On-dodecyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O-methoxyethoxyethyl ether, p-methylthiophenyl-2 -Morpholinopropyl ketone oxime-O-p-methoxycarbonylbenzyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O-methoxycarbonylmethyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O -Ethoxycarbonyl methyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O-4-butoxycarbonylbutyl ether, p-methylthiophenyl-2
-Morpholinopropyl ketone oxime-O-2-ethoxycarbonyl ethyl ether, p-methylthiophenyl-2-morpholinopropyl ketone oxime-O-methoxycarboyl-3-propenyl ether, p-methylthiophenyl-2-morpholinopropyl Ketone oxime-O-benzyloxy carbonyl methyl ether etc. are mentioned.

Examples of the hexaarylbiimidazole include 2,2'-bis (o-chlorophenyl)-
4,4 ′, 5,5′-tetraphenylbiimidazole,
2,2'-bis (o-bromophenyl) -4,4 ', 5
5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4 , 4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (o,
o'dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2, 2'-bis (o-methylphenyl) -4,
4 ', 5,5'-tetraphenylbiimidazole, 2,
2'-bis (o-trifluoromethylphenyl) -4,
4 ', 5,5'-tetraphenyl biimidazole etc. are mentioned. These biimidazoles are, for example, Bu
ll. Chem. Soc. Japan, 33, 565
(1960) and J. Org. Chem, 36 (16)
It can be easily synthesized by the method described in 2262 (1971).

Examples of the ketoxime ether include 3-benzoyloxyiminobutan-2-one, 3-
Acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-
1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-
Examples include on.

The above-mentioned polymerization initiators may be used alone or in combination of two or more, and it is also possible to use several compounds in combination of different kinds. The content of the polymerization initiator is 0.1% of the total solid content of the photosensitive resin composition.
-50 mass% is preferred, and 0.5-30 mass% is more preferred.

-Colorants such as Dyes and Pigments-When the transfer material for forming a reflection plate of the present invention is colored, the photosensitive resin layer may contain colorants such as organic pigments, inorganic pigments or dyes. it can. As a yellow pigment, for example,
C. I. Pigment Yellow 20, C.I. I. Pigment Yellow 24, C.I. I. Pigment Yellow 83, C.I.
I. Pigment Yellow 86, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 109, C.I.
I. Pigment Yellow 110, C.I. I. Pigment Yellow 117, C.I. I. Pigment Yellow 125,
C. I. Pigment Yellow 137, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 13
9, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 1
48, C.I. I. Pigment Yellow 153, C.I. I. Pigment Yellow, C.I. I. Pigment Yellow 15
4, C.I. I. Pigment Yellow 166, C.I. I. Pigment Yellow 168, Monolight Yellow GT
(C.I. Pigment Yellow 12), Permanent
Yellow GR (CI Pigment Yellow 17) and the like.

Examples of orange pigments include C.I. I.
Pigment Orange 36, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 51, C.I. I. Pigment Orange 55, C.I. I. Pigment Orange 5
9, C.I. I. Pigment Orange 61 and the like.

Examples of red pigments include C.I. I. Pigment Red 9, C.I. I. Pigment Red 97, C.I.
I. Pigment Red 122, C.I. I. Pigment Red 123, C.I. I. Pigment Red 149, C.I. I.
Pigment Red 168, C.I. I. Pigment Red 1
77, C.I. I. Pigment Red 180, C.I. I. Pigment Red 192, C.I. I. Pigment Red 20
9, C.I. I. Pigment Red 215, C.I. I. Pigment Red 216, C.I. I. Pigment Red 217,
C. I. Pigment Red 220, C.I. I. Pigment Red 223, C.I. I. Pigment Red 224, C.I.
I. Pigment Red 226, C.I. I. Pigment Red 227, C.I. I. Pigment Red 228, C.I. I.
Pigment Red 240, C.I. I. Pigment Red 4
8: 1, Permanent Carmin FBB (CI Pigment Red 146), Permanent Ruby FBH
(C. I. Pigment Red 11), Fastel Pink B Spla (C. I. Pigment Red 81) and the like.

Examples of violet pigments include C.I.
I. Pigment Violet 19, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 2
9, C.I. I. Pigment Violet 30, C.I. I. Pigment Violet 37, C.I. I. Pigment Violet 40, C.I. I. Pigment Violet 50 and the like.

As the blue pigment, for example, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 15:
1, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6, C.I. I. Pigment Blue 2
2, C.I. I. Pigment Blue 60, C.I. I. Pigment Blue 64, Victoria Pure Blue BO (C.
I. 42595) and the like.

Examples of green pigments include C.I. I. Pigment Green 7, C.I. I. Pigment Green 36 and the like.

Examples of brown pigments include C.I. I. Pigment Brown 23, C.I. I. Pigment Brown 2
5, C.I. I. Pigment Brown 26 and the like.

As the black pigment, for example, Monolight First Black B (CI Pigment Black 1), C.I. I. Pigment Black 7 and Fat Black HB (C.I.26150).

Other examples include carbon black and auramine (C.I.41000). The colorant such as the above organic pigment, inorganic pigment, or dye is 1
The species may be used alone, or two or more species may be used in combination.

When the above colorant is used, the particle size of the pigment or dye is preferably 5 μm or less, and 1
More preferably, it is less than or equal to μm. Since the photosensitive resin layer is a thin layer, if the particle size of the pigment or the like is not within the above range, it cannot be uniformly dispersed in the resin layer, which is not preferable.

The amount of the colorant such as the dye or pigment added is preferably 0.01 to 30% by mass of the total solid content of the photosensitive resin composition.

-Other Components- The photosensitive resin composition may contain other components such as a thermoplastic binder and a compatible plasticizer.

Examples of the thermoplastic binder include, for example,
Known binders such as ethylenically unsaturated compounds may be mentioned.

Examples of the compatible plasticizer include polypropylene glycol, polyethylene glycol, dioctyl phthalate, diheptyl phthalate, dibutyl phthalate, tricresyl phosphate, cresyl diphenyl phosphate biphenyl diphenyl phosphate and the like. The binder and the plasticizer may be added in an amount that does not impair the effects of the present invention.

The photosensitive resin layer is prepared by dissolving each of the above components in an organic solvent to prepare a coating solution (coating solution for coating the photosensitive resin layer), and forming irregularities by a known coating method. It can be formed by coating on the deformed layer.
The organic solvent is not particularly limited, and the same one as that which can be used for the preparation of the deformation layer coating liquid can be used.

The layer thickness of the photosensitive resin layer (portion having no uneven portion) is preferably 0.5 to 10 μm,
6 μm is more preferable. The layer thickness of the photosensitive resin layer,
If it is less than 0.5 μm, pinholes are likely to occur during the application of the photosensitive resin layer coating liquid, which may lower the production suitability. On the other hand, if it exceeds 10 μm, the unexposed portion is removed during development. May take a long time.

-Intermediate Layer-The reflective plate-forming transfer material may be provided with an intermediate layer between the photosensitive resin layer and the deformable layer, if necessary. Since an organic solvent is used in the formation of the photosensitive resin layer and the deformable layer, if the intermediate layer is located between them,
It is possible to prevent both layers from mixing with each other. Further, when the oxygen barrier ability of the intermediate layer is lowered, the polymerization sensitivity of the photosensitive resin layer is lowered, so that not only the amount of light at the time of exposure is increased or the exposure time is lengthened, but also the resolution is lowered. Therefore, it is preferable that the oxygen permeability is low.

The intermediate layer is mainly composed of a resin component that can be dispersed and dissolved in water or an aqueous alkali solution, and may contain other components such as a surfactant, if necessary. As the resin component constituting the intermediate layer, known ones can be used. For example, the polyvinyl ether / maleic anhydride polymer described in JP-A-46-2121 and JP-B-56-40824. , Water-soluble salts of carboxyalkyl cellulose, water-soluble cellulose ethers,
Water-soluble salts of carboxyalkyl starch, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamides,
Examples include water-soluble polyamides, water-soluble salts of polyacrylic acid, gelatin, ethylene oxide polymers, water-soluble salts of the group consisting of various starches and the like, styrene / maleic acid copolymers, maleate resins, and the like. These may be used alone or in combination of two or more. Among these, it is preferable to use a hydrophilic polymer, and it is preferable to use at least polyvinyl alcohol among the hydrophilic polymers, and it is particularly preferable to use polyvinyl alcohol and polyvinylpyrrolidone in combination.

The polyvinyl alcohol is appropriately selected depending on the intended purpose without any limitation, but the saponification rate is preferably 80% or more. When the polyvinylpyrrolidone is used, its content is preferably 1 to 75% by volume, more preferably 1 to 60% by volume, and preferably 10 to 50% by volume based on the solid content of the intermediate layer. % Is particularly preferred. If the content is less than 1% by volume, sufficient adhesiveness to the photosensitive resin layer may not be obtained, while if it exceeds 75% by volume, the oxygen barrier ability may be reduced. , Not preferable.

For the intermediate layer, the resin components and the like are dissolved and dispersed in an aqueous solvent to prepare a coating liquid (intermediate layer coating liquid),
For example, it can be formed by coating on the deformable layer by a known coating method such as spin coating. Examples of the water-based solvent include a solvent containing water such as distilled water as a main component, and if desired, a solvent having a compatibility with water such as alcohol or a salt added thereto within a range not impairing the effects of the present invention.

The thickness of the intermediate layer is about 0.1-5.
μm is preferable, and 0.5 to 2 μm is more preferable. If the layer thickness is less than about 0.1 μm, the oxygen permeability may be too high and the sensitivity of polymerization of the photosensitive resin layer may be reduced, while if it exceeds about 5 μm, the layer may be long during development and removal of the intermediate layer. It may take time.

-Cover Film- A cover film is preferably provided on the photosensitive resin layer for the purpose of protecting it from stains and damage during storage. The cover film can be selected from those that can be easily peeled from the photosensitive resin layer, and may be made of the same or similar material as the temporary support. Specifically, silicone paper, polyolefin, polytetrafluoroethylene sheet and the like are preferable, and polyethylene and polypropylene film are more preferable.

The thickness of the cover film is about 5
˜100 μm is preferable, and 10˜30 μm is more preferable.

<Second Transfer Material for Forming Reflecting Plate> The transfer material for forming a reflecting plate of the present invention is, in a second aspect, provided with at least one resin layer on a temporary support. The surface of the body on the side of the resin layer has (1) a depth of 2% or more and 200% or less of the thickness of the resin layer or a protruding height, and a size in the surface direction of 1 to 15 μm, which is irregular. The embossed portion is provided on the concave and convex portion arranged in. Further, the transfer material for forming a reflection plate of the present invention is, in the second aspect, provided with (2) a depth of 2% or more and 200% or less of a thickness of the resin layer on a surface of the deformation layer on the resin layer side, or An uneven portion having a protruding height and a size in the plane direction of 1 to 5 μm is provided by embossing.

The second reflection plate-forming transfer material has the same structure as the first reflection plate-forming transfer material except that it does not have a deformation layer and that the temporary support is embossed. Will be omitted.

<Third Reflective Plate-Forming Transfer Material> In the third embodiment, the reflective plate-forming transfer material of the present invention comprises at least one resin layer provided on a temporary support. As the body, at least the surface of the temporary support on the side of the resin layer is made of a material having an uneven portion having a depth or a protruding height of 2% or more and 200% or less of the thickness of the resin layer.

As the temporary support having the uneven portions, if a material that is necessarily formed with the uneven portions when the temporary support is formed is used, the subsequent processing is unnecessary and the manufacturing cost can be reduced. For example, of the cold-rolled aluminum foil, a single-gloss aluminum foil is suitable. When the aluminum foil is rolled, it passes between a pair of two rollers and becomes a glossy surface by the action of the rollers. However, when the thickness of the aluminum foil is reduced, the aluminum foil is rolled in two layers, and at this time, it faces each other. The matte surfaces are matte surfaces having minute irregularities on the surface.

In the third transfer material for forming a reflecting plate, there is no deformation layer, and at least the surface of the temporary support on the resin layer side has a depth of 2% or more and 200% or less of the resin layer thickness. The structure is the same as that of the first reflection plate forming transfer material except that the material having the concave-convex portion having the protrusion height or the protruding height is used, and the description thereof will be omitted.

<Method of Manufacturing Transfer Material for Forming Reflector> In the first embodiment of the method for manufacturing transfer material for forming reflector, at least one deformation layer and at least one layer are provided on the temporary support. And a resin layer of 1) having a depth or a protrusion height of 2% or more and 200% or less of the thickness of the resin layer on the surface of the deformable layer on the resin layer side. The size in the direction is 1 to 15 μm, and the irregularities are arranged irregularly, and (2) the depth or the protruding height is 2% or more and 200% or less of the thickness of the resin layer, and the size in the plane direction. 1-5
Any of the uneven portions of μm is provided by embossing.

As a second aspect of the method for producing a transfer material for forming a reflection plate of the present invention, at least one resin layer is provided on the temporary support, and the temporary support is provided on the resin layer side. (1) has a depth or a protrusion height of 2% or more and 200% or less of the thickness of the resin layer, and has a size in the plane direction of 1 to
15 μm, irregularly arranged irregularities and (2)
Any one of the concavo-convex portions having a depth or a protruding height of 2% or more and 200% or less of the thickness of the resin layer and having a size in the plane direction of 1 to 5 μm is provided by embossing.

In the manufacturing methods of the first and second aspects, the method of forming the uneven portion on the deformable layer or the temporary support by embossing is as described above. In addition, the manufacturing method of the reflection plate forming transfer material of the first and second aspects of the present invention,
Except for the above points, it can be produced by a known method.

Specifically, the manufacturing method of the second aspect will be described by way of example. The deformation layer coating liquid is applied on the temporary support and dried to form a deformation layer, and the deformation layer is embossed. Then, the uneven portion is formed. It can be formed by applying a coating solution prepared by dissolving the photosensitive resin composition on the deformable layer having the uneven portion and then drying the coating solution to form a photosensitive resin layer. Alternatively, by providing a photosensitive resin layer on the cover film, on the other hand, providing a deformation layer having an uneven portion formed on the temporary support, and by bonding each so that the deformation layer and the photosensitive resin layer are in contact with each other. The transfer material for forming a reflection plate of the present invention can be manufactured.

As will be described later, in the process of bringing the transfer material into close contact with the substrate, which is the transfer target, and peeling the temporary support of the transfer material, the temporary support and the substrate are charged, and as a result, the surrounding dust and the like are removed. Dust and the like are attached to the photosensitive resin layer after attracting and peeling, and an unexposed portion is formed in the subsequent exposure process, and that portion becomes a factor of forming a pinhole, so for the purpose of preventing charging, It is preferable to reduce the surface electric resistance to 10 ¹³ Ω or less by providing a conductive layer on at least one surface of the temporary support or using a temporary support having conductivity.

To give conductivity to the temporary support, a conductive substance may be contained in the temporary support. For example, a method of previously kneading fine particles of a metal oxide and an antistatic agent is suitable. Examples of the metal oxide include zinc oxide, titanium oxide, tin oxide, aluminum oxide, indium oxide,
Examples thereof include fine particles of a crystalline metal oxide such as silicon oxide, magnesium oxide, barium oxide, molybdenum oxide, and / or a composite oxide thereof.

Examples of the antistatic agent include Electrostripper A (manufactured by Kao Corporation), Elenon No. 19 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and the like, alkylphosphate-based anionic surfactants; amogen K (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and other amphoteric surfactants; Nissan Nonion L (Nippon Yushi and Polyoxyethylene fatty acid ester-based nonionic surface active agents; Emulgen 106, 120, 1
47, 420, 220, 905, 910 (Kao Corporation)
(Manufactured by Nippon Oil & Fat Co., Ltd.) and polyoxyethylene alkyl ether-based nonionic surfactants are preferable. Other nonionic surfactants include polyoxyethylene alkylphenol ether-based, polyhydric alcohol fatty acid ester-based, polyoxyethylene sorbitan fatty acid ester-based, and polyoxyethylene alkylamine-based surfactants.

When a conductive layer is provided on the temporary support,
The conductive layer can be appropriately selected and used from known ones. As the conductive material used for the conductive layer, ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂
At least one crystalline metal oxide selected from O ₃ , SiO ₂ , MgO, BaO, MoO ₃ and / or the like, and / or
Examples thereof include fine particles of the composite oxide. The method of incorporating these is preferable in that it is not affected by the humidity environment and has a stable conductive effect.

The volume resistance value of the fine particles of the crystalline metal oxide or its composite oxide is preferably 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less. Also,
The particle diameter is preferably 0.01 to 0.7 μm, more preferably 0.02 to 0.5 μm.

The method for producing fine particles of the above crystalline metal oxide and its composite oxide is described in detail in JP-A-56-143430. That is, first, a method in which metal oxide fine particles are produced by firing and heat treatment is performed in the presence of a heteroatom for improving conductivity, and secondly, conductivity is improved when producing metal oxide fine particles by firing. Thirdly, a method of allowing different atoms to coexist, and a third method of introducing oxygen defects by lowering the oxygen concentration in the atmosphere when producing the metal fine particles by firing are described. As a specific example including a heteroatom, Zn, Al, In, Ti, etc.
Nb, Ta, etc. for O ₂ , Sb, N for SnO ₂
b, the presence of a halogen element, etc. may be mentioned.

The addition amount of the heteroatom is 0.01 to 3.
0 mol% is preferable, and 0.1-10 mol% is more preferable. The amount of conductive particles used is 0.05 to 20.
preferably ^{g / m 2, 0.1~10g / m} 2 is more preferable.

In the conductive layer provided on the transfer material, as a binder, a cellulose ester such as gelatin, cellulose nitrate, cellulose triacetate, cellulose diacetate, cellulose acetate butyrate or cellulose acetate propionate; vinylidene chloride,
A homopolymer or copolymer containing vinyl chloride, styrene, acrylonitrile, vinyl acetate, an alkyl acrylate having 1 to 4 carbon atoms, vinylpyrrolidone or the like; soluble polyester, polycarbonate, soluble polyamide or the like can be used.

When the conductive particles are dispersed in these binders, a dispersion liquid such as a titanium dispersant or a silane dispersant may be added. Further, a binder cross-linking agent or the like can be added if necessary.

Examples of the titanium-based dispersant include, for example, US Pat. Nos. 4,069,192 and 4,080,
Examples thereof include titanate coupling agents and Planeact (manufactured by Ajinomoto Co., Inc.) described in JP-A No. 353. Examples of the silane-based dispersant include vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. , "Silane coupling agent" (manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the binder crosslinking agent include epoxy crosslinking agents, isocyanate crosslinking agents, aziridine crosslinking agents, and epoxy crosslinking agents.

The conductive layer may be obtained by dispersing conductive fine particles in a binder and coating the same on a temporary support, or by subjecting the temporary support to an undercoating treatment (for example, an undercoat layer). It can be provided by attaching conductive fine particles.

The conductive layer may be provided on the surface of the temporary support opposite to the surface coated with the photosensitive resin layer. In this case, in order to secure sufficient scratch resistance, the conductive layer is electrically conductive. It is preferable to further provide a hydrophobic polymer layer on the functional layer. The hydrophobic polymer layer may be applied in a state where the hydrophobic polymer is dissolved in an organic solvent or in the state of an aqueous latex, and the application amount thereof is preferably about 0.05 to 1 g / m ^{2 in} dry mass. .

Examples of the hydrophobic polymer include cellulose esters such as nitrocellulose and cellulose acetate; vinyl-based polymers containing vinyl chloride, vinylidene chloride, vinyl acrylate and the like; polymers such as organic solvent-soluble polyamide and polyester. You can

For the purpose of imparting slipperiness to the hydrophobic polymer layer, a slipping agent such as an organic carboxylic acid amide described in JP-A-55-79435 can be used. Also, a matting agent or the like can be used if necessary. Even if such a hydrophobic polymer layer is provided, the effect of the conductive layer is not substantially affected.

When an undercoat layer is provided, it is not disclosed in JP-A-51-13.
5526, U.S. Pat. Nos. 3,143,421, 3,586,508, and 2,698.
235 and 3,567,452, and the like, vinylidene chloride copolymers, JP-A-51-11412
No. 0, U.S. Pat. No. 3,615,556, and other diolefin-based copolymers such as butadiene;
Glycidyl acrylate- or glycidyl methacrylate-containing copolymers described in JP-A-58469, polyamide / epichlorohydrin resins described in JP-A-48-24923, and maleic anhydride described in JP-A-50-39536. An acid-containing copolymer or the like can be used.

In the present invention, JP-A-56-8250 is used.
4, JP-A-56-143443, JP-A-5
7-104931, JP-A-57-118242, JP-A-58-62647, and JP-A-60-2.
The conductive layer described in Japanese Patent No. 58541 can also be used if necessary.

When a conductive layer is coated on the temporary support,
Roller coat, air knife coat, gravure coat,
Application by known methods such as bar coating and curtain coating
can do. To obtain sufficient antistatic effect
Is the surface electricity of the conductive layer or the temporary support having conductivity.
Resistance value is 10^ThirteenΩ or less is preferable and 10
¹²It is more preferably Ω or less.

Further, in order to prevent strong adhesion of the photosensitive resin layer to the temporary support, a lubricant composition containing known fine particles on the surface of the temporary support, a release agent composition containing a silicone compound and the like are used. It can also be applied.

When a conductive layer is provided on the surface of the temporary support on which the deformation layer is not provided, the temporary support may be provided with, for example, glow discharge for the purpose of improving the adhesion between the deformation layer and the temporary support. Surface treatment such as treatment, corona treatment, and ultraviolet irradiation treatment, undercoating treatment of a phenolic substance, polyvinylidene chloride resin, styrene butadiene rubber, gelatin, or a combination of these treatments can be performed.

The film for the temporary support can be formed by extrusion, but the conductive material or the conductive layer is contained in the same or different plastic raw material as the temporary support, and the film is extruded simultaneously with the film. In that case, a conductive layer having excellent adhesiveness and scratch resistance can be easily obtained. In this case, it is not necessary to provide the hydrophobic polymer layer or the undercoat layer, and this is the most preferable embodiment as the conductivity-imparting temporary support that constitutes the transfer material. The main application of the transfer material for forming a reflector of the present invention is preferably an underlayer of a reflector or a resin layer for forming a reflective electrode in a liquid crystal cell.

<Reflector> Next, the reflector of the present invention is a resin layer having an uneven portion on the surface formed by transferring the above-mentioned transfer material for forming a reflector to a substrate, exposing, developing and baking. A light-reflecting functional material is formed thereon.

First, the cover film of the transfer material for forming the reflection plate is removed, and the photosensitive resin layer is attached to the substrate which is the transfer target under pressure and heating. A conventionally known laminator, a vacuum laminator, or the like can be used for bonding, and an auto-cut laminator can also be used to further improve productivity. After that, the temporary support is peeled off, the photosensitive resin layer is exposed through a predetermined mask, the deformation layer and the intermediate layer, and then developed. The development can be carried out by a known method, using a solvent or an aqueous developing solution, particularly an alkaline aqueous solution or the like, immersing the substrate after exposure or spraying with a spray or the like, and further rubbing with a brush or the like, Alternatively, it is performed by processing while irradiating ultrasonic waves.

After bonding the photosensitive resin layer of the transfer material for forming a reflection plate and the substrate which is the transferred material, the temporary support is peeled off at the interface with the deformable layer, and the deformable layer is formed from above the deformable layer. And the photosensitive resin layer is patterned (exposed) through the intermediate layer. The exposure is 300 to 500n
It can be performed by irradiating light having a wavelength of m.
High pressure mercury lamp, super high pressure mercury lamp, metal halide lamp, H
Examples thereof include g-Xe lamp.

As the patterning method,
For example, a method using a photolithography method, a method of arranging an exposure mask above the deformable layer and exposing in a pattern through the mask, a method of using an exposure means such as a contact type proximity exposure apparatus, and the like can be mentioned. In the patterning by the above method, the exposure amount is preferably 3 to 10 times the minimum exposure amount at which the photosensitive resin composition causes polymerization and curing, and the proximity amount is 40 to 150.
μm is preferred.

After the exposure, development processing is performed to remove the deformable layer and the unnecessary portion (uncured portion) of the photosensitive resin layer.

The development can be carried out by a known method. For example, (a) the substrate itself after exposure is immersed in a developing bath using a solvent or an aqueous developer, especially an aqueous alkali solution, (b) exposure. It can be carried out by spraying the substrate afterwards with a spray or the like, and if necessary, rubbing with a rotating brush or a wet sponge or irradiating with ultrasonic waves for the purpose of enhancing the solubility.

As the alkaline aqueous solution, a dilute aqueous solution of an alkaline substance is preferable, and a solution obtained by adding a small amount of a water-miscible organic solvent can also be suitably used. As the alkaline substance, sodium hydroxide,
Alkali metal hydroxides such as 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 such as sodium silicate and potassium silicate Alkali metal metasilicates such as silicates, sodium metasilicate, potassium metasilicate, etc., triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, trisodium phosphate, etc. Is mentioned.

The concentration of the alkaline substance in the alkaline aqueous solution is preferably 0.01 to 30% by mass,
Is preferably 8 to 14.

As the water-miscible organic solvent,
Methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone,
γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone and the like can be mentioned. The amount of the organic solvent added is preferably 0.1 to 30% by mass.

Various known surfactants may be added to the alkaline aqueous solution. The concentration of the surfactant is preferably 0.01 to 10% by mass. The temperature during development is usually preferably around room temperature to 40 ° C. Furthermore, a step of washing with water may be added after the development processing. After the development processing, 200 to 260 is further added.
Bake at ℃.

In this way, the resin layer having the uneven portion on the surface is formed on the substrate. Next, a light-reflecting functional material layer is formed on this uneven portion. As the light reflection functional material,
The material is not particularly limited as long as it has light reflectivity, but a metal material such as Al or Ag is suitable from the viewpoint of forming the reflective electrode. The formation of such a metal film can be performed by a sputtering method or the like. The reflection plate can be preferably used as one reflection electrode of a liquid crystal display device.

<Liquid Crystal Display Device and Manufacturing Method Thereof> In the liquid crystal display device of the present invention, at least a part of the first substrate having a light reflecting function is formed on the surface facing the second substrate. And a second substrate facing the first substrate, and a liquid crystal layer sealed between the first and second substrates, the first substrate and the first electrode. In between, a resin layer having an uneven portion on the surface formed in a process including transfer using the transfer material for forming a reflection plate of the present invention is provided. The first and second electrodes may each be formed in a matrix. Further, the first electrode may be patterned for each pixel, and the second electrode may be formed in a solid shape.

The resin layer has an uneven portion formed on the surface by using the transfer material for forming a reflection plate of the present invention by a process including transfer, and the uneven portion has a continuous wavy shape. It is preferable to have it because good reflection characteristics can be obtained over a wide area. The uneven portion is
Diameter 0.7-30 μm (circle or ellipse), height 0.1
A large number of 1.5 μm convex portions or concave and convex portions are formed. The appropriate range of this shape differs depending on the application of the liquid crystal display device. In the case of complete personal use, it is preferable that the uneven portion having a diameter of 5 μm and a height of 0.5 μm is spread over about 70% of the pixel area. Further, the unevenness may be an elliptical shape as well as a substantially circular shape or a circular shape. Further, these diameters are randomly changed and arranged to prevent the occurrence of moire. In addition, the irregularities may be in the shape of a cone or a pyramid.

It is preferable to use a TFT active matrix substrate as the substrate having the switching element. As the TFT active matrix substrate, a commonly used TFT active matrix substrate can be used without limitation. For example, a gate signal line and an additional capacitance electrode are formed on an active matrix substrate (array substrate), a gate insulating film is formed thereon, and then a semiconductor layer and a channel protective layer are formed, and further, a source and a drain of a TFT are formed. Then, a metal layer and an ITO film are formed by a sputtering method, and these are patterned to form a drain signal line and a source signal line.

It is preferable that the TFT (thin film transistor) active matrix layer is formed of amorphous silicon, a low temperature polysilicon base material, or a continuous grain silicon base material.

The method of manufacturing a liquid crystal display device according to the present invention comprises a first substrate having a first electrode having a light reflecting function, at least a part of which is formed on a surface facing the second substrate, and the first substrate.
In the method of manufacturing a liquid crystal display device, the method further includes: a second substrate disposed to face the first substrate; and a liquid crystal layer sealed between the first and second substrates. The resin material for forming a reflection plate of the present invention is used between the electrode and the electrode to form a resin layer having an uneven portion on the surface in a process including transfer. Further, specifically, first, a plurality of wirings are provided on an insulating substrate made of glass, and after performing a surface treatment or the like, an insulating film, a semiconductor film, etc. are formed to form switching elements in an array. .

Next, the reflection plate-forming transfer material of the present invention is transferred so as to cover almost the entire surface of the substrate on which the switching elements are formed. This transfer is performed by a laminator, and if necessary, the surface of the substrate is subjected to pretreatment such as silane coupling. Then, after exposure using a predetermined exposure mask, development is performed with a developing solution such as a TMAH aqueous solution to remove the resin layer in the contact holes and alignment mark portions. At this stage, the surface of the resin layer is uneven. The exposure performed here is 20 mJ /
cm ² is sufficient, the exposure time is sufficiently shorter than 30 seconds, and the tact time of the manufacturing line can be set to about 1 minute or less, about 30. After this is further cured by post exposure and / or post bake, a reflective layer made of Al and / or Ag or the like is formed thereon. At this time, it is connected to the switching element through the contact hole. Further, the reflective layer is pattern-etched to form a reflective electrode that is independent for each pixel and is connected to the switching element for each pixel. An alignment film is formed on this, and rubbing treatment or the like is performed.

On the other substrate, a color filter is formed in a portion facing the reflection electrode (a black matrix is formed if necessary), ITO (Indium Tin).
Oxide) is formed on the transparent electrode. The two substrates are laminated so that the reflective electrode and the color filter are opposed to each other, and liquid crystal is injected between them to manufacture a reflective liquid crystal display device.

As the liquid crystal display device, a color filter on array (COA) other than the above-mentioned one is used.
Those having either or both of the structure and the semi-transmissive structure can be preferably used.

The COA structure is described in, for example, Japanese Patent Laid-Open No. 10-
As described in JP-A-206888 and the like, a color filter-integrated drive substrate in which a color filter is directly formed on the drive side substrate and a counter substrate provided with a counter electrode (conductive layer) are opposed to each other with a spacer interposed therebetween. It is configured by arranging and arranging a liquid crystal material in the gap portion, and by forming a color filter on the reflective electrode, it is possible to widen the bonding margin at the time of high definition and improve the yield and the aperture ratio. it can.

The semi-transmissive structure is a type of reflective liquid crystal display device having both the function of reflecting light from the front for display and the function of transmitting light from the back for display. "Half mirror type" configured so that light from the back surface can also be transmitted by a method such as thinning the reflection layer provided for reflecting light, and a region that reflects light within one pixel , "In-pixel division type" that also has a region that transmits light.

The half mirror type is described in, for example, Japanese Patent Laid-Open No.
No. 01-100197 and the like. Although the structure is simple, the transmitted color of the backlight is transmitted through the color filter for reflection, which has a low optical density, so the displayed color is pale.

The "in-pixel division type" is described in, for example, Japanese Patent Laid-Open No. 2001-174797, as shown in FIG. The color filter corresponding to the pixel portion having the reflection function is used as the reflection color filter having low optical density, and the color filter corresponding to the pixel portion having the transmission function is used as the transmission color filter having high optical density. As a result, good color reproducibility can be obtained in both the reflective type and the transmissive type. In FIG. 1, 30 is a photosensitive resin layer and 31 is a substrate. Further, in the "divided type within a pixel", insulation on the TFT substrate side is performed so that the liquid crystal layer corresponding to the pixel portion having the reflection function is thin and the liquid crystal layer corresponding to the pixel portion having the transmission function is thick. By setting the thickness of the film, the thickness of the color filter, the thickness of the overcoat, and the like, good contrast can be obtained in both reflection and transmission.

[0148]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

[Example 1] -Preparation of transfer resin film- A polyethylene terephthalate film temporary support having a thickness of 75 µm (undercoat layer-provided product) was coated with a deformation layer coating solution having the following formulation H1 to give a dry film thickness of 14 µm. Of the deformed layer was formed.

[0150] <Deformation layer coating liquid formulation H1:> ・ Methyl methacrylate / 2-ethylhexyl acrylate / benzyl   Methacrylate / methacrylic acid copolymer (copolymerization composition ratio (molar ratio) =   55/30/10/5, mass average molecular weight = 100,000, Tg≈70 ° C.)                                                                 7 parts by mass Styrene / acrylic acid copolymer (copolymerization composition ratio (molar ratio) = 65/35,   Mass average molecular weight = 10,000, Tg≈100 ° C.) 7 parts by mass ・ 2 equivalents of octaethylene glycol monomethacrylate are removed from bisphenol A. Water-condensed compound (Shin Nakamura Chemical Co., Ltd. BPE-500) 7 parts by mass -Photopolymerization initiator IRG184 (CAS947-19-3) 10 parts by mass ・ Methyl ethyl ketone 50 parts by mass

The deformed layer was embossed by the following method to form an uneven portion, and then irradiated with ultraviolet rays from an ultra-high pressure mercury lamp to fix the shape of the deformed layer. <Embossing method> When the deformation layer is applied and dried, the embossing roller [surface 1 cm
1.5 million protrusions per ² (bottom diameter 8-15 μm,
A partial spherical mold having a height of 0.98 μm) is provided, the embossing roller is temperature-controlled at 100 ° C., and the deforming layer is pressed with a force of a linear pressure of 5 t / m to make the surface of the deforming layer uneven. The part was molded.

Next, a photosensitive resin layer solution C1 having the following formulation was applied onto the deformable layer and dried to obtain a dry film thickness of 3.3 μm.
m photosensitive resin layer was provided and covered with a protective film to prepare a transfer resin film 1. The surface of this transfer resin film is smooth, but after transfer and development (described later), the surface was observed by SEM to find 1.5 million protrusions per 1 cm ² of the surface (bottom diameter 8 to 15 μm, height 0.98 μm). Partial spherical type) was formed.

[0153] <Photosensitive resin layer solution formulation: C1> ・ Polymer solution 240 parts by mass   Styrene / maleic acid copolymer benzylamine modified product = 68/32 (molar ratio) ・ Dipentaerythritol hexaacrylate 200 parts by mass ・ Cyclohexanone 730 parts by mass -Photopolymerization initiator IRG184 (CAS947-19-3) 10 parts by mass (Methyl ethyl ketone is added appropriately)

<Substrate cleaning> 320 mm long × 400 m wide
The m-th TFT substrate was ultrasonically cleaned in ultrapure water at room temperature for 1 minute, drained by air blow, and then dried.

<Washing of Substrate> After peeling the protective film of the transfer resin film, the temperature is 130 ° C. and the linear pressure is 100 N /.
cm, and the conveying speed was 3.0 m / min. After peeling off the temporary support, pattern exposure of 20 mJ / cm ² was performed with an ultra-high pressure mercury lamp. The exposure time at this time was 3 seconds.

Then, using a 2.38% TMAH aqueous solution,
Development was carried out at 60 ° C. for 60 seconds to obtain a pattern image in which the contact hole portion, the transparent region and the alignment mark portion were removed.

<Preparation of Reflective Electrode> An Al layer was formed by a sputtering method in order to form a first electrode (referred to as a reflective electrode) having a light reflecting function. At this time, the thickness of the Al layer is 0.5 μm, and the film forming conditions are a substrate temperature of 100 ° C. and Ar.
The pressure was 0.5 Pa and the RF power was 3.4 W / cm ² . Subsequently, the Al layer was patterned into a predetermined shape by photolithography and etching to form a first electrode having a light reflecting function. By reflecting the uneven shape formed on the surface of the photosensitive resin layer in the first electrode having the light reflecting function, a reflective electrode having an uneven portion was obtained.

Next, an alignment film (not shown) made of polyimide was applied on the entire surface of the substrate, baked at 150 ° C. for 2 hours, and then rubbed. Next, as a counter substrate, a counter substrate was prepared in which a color filter and a transparent electrode made of ITO were formed on a glass substrate at a position facing the reflective electrode, and alignment film coating, firing, and rubbing were performed. These two substrates were made to face each other via a spacer so as to have a predetermined cell thickness (not shown), and were bonded together by a seal portion. Subsequently, liquid crystal was injected and sealed between the substrates to manufacture a liquid crystal display device.

[Embodiment 2] In Embodiment 1, the thickness is 75
A polyethylene terephthalate film temporary support having a thickness of μm was embossed in the same manner as in Example 1, and the same photosensitive resin layer solution C1 as in Example 1 was applied onto the temporary support and dried to obtain a dry film thickness. A 3.3 μm photosensitive resin layer was formed and covered with a protective film to prepare a transfer resin film. The surface of this transfer resin film is smooth, but after transfer and development (described later), the surface was observed by SEM to find 1.5 million protrusions per 1 cm ² of the surface (bottom diameter 8 to 15 μm, height 0.98 μm). Partial spherical type) was formed. Next, after peeling off the protective film of the transfer resin film, it was laminated at a temperature of 130 ° C., a linear pressure of 100 N / cm and a conveying speed of 3.0 m / min. After peeling off the temporary support, pattern exposure of 20 mJ / cm ² was performed with an ultra-high pressure mercury lamp. The exposure time at this time was 3 seconds. A liquid crystal display device was assembled in the same manner.

Example 3 In Example 1, a 25 μm thick single-gloss aluminum foil was used as a temporary support, and the same photosensitive resin layer solution C1 as in Example 1 was used on the rough surface side of the single-gloss aluminum foil. Coated and dried to a dry film thickness of 3.3μ
m photosensitive resin layer is formed and covered with a protective film,
A transfer resin film was prepared. Although the surface of this transfer resin film was smooth, irregular surface irregularities were formed on the surface after transfer and development (described later) by SEM observation. Next, after peeling off the protective film of the transfer resin film, it was laminated at a temperature of 130 ° C., a linear pressure of 100 N / cm and a conveying speed of 3.0 m / min. After peeling off the temporary support, pattern exposure of 20 mJ / cm ² was performed with an ultra-high pressure mercury lamp. The exposure time at this time was 3 seconds. A liquid crystal display device was assembled in the same manner.

[Comparative Example 1] A liquid crystal display was prepared in the same manner as in Example 1 except that the resin layer having an uneven portion formed on the TFT substrate was formed as follows based on the description of Japanese Patent Application Laid-Open No. 11-153804. The device was made.

A photo-curable resin containing a photo-polymerizable oligomer, a photo-polymerizable monomer and a photo-polymerization initiator as main components was applied to the entire surface of the substrate. Pentaerythritol, which is an ester acrylate, was used as the photopolymerizable oligomer, and neopentyl glycol diacrylate was used as the photopolymerizable monomer. To this, 2% by mass of a photopolymerization initiator was added. This was applied to the entire surface of the substrate so as to have a film thickness of 3 μm. The convex portions were formed using a semi-transmissive mask in which the light transmittance of the transparent portion of the exposure mask was partially changed. The irradiation energy at this time is 1200 m
It was ^{J / cm 2 ~1500mJ / cm 2} . On this occasion,
The exposure time required 240 seconds.

Comparing Examples 1 to 3 with Comparative Example 1,
In Examples 1 to 3, the exposure time for forming the uneven portion is 3
It is obvious that the comparative example 1 takes 240 seconds, the tact time of the production line is as long as 3 minutes or more, and the productivity is inferior.

[0164]

According to the present invention, it is possible to solve the above-mentioned problems and to provide a reflective electrode having a good reflective property by a simple process, particularly in OA equipment, personal computers, portable information terminals and the like. Among the liquid crystal display devices used, it is possible to efficiently and inexpensively manufacture a reflective liquid crystal display device that utilizes room lighting or external light such as sunlight.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing an intra-pixel split type transflective LCD.

[Explanation of symbols]

30 Photosensitive resin layer 31 substrate 32 reflector

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI theme coat (reference) G02F 1/1343 G02F 1/1343 F term (reference) 2H042 BA03 BA12 BA20 DA02 DA04 DA11 DA21 DA22 2H091 FA16Y FB04 FD06 FD23 GA02 GA03 LA16 2H092 GA13 GA19 HA04 HA05 HA28 NA01 PA12 4F100 AB10A AB33A AK01B AK25 AK42 AR00C AT00A BA02 BA03 BA07 BA10B CA30 EH46 EH66 EJ15 EJ19 EJ54 EJ86 GB04 A04 PC04 A04 PC04 A04A04A04A04A04A02

Claims (15)

[Claims] 1. A temporary support, on which at least one deformation layer and at least one resin layer are provided in this order,
The surface of the deformable layer on the resin layer side (1) has a depth or a protrusion height of 2% or more and 200% or less of the resin layer thickness, and has a size in the plane direction of 1 to 15 μm, Irregularly arranged uneven portions, and (2) 2% or more of the resin layer thickness 2
A reflection plate-forming transfer material, characterized in that any one of uneven portions having a depth or a protrusion height of 00% or less and a size in the surface direction of 1 to 5 μm is provided by embossing. 2. At least one resin layer is provided on a temporary support, and the surface of the temporary support on the side of the resin layer comprises:
(1) An irregularly arranged uneven portion having a depth or a protruding height of 2% or more and 200% or less of the resin layer thickness, a size in the plane direction of 1 to 15 μm, and (2) ) A concave or convex portion having a depth or a protrusion height of 2% or more and 200% or less of the resin layer thickness and having a surface direction size of 1 to 5 μm is provided by embossing. A transfer material for forming a reflector. 3. A temporary support having at least one resin layer provided thereon, and as the temporary support, at least the surface of the temporary support on the resin layer side is 2% or more of the thickness of the resin layer 20.
A transfer material for forming a reflection plate, which is made of a material having an uneven portion having a depth or a protruding height of 0% or less. 4. The transfer material for forming a reflection plate according to claim 3, wherein the temporary support material is a single-gloss aluminum foil. 5. The transfer material for forming a reflection plate according to claim 1, wherein the resin layer is an alkali-soluble photosensitive resin layer. 6. The transfer material for forming a reflection plate according to claim 1, wherein the resin layer is a photosensitive resin layer containing no alkali-soluble colorant. 7. A temporary support, on which at least one deformation layer and at least one resin layer are provided in this order,
The surface of the deformable layer on the resin layer side (1) has a depth or a protrusion height of 2% or more and 200% or less of the resin layer thickness, and has a size in the plane direction of 1 to 15 μm, Irregularly arranged uneven portions, and (2) 2% or more of the resin layer thickness 2
A method for producing a transfer material for forming a reflection plate, characterized in that any one of the uneven portions having a depth or a protruding height of 00% or less and a size in the surface direction of 1 to 5 μm is provided by embossing. . 8. A resin layer of at least one layer is provided on a temporary support, and the surface of the temporary support on the side of the resin layer comprises:
(1) An irregularly arranged uneven portion having a depth or a protruding height of 2% or more and 200% or less of the resin layer thickness, a size in the plane direction of 1 to 15 μm, and (2) ) It is characterized in that any one of the concavo-convex portions having a depth or a protrusion height of 2% or more and 200% or less of the resin layer thickness and a size in the plane direction of 1 to 5 μm is provided by embossing. A method for manufacturing a transfer material for forming a reflector. 9. The reflection plate-forming transfer material according to claim 1, which is transferred onto a substrate, exposed, and developed.
A reflector comprising a resin layer having an uneven surface on which a light-reflecting functional material layer is formed by baking. 10. A liquid crystal display device using the reflection plate according to claim 9 as one reflection electrode. 11. A first electrode having a light reflecting function is a second electrode.
A first substrate formed at least partially on a surface facing the first substrate, a second substrate facing the first substrate, and a first substrate and a second substrate. A liquid crystal display device including a liquid crystal layer that includes a transfer process, the process including transfer between the first substrate and the first electrode using the transfer material for forming a reflection plate according to claim 1. A liquid crystal display device comprising a resin layer having irregularities on the surface formed by. 12. The liquid crystal display device according to claim 11, wherein the liquid crystal display device has a color filter on array (COA) structure. 13. The liquid crystal display device according to claim 11, wherein the liquid crystal display device has a semi-transmissive structure. 14. The liquid crystal display device according to claim 11, wherein the liquid crystal display device has a color filter on array (COA) structure and a transflective structure. 15. The first electrode having a light reflecting function is the second electrode.
A first substrate formed at least partially on a surface facing the first substrate, a second substrate facing the first substrate, and a first substrate and a second substrate. In a method for manufacturing a liquid crystal display device including a liquid crystal layer, a transfer material for forming a reflection plate according to any one of claims 1 to 6 is used between the first substrate and the first electrode. A method of manufacturing a liquid crystal display device, comprising forming a resin layer having irregularities on a surface in a step including