JP2003248109A - Transfer material for reflection plate formation, its manufacturing method, reflection plate, as well as liquid crystal display device and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid crystal display device excellent reflection characteristics in a simple process, and its manufacturing method, a transfer material for reflection plate formation used therefor, and its manufacturing method. <P>SOLUTION: In the transfer material for the reflection plate formation and its manufacturing method, at least one layer of applied layers and an alkali-soluble photosensitive resin layer are provided on a temporary support in this order. At least, one layer of the applied layers contains beads, and an interface of the temporary support side of the photosensitive resin layer is unevenly formed. The liquid crystal display device and its manufacturing method are provided with a first substrate in which a first electrode having a light reflection function is at least partially formed on a face opposite to a second substrate, the second substrate opposite to the first substrate, a liquid crystal layer sealed between the first and the second substrates, and a resin layer having unevenness on a surface formed in a process including transfer by using the transfer material for the reflection plate formation between the first substrate and the first electrode. <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 relates to a transfer material for forming a reflector and a method for manufacturing the same, a reflector manufactured from this transfer material, and a liquid crystal display device having a reflective electrode having good reflection characteristics by a simple process, and a method for manufacturing the same. 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 coating layer and an alkali-soluble photosensitive resin layer are provided in this order on a temporary support, and at least one coating layer contains beads, The transfer material for forming a reflection plate is characterized in that an interface of the resin layer on the temporary support side is formed to be uneven. <2> At least one thermoplastic resin layer, at least one intermediate layer, and an alkali-soluble photosensitive resin layer are provided in this order on a temporary support, and the thermoplastic resin layer and / or The transfer material for forming a reflection plate is characterized in that the intermediate layer contains beads, and the interface of the photosensitive resin layer on the temporary support side is formed to be uneven. <3> At least one coating layer and an alkali-soluble photosensitive resin layer are provided in this order on a temporary support, and the photosensitive resin layer contains beads, and the photosensitive resin layer contains It is a transfer material for forming a reflection plate, characterized in that the interface on the temporary support side is formed to be uneven. <4> At least one thermoplastic resin layer, at least one intermediate layer, and an alkali-soluble photosensitive resin layer are provided in this order on a temporary support, and the photosensitive resin layer comprises beads. It is a transfer material for forming a reflection plate, characterized in that the interface of the photosensitive resin layer on the side of the temporary support is unevenly formed. <5> The transfer material for forming a reflection plate according to any one of <1> to <4>, wherein the alkali-soluble photosensitive resin layer does not contain a colorant. <6> In a method for producing a transfer material for forming a reflection plate, which comprises at least one coating layer and an alkali-soluble photosensitive resin layer provided in this order on a temporary support, at least one coating layer is provided. Forming a reflection plate, characterized in that the coating layer is coated and dried by containing beads, and the photosensitive resin layer is coated to form irregularities on the interface of the photosensitive resin layer on the temporary support side. It is a method of manufacturing a transfer material for use. <7> In the method for producing a transfer material for forming a reflection plate, which comprises at least one coating layer and an alkali-soluble photosensitive resin layer provided in this order on a temporary support, beads are added to the photosensitive resin layer. After forming and coating the photosensitive resin layer, the beads are removed with a developing solution to form irregularities on the interface of the photosensitive resin layer on the temporary support side, thereby forming a reflection plate. It is a method of manufacturing a transfer material for use. <8> The method for producing a transfer material for forming a reflection plate according to <7>, wherein the beads contained in the photosensitive resin layer are alkali developable, or alkali developable and polymerization-inhibitory. <9> The above <6> in which the photosensitive resin layer does not contain a colorant.
The method for producing a transfer material for forming a reflection plate according to any one of <1> to <8>. <10> The reflection plate-forming transfer material according to any one of <1> to <5> is transferred onto a substrate, exposed, developed, and baked to form a resin layer having unevenness on the surface. It is a reflector formed by forming a light reflecting functional material layer. <11> A liquid crystal display device using the reflection plate according to <10> as one reflection electrode. <12> 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 unevenness on the surface formed in a process including transfer using the reflection plate-forming transfer material according to any one of <1> to <5>. A characteristic liquid crystal display device. <13> The liquid crystal display device according to <12>, which has a color filter on array (COA) structure. <14> The liquid crystal display device is the liquid crystal display device according to <12>, which has a semi-transmissive structure. <15> The liquid crystal display device according to <12>, which has a color filter on array (COA) structure and a transflective structure. <16> 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. 5> The method for manufacturing a liquid crystal display device, which comprises using the transfer material for forming a reflection plate according to any one of 5> to form a resin layer having irregularities on a surface in a process including transfer.

According to the reflection plate-forming transfer material described in any one of the above items <1> to <5>, beads are contained in any of the coating layer, the intermediate layer, and the photosensitive resin layer, and the photosensitive material is formed. By forming irregularities on the interface of the functional resin layer on the temporary support side, a reflective electrode having good reflective characteristics can be efficiently manufactured by a simple process.

Therefore, according to the present invention, by a simple process, a reflective electrode having good reflective characteristics,
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.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. <Transfer Material for Forming Reflector> In the first embodiment of the transfer material for reflector formation of the present invention, at least one coating layer and an alkali-soluble photosensitive resin layer are provided in this order on a temporary support. The interface of the photosensitive resin layer on the side of the temporary support is unevenly formed. In this case, in order to form irregularities on the photosensitive resin layer, at least one layer of the coating layer or the photosensitive resin layer contains beads. The beads contained in each layer will be described later.

A second aspect of the transfer material for forming a reflection plate of the present invention is to provide at least one thermoplastic resin layer on a temporary support,
At least one intermediate layer and a photosensitive resin layer are provided in this order, and the interface of the photosensitive resin layer on the temporary support side is formed to be uneven. In this case, beads are contained in the thermoplastic resin layer and / or the intermediate layer or the photosensitive resin layer in order to form irregularities in the photosensitive resin layer. The beads contained in each layer will be described later.

FIG. 1 is a schematic cross-sectional view showing an embodiment of the reflection plate forming transfer material. The reflection plate forming transfer material 10 comprises a temporary support 1, a thermoplastic resin layer 2 and an intermediate layer. 3, a photosensitive resin layer 4 is provided in this order, and the intermediate layer 3 contains beads 5. As a result, the unevenness 6 is formed on the interface of the photosensitive resin layer 4 on the temporary support side.
In addition, it is preferable that the photosensitive resin layer does not contain a colorant in order to use it as a base of a reflection plate or a reflection electrode in a liquid crystal cell. However, the photosensitive resin layer may be colored for the purpose of removing stray light.

-Shape and size and number of unevenness-The shape of the bottom surface of the unevenness is not particularly limited, but a square, a rectangle, a circle, an ellipse or the like is preferable. One side (or diameter) when the shape of the bottom surface of the unevenness is square or circular
Is preferably 1 to 100 μm, more preferably 2 to 5
It is about 0 μm. When the shape of the bottom surface of the unevenness is rectangular or elliptical, the short side (or short diameter) is preferably 1 to 10.
It is 0 μm, more preferably about 2 to 50 μm. Note that a rectangle or an ellipse having a short side (minor axis) of 5 μm and a long side (major axis) of 100 μm is closer to a line than a figure, but the present invention includes all such irregularities. . Further, in the present invention, it is preferable to prevent the occurrence of coloring or stripes due to diffraction by randomly arranging the sizes and shapes of the irregularities and arranging them. The number of the irregularities varies depending on the application of the liquid crystal display device, etc., but is 1 to 1000 per pixel, more preferably 10
It is 300. It is desirable that the irregularities are arranged irregularly and have a continuous wave shape from the viewpoint that good reflection characteristics can be obtained. Further, as will be described later, when the reflecting plate-forming transfer material is formed on the reflecting plate, it has a predetermined pitch and PV value.

The irregularities formed on the surface of the photosensitive resin layer are appropriately selected depending on the intended purpose without any restriction.
From the viewpoint of easily and efficiently forming unevenness, unevenness is formed at the interface of the photosensitive resin layer on the temporary support side by the method for producing a transfer material for forming a reflection plate described below.

The reflection plate-forming transfer material comprises at least one coating layer and an alkali-soluble photosensitive resin layer provided in this order on a temporary support, and the coating layer is made of a thermoplastic resin. A layer, an intermediate layer, and the like are included, and further, other layers appropriately selected are included 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 thermoplastic resin layer to such an extent that transfer is not hindered.
It is preferably chemically and thermally stable and flexible. Specifically, Teflon ^(R) , polyethylene terephthalate,
Preferable examples include thin film sheets of polycarbonate, polyethylene, polypropylene and the like, or laminates thereof.

In order to ensure good releasability between the temporary support and the thermoplastic resin, it is preferable that surface treatment such as glow discharge is not performed and an undercoat layer such as gelatin is not provided.

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

—Thermoplastic Resin Layer— The thermoplastic resin layer is provided as the first layer on the temporary support, mainly contains the thermoplastic resin, and may contain other components as necessary. Good. As the thermoplastic resin, alkali development after transfer is possible, or removal processing is possible when the thermoplastic resin overflows into the surrounding and contaminates the substrate to be transferred depending on the transfer conditions at the time of transfer. From the viewpoint of, a resin soluble in an alkaline aqueous solution is preferable. Furthermore, the thermoplastic resin layer also functions as a cushioning material that prevents transfer defects that may occur due to unevenness on the conductive pattern film when transferring onto the conductive film of the substrate that is the transfer target. In view of the above, a resin having sufficient plasticity that can be deformed in accordance with the unevenness at the time of heating and contacting is preferable.

In addition, the transfer material for forming the reflection plate is particularly thermoplastic when it is formed by sequentially laminating a thermoplastic resin layer on the temporary support, an intermediate layer described later, and a photosensitive resin layer. It is desirable to make the adhesive strength between the resin layer and the temporary support smaller than the adhesive strength between the other layers, so that after the transfer, the temporary support can be removed easily and without destruction of the thermoplastic resin layer. Therefore, it is possible to uniformly expose the photosensitive resin layer after removing the temporary support.

From the above points, the thermoplastic resin is alkali-soluble and has a substantial softening point of 80 ° C.
The following resins are preferred. Examples of the thermoplastic resin having a softening point of 80 ° C. or lower include saponified products of ethylene and an acrylic ester copolymer, saponified products of styrene and a (meth) acrylic ester copolymer, vinyltoluene and (meth). Saponified products such as acrylic acid ester copolymers, poly (meth) acrylic acid esters, and saponified products such as (meth) acrylic acid ester copolymers of butyl (meth) acrylate and vinyl acetate, etc. It may be a single substance or a combination of two or more types.

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, it is substantially softened by adding various plasticizers compatible with the organic polymer substance into the organic polymer substance. 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 organic polymer material is used, various polymers, supercooling materials, and adhesion improving agents are used in order to control the adhesive force with a temporary support 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 thermoplastic resin layer may contain beads for the purpose of forming irregularities on the interface of the photosensitive resin layer on the temporary support side. A bead is contained in a thermoplastic resin layer to form a convex portion, and a flat convex portion is formed by applying an intermediate layer on the thermoplastic resin layer, and a photosensitive resin layer is applied on the intermediate layer. As a result, a recess is formed in the photosensitive resin layer. The beads are spherical,
It is preferably alkali-soluble and soluble in a developing solution. The average particle size of the beads is preferably 0.5 to 50 μm, more preferably 1 to 30 μm. When beads are added to the thermoplastic resin layer, it is preferable to use a size larger than the beads added to the intermediate layer.

The beads are described in, for example, (i) "Recent Chemical Industry Special Technology (1975)", Maruzen Co., Ltd., pages 93 to 109, "4. Microcapsule Technology". Microcapsules (particle diameter 0.5 to 50 μm) prepared by a chemical technique, a physicochemical technique, or other methods described in (ii) Particles of 0.5 to 50 μm among the particles described on page 112. Stuff, (ii
i) "Synthetic Resin Emulsion (1978)" Among the emulsions described on pages 1 to 184 issued by Kobunshi Publishing Co., Ltd., those having a particle size of 0.5 to 50 µm, (iv)
"Latest microcapsules-its manufacturing method, properties and applications (19
1987) ”, among the microcapsules described on pages 1 to 75 of Sankyo Publishing Co., Ltd., having a particle diameter of 0.5 to 50 μm.
And (v) "Chemipearl" (polyolefin dispersion) manufactured by Mitsui Chemicals, Inc., and the like. The amount of the beads added is the thermoplastic resin layer composition 10
The amount is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass, relative to 0 parts by mass.

The thermoplastic resin layer is prepared by dissolving the thermoplastic resin and, if necessary, other components in an organic solvent to prepare a coating solution (thermoplastic resin layer coating solution), for example, spin coating. It can be formed by coating or the like on the temporary support by any known 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.

Further, 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.

The thickness of the thermoplastic resin layer is 6 to
100 μm is preferable, and 6 to 50 μm is more preferable.
If the layer thickness is less than 6 μm, the irregularities of 1 μm or more on the conductive film may not be completely absorbed,
On the other hand, when it exceeds 100 μm, developability and manufacturing suitability may be deteriorated.

-Intermediate Layer- The intermediate layer is provided on the photosensitive resin layer, and when the reflection plate-forming transfer material has a thermoplastic resin layer, the photosensitive resin layer and the thermoplastic resin layer. It is provided between and. Since an organic solvent is used in the formation of the photosensitive resin layer and the thermoplastic resin layer, when 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 which 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.

The intermediate layer preferably contains beads for the purpose of forming irregularities on the interface of the photosensitive resin layer on the temporary support side. When beads are included in the intermediate layer to form a convex portion, and the photosensitive resin layer is applied and dried on the intermediate layer, the size of the beads in the thickness direction becomes small and becomes a lens shape, and the concave portion is formed in the photosensitive resin layer. Is formed. The beads are preferably flexible, spherical, alkali-soluble, and soluble in a developing solution. The refractive index of the beads is preferably almost the same as that of the intermediate layer. The average particle size of the beads is preferably 0.5 to 50 μm, more preferably 1 to 30 μm.

As the beads, those similar to the thermoplastic resin layer can be used. The addition amount of the beads is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the intermediate layer composition.

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 thermoplastic resin 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 layer 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.

-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 photopolymerization system. 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 below. 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 monomers, prepolymers, 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 (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid) and an aliphatic polyhydric alcohol compound, an unsaturated carboxylic acid Examples thereof include amides of acids and aliphatic polyvalent amine compounds.

As the ester (monomer) of the unsaturated carboxylic acid and the aliphatic polyhydric alcohol compound, 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 triethylene 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.

Examples of the amide (monomer) of the unsaturated carboxylic acid and the aliphatic polyvalent amine compound include, 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.

Another example is 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 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 preferable. 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 mgKOH / 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 from 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, hexaarylbiimidazole, 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).

[0072]

[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 of different kinds together. 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.

The photosensitive resin layer may contain beads for the purpose of forming irregularities on the interface of the photosensitive resin layer on the temporary support side. As the beads, those similar to the thermoplastic resin layer and the intermediate layer can be used. As a result, convex portions are formed on the photosensitive resin layer.

The beads are preferably alkali-developable, or alkali-developable and polymerization-inhibitory in that the beads can be removed with a developing solution at the time of development to form recesses in the photosensitive resin layer. .

The amount of the beads added is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass, relative to 100 parts by mass of the photosensitive resin layer composition.

-Colorants such as dyes and pigments-When the transfer material for forming a reflector 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, 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 coloring agent such as the dye or pigment added is preferably 0.01 to 30% by mass based on 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 as necessary to prepare a coating solution (coating solution for coating the photosensitive resin layer), and using a known coating method, a temporary support,
It can be formed by coating on a layer including an intermediate layer. The organic solvent is not particularly limited and may be the same as that which can be used for preparing the coating liquid for the thermoplastic resin layer.

The layer thickness of the photosensitive resin layer (portion having no unevenness) is preferably 0.5 to 10 μm, and 1 to 6
μm is more preferable. The thickness of the photosensitive resin layer is 0.
If it is less than 5 μm, pinholes are likely to occur during the application of the coating solution for the photosensitive resin layer, which may lower the production suitability. On the other hand, if it exceeds 10 μm, it may take a long time to remove the unexposed portion during development. It may take time. Further, the volumetric shrinkage rate of the photosensitive resin layer during heat curing (at the time of baking) is 50 to
It is preferably 90%, more preferably 70 to 90%. As a result, it is possible to form a surface shape in which the resin layer finally obtained has a surface roughness (unevenness) effective as a reflection plate.

-Cover Film A cover film is preferably provided on the photosensitive resin layer for the purpose of protecting it from dirt 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.

<Method of Manufacturing Transfer Material for Forming Reflector> In the first embodiment of the method for manufacturing the transfer material for forming reflector, at least one coating layer and an alkali-soluble material are provided on the temporary support. In the method for producing a transfer material for forming a reflection plate comprising a photosensitive resin layer in this order, at least one of the coating layers contains beads, and the coating layer is coated and dried, and then the photosensitive layer is formed. A resin layer is applied to form irregularities on the interface of the photosensitive resin layer on the temporary support side.

In a second embodiment of the method for producing a transfer material for forming a reflector of the present invention, at least one coating layer and an alkali-soluble photosensitive resin layer are provided in this order on a temporary support. In the method for producing a transfer material for forming a reflection plate, the photosensitive resin layer is made to contain beads, the photosensitive resin layer is applied and dried, and then the beads are removed with a developing solution to obtain the photosensitive resin layer. The unevenness is formed on the interface on the temporary support side. In this case, the beads contained in the photosensitive resin layer are preferably alkali developable, or alkali developable and polymerization-inhibiting.

The manufacturing method of the transfer material for forming a reflecting plate according to the first and second aspects of the present invention can be manufactured by a known method except for the above points.

Specifically, first, a coating solution prepared by dissolving a thermoplastic resin in a solvent (coating solution for a thermoplastic resin layer) is applied onto the temporary support and dried to form a thermoplastic resin layer. Then, a coating solution (a coating solution for the intermediate layer) formed by using a solvent that does not dissolve the thermoplastic resin layer is applied on the thermoplastic resin layer, and the intermediate layer is provided by drying, and the intermediate layer is formed on the intermediate layer. It can be formed by dissolving the photosensitive resin composition in a solvent that does not dissolve the intermediate layer, applying a prepared coating solution, and drying the coating solution to form the photosensitive resin layer. Alternatively, a photosensitive resin layer is provided on the cover film, while a thermoplastic resin layer and an intermediate layer are provided on the temporary support, and they are attached so that the intermediate layer and the photosensitive resin layer are in contact with each other. Alternatively, a photosensitive resin layer and an intermediate layer are provided on the cover film, while a thermoplastic resin layer is provided on the temporary support so that the intermediate layer and the photosensitive resin layer are in contact with each other in the same manner as above. By laminating, the transfer material for forming a reflection plate of the present invention can be manufactured.

As will be described later, in the process in which the transfer material is brought into close contact with the substrate which is the transfer target and the temporary support of the transfer material is peeled off, 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 the composite oxide thereof 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-mentioned 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-based dispersant or a silane-based 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 prepared by dispersing conductive fine particles in a binder and coating it 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 which is opposite to the surface coated with the photosensitive resin layer. In this case, in order to secure sufficient scratch resistance, the conductive layer is formed. 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 a slip property to the hydrophobic polymer layer, a slip 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 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 the side where the thermoplastic resin layer is not provided, the temporary support is provided with the purpose of improving the adhesiveness between the thermoplastic resin layer and the temporary support. For example, surface treatment such as glow discharge treatment, corona treatment, and ultraviolet irradiation treatment, undercoating treatment with 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 formed by transferring the above-mentioned transfer material for forming a reflector to a substrate, exposing it, developing it, and baking it on a resin layer having irregularities on the surface. A light-reflecting functional material is formed on the.

First, the cover film of the reflection plate-forming transfer material is removed, and the photosensitive resin layer is attached to the substrate that 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 thermoplastic resin 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 the photosensitive resin layer of the reflection plate-forming transfer material and the substrate that is the transfer target are bonded together, the temporary support is peeled off at the interface with the thermoplastic resin layer, and the thermoplastic resin layer The photosensitive resin layer is patternwise exposed (patterned) from above through the thermoplastic resin layer and the intermediate layer. The exposure can be performed by irradiation with light having a wavelength of 300 to 500 nm, and examples of the light source include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, and a Hg-Xe lamp.

Further, as the patterning method,
For example, a method by a photolithography method, a method of arranging an exposure mask above the thermoplastic resin layer and exposing in a pattern through the mask, a method of using an exposure means such as a contact type proximity exposure device, and the like can be mentioned. . In 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 4
0 to 150 μm is preferable.

After the exposure, a development process is carried out to remove the thermoplastic resin layer, the alkali-soluble intermediate 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 exposed substrate itself is immersed in a developing bath using a solvent or an aqueous developing solution, especially an alkaline aqueous solution, and (b) exposure. This can be carried out by spraying a 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 to which a small amount of a water-miscible organic solvent is added 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 aqueous alkaline 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 irregularities on the surface is formed on the substrate. Next, a light-reflecting functional material layer is formed on the irregularities. The light reflecting functional material is not particularly limited as long as it has light reflectivity, but a metal material such as Al or Ag is preferable 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. A liquid crystal display device can be formed by using the reflection plate as one reflection electrode.

The unevenness formed on the reflection plate 20 is shown in FIG.
As shown in FIG. 4, irregularly large and small convex portions 10 are formed, or as shown in FIG. 3, it is formed in a wave shape having alternating peaks 11 and valleys 12, or as shown in FIG. As described above, the peaks 11 and the valleys 12 may be alternately formed in a semi-cylindrical shape. In this case, two orthogonal directions (Fig.
4, the pitch (see FIG. 5) of at least one of the irregularities in the XY direction) is preferably 3 to 50 μm, and more preferably 10 to 30 μm. The PV value (see FIG. 5) is preferably 0.1 to 2.0 μm, more preferably 0.2 to 0.8 μm. In addition, the unevenness is measured by using a surface roughness meter and is represented by an average value.

<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 the 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 irregularities 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 unevenness formed on the surface by using the above-mentioned transfer material for forming a reflector of the present invention by a process including transfer, and the unevenness has a continuous wavy shape. It is preferable that good reflection characteristics can be obtained over a wide area. The unevenness has a diameter of 0.7 to 30 μm (circle or ellipse) and a height of 0.1 to 1.5.
A large number of μm convex portions or irregularities are formed. This shape is
The appropriate range varies depending on the application of the liquid crystal display device. For completely personal use, diameter 5 μm, height 0.5 μ
It is preferable that the unevenness of m 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. Also, these diameters are randomly changed and arranged,
Prevent moiré. In addition, the irregularities may be in the shape of a cone or a pyramid.

A TFT active matrix substrate is preferably used 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;
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 above-mentioned transfer material for forming a reflection plate of the present invention is used between an electrode and an electrode to form a resin layer having unevenness 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. .

Then, 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 reflective 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. 6, 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.

[0147]

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 resin film for transfer-A coating solution of the following formulation H1 was applied to a polyethylene terephthalate film temporary support having a thickness of 75 μm to give a dry film thickness of 1
A 4 μm thermoplastic resin layer was formed. <Thermoplastic resin layer 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 / in bisphenol A Compound obtained by dehydration condensation of 2 equivalents of octaethylene glycol monomethacrylate (BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.) 7 parts by mass / methyl ethyl ketone 50 parts by mass

Next, an intermediate layer coating solution P1 having the following composition was applied onto the thermoplastic resin layer and dried at 100 ° C. for 2 minutes to form an intermediate layer having a thickness of 1.6 μm. On this occasion,
Beads were contained in the coating liquid for the intermediate layer, and since the beads were supple, they were flattened during the drying, and irregularities were formed on the surface of the intermediate layer. <Intermediate layer formulation P1:> 100 parts by mass of polyvinyl alcohol (PVA 205 manufactured by Kuraray Co., Ltd., saponification rate = 80%) 50 parts by mass of polyvinylpyrrolidone (PVP manufactured by GAF Corporation, K-90) Resin beads (average) Particle size 5 μm) 20 parts by mass (microcapsules using rapeseed oil as core material and aliphatic isocyanate as wall material) -Distilled water 4000 parts by mass

Next, the following photosensitive resin layer solution C1 was applied and dried to provide a photosensitive resin layer having a dry film thickness of 3.3 μm, which was covered with a protective film to prepare a transfer resin film. The surface of this transfer resin film is smooth, but the surface after transfer and development (described later) was observed by SEM to have a pitch of 10 to 40 μm and a PV value of 0.1 to 0.5 μm.
Unevenness was formed. <Photosensitive resin layer solution 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 (CAS 947-19-3) 10 parts by mass (methyl ethyl ketone is appropriately added)

<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.

<Formation of Resin Layer> After peeling off the protective film of the transfer resin film, the temperature is 130 ° C. and the linear pressure is 100 N.
/ Cm, and the transport 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.

Next, a developer D1 having the following composition was shower-developed at 38 ° C. for 35 seconds to remove the thermoplastic resin layer and the intermediate layer. <Composition of developer D1> -Ultrapure water 97 parts by mass-Triethanolamine 3 parts by mass (alkali metal concentration 50 ppb)

Subsequently, with a developer D2 having the following composition, 33
Shower development was performed at 26 ° C. for 26 seconds, the photosensitive resin layer was developed, and a pattern image was obtained in which contact hole portions (holes for connecting an Al layer and a TFT described below) and transparent portions were removed. <Developer D2> -monoethanolamine 0.2 mole / L-acetic acid 0.1 mole / L-dipolyoxyethylene alkylamine 1 mass% (alkali metal concentration 50 ppb)

Next, in order to form a first electrode having a light reflecting function, an Al layer was formed by sputtering. At this time, the film thickness of the Al layer is 0.5 μm, and the film forming conditions are a substrate temperature of 100 ° C., an Ar pressure of 0.5 Pa, and an RF power of 3.4.
It was 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. The first electrode having the light reflecting function reflected the uneven shape formed on the surface of the photosensitive resin layer (C1 layer) to obtain a reflective electrode having unevenness.

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 side substrate, a counter side 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 application of an alignment film, 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.

Example 2 The procedure of Example 1 was repeated except that the resin beads were removed from the intermediate layer formulation P1 and the photosensitive resin layer solution C2 having the following formulation was used instead of the photosensitive resin layer solution C1.
Was applied and dried to form a photosensitive resin layer having a dry film thickness of 3.3 μm in the same manner as in Example 1. A transfer resin film was prepared. The surface of this resin film for transfer is smooth, but the surface after transfer and development was observed by SEM to have a pitch of 10 to 40 μm and a PV value of 0.1 to 0.5 μm.
Unevenness was formed. <Photosensitive resin layer solution C2> -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 Resin beads (average particle size 5 μm) 20 parts by mass (microcapsules using rapeseed oil to which polymerization-inhibited phenothiazine was added as a core material and aliphatic isocyanate as a wall material) ) (Add methyl ethyl ketone as appropriate)

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. Then, a liquid crystal display device was assembled in the same manner as in Example 1.

[Comparative Example 1] A liquid crystal display device was prepared in the same manner as in Example 1 except that the resin layer having irregularities to be formed on the TFT substrate was formed as follows based on the description of JP-A-11-153804. Was produced.

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 and 2 with Comparative Example 1,
In Examples 1 and 2, the exposure time for forming unevenness is 3 seconds, whereas in Comparative Example 1, it takes 240 seconds, and the tact time of the manufacturing line is as long as 3 minutes or more, resulting in poor productivity. It is clear.

[0162]

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 a transfer material for forming a reflection plate according to an example of the present invention.

FIG. 2 is a schematic diagram showing an example of unevenness.

FIG. 3 is a schematic view showing an example of unevenness.

FIG. 4 is a schematic view showing an example of unevenness.

FIG. 5 is an explanatory diagram showing a pitch of unevenness and a PV value.

FIG. 6 is a schematic cross-sectional view showing an intra-pixel division type transflective LCD.

[Explanation of symbols]

1 temporary support 2 Thermoplastic resin layer 3 Middle class 4 Photosensitive resin layer 5 beads 6 unevenness 10 Transfer material for reflector formation

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H042 AA02 AA04 AA26 BA02 BA03                       BA12 BA15 BA20 DA11 DA17                       DA21 DA22                 2H091 FA02Y FA16Y FB02 FB11                       FC10 FC23 FC26 FD17 GA01                       GA02 GA13 LA12

Claims (16)

[Claims] 1. A temporary support, on which at least one coating layer and an alkali-soluble photosensitive resin layer are provided in this order, and at least one coating layer contains beads, A reflection plate-forming transfer material, characterized in that an interface of the resin layer on the side of the temporary support is formed to be uneven. 2. A temporary support, on which at least one thermoplastic resin layer, at least one intermediate layer, and an alkali-soluble photosensitive resin layer are provided in this order, and the thermoplastic resin layer and / Or the intermediate layer contains beads, and the interface of the photosensitive resin layer on the temporary support side is formed to be uneven, and a transfer material for forming a reflection plate. 3. A temporary support, on which at least one coating layer and an alkali-soluble photosensitive resin layer are provided in this order, the photosensitive resin layer containing beads, and the photosensitive resin layer. 2. The transfer material for forming a reflection plate, wherein the interface on the side of the temporary support is formed to be uneven. 4. A temporary support, on which at least one thermoplastic resin layer, at least one intermediate layer, and an alkali-soluble photosensitive resin layer are provided in this order, and the photosensitive resin layer is A transfer material for forming a reflection plate, which comprises beads, and the interface of the photosensitive resin layer on the side of the temporary support is unevenly formed. 5. The transfer material for forming a reflection plate according to claim 1, wherein the alkali-soluble photosensitive resin layer does not contain a coloring agent. 6. A method of manufacturing a transfer material for forming a reflection plate, comprising a temporary support and at least one coating layer and an alkali-soluble photosensitive resin layer provided in this order on the temporary support. Reflection characterized by containing beads in a layer, coating and drying the coating layer, and then coating the photosensitive resin layer to form irregularities on the interface of the photosensitive resin layer on the temporary support side. A method of manufacturing a transfer material for plate formation. 7. A method of manufacturing a transfer material for forming a reflection plate, comprising a temporary support and at least one coating layer and an alkali-soluble photosensitive resin layer, which are provided in this order on the temporary resin. After the beads are contained and the photosensitive resin layer is applied and dried, the beads are removed with a developer,
A method for producing a transfer material for forming a reflection plate, comprising forming irregularities on an interface of the photosensitive resin layer on the temporary support side. 8. The method for producing a transfer material for forming a reflection plate according to claim 7, wherein the beads contained in the photosensitive resin layer are alkali developable, or alkali developable and polymerization inhibiting. 9. The method for producing a transfer material for forming a reflection plate according to claim 6, wherein the photosensitive resin layer does not contain a coloring agent. 10. The light-transmitting light on a resin layer having unevenness on the surface formed by transferring the reflection plate-forming transfer material according to claim 1 onto a substrate, exposing, developing and baking. A reflective plate formed by forming a reflective functional material layer. 11. A liquid crystal display device using the reflection plate according to claim 10 as one reflection electrode. 12. 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. A liquid crystal display device including a liquid crystal layer, wherein the first substrate and the first electrode are provided between the first substrate and the first electrode.
A liquid crystal display device comprising a resin layer having irregularities on a surface formed in a process including transfer using the reflection plate-forming transfer material described in any one of 1. 13. The liquid crystal display device according to claim 12, wherein the liquid crystal display device has a color filter on array (COA) structure. 14. The liquid crystal display device according to claim 12, wherein the liquid crystal display device has a semi-transmissive structure. 15. The liquid crystal display device according to claim 12, wherein the liquid crystal display device has a color filter on array (COA) structure and a transflective structure. 16. 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. 7. A method for manufacturing a liquid crystal display device, comprising: a liquid crystal layer that is provided between the first substrate and the first electrode.
A method for manufacturing a liquid crystal display device, which comprises forming the resin layer having unevenness on the surface in a step including transfer using the transfer material for forming a reflection plate described in any one of 1.