JPH09258202A - Production of spatial optical modulator and spatial optical modulator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to form a light shielding layer which is adequate for mass production and has good uniformity of film thickness and high light shieldability with a simple manufacturing process without requiring the utilization of a costly device. SOLUTION: The spatial optical modulator having a structure in which a laminated structural body having a photoconductive layer, light shielding layer, light reflection layer and liquid crystal layer in this order, is held by two sheets of transparent substrates provided with transparent electrodes on the inner side is produced. At this time, the precursor light shielding layer contg. a compsn. which is a photosensitive resin compsn. having an alkaline-soluble binder, photopolynm. initiator, addition polymerizable monomer contg. ethylenic unsatd. double bonds and 92 kinds of coloring agents, is substantially black in hue, and is :2 in the transmittability of visible light regions and is 1:1 to 20:1 in the ratio of the transmittability between the visible light regions and UV regions when the compsn. of 1 to 3μm thickness is formed is formed to a sheet form. This precursor light shielding layer is brought into contact with the layer which is the adjacent layer in the spatial optical modulator and, further, the precursor light shielding layer is stuck to the adjacent layer by heat, by which the light shielding layer is obtd.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for manufacturing a spatial light modulator and a spatial light modulator.

[0002]

2. Description of the Related Art A spatial light modulator is basically a laminated structure in which a photoconductive layer, a light reflecting layer, and a liquid crystal layer are sequentially arranged between two transparent substrates having transparent electrodes attached to the inside thereof. However, it has a sandwiched structure.

Such a spatial light modulator has the following functions. When voltage is applied between the transparent electrodes and light is irradiated in a pattern from the writing side (transparent substrate side near the photoconductive layer), the resistance of the photoconductive layer decreases at the light irradiation part, and A predetermined voltage is applied to the liquid crystal layer in the adjacent portion via the. Then, the liquid crystal layer in that portion exerts an optical effect such as a birefringence effect. In that state, when reading light is irradiated from the reading side (the side opposite to the writing side),
The light passes through the liquid crystal layer where the optical effect is exerted, is reflected by the light reflection layer, passes through the liquid crystal layer, and is emitted from the spatial light modulator. The light is optically modulated by the optical effect of the liquid crystal. That is, the modulated light is affected by the writing light and recognizes the pattern of the writing light.

Since the reading light is not completely reflected by the light reflecting layer, a light shielding layer is provided between the photoconductive layer and the light reflecting layer so that a part of the reading light does not enter the highly sensitive photoconductive layer. Things are also common.

As the light-shielding layer, many materials and manufacturing methods are known. Typical methods will be described below.

Japanese Unexamined Patent Publication No. 7-5488 discloses a method of forming a light-shielding layer from manganese oxide and silicon dioxide by sputtering or vacuum deposition (method 1).

Japanese Unexamined Patent Publication No. 6-283731 discloses a method of forming an amorphous light-shielding layer composed of Si, Ge, and C by plasma CVD using monosilane, germanium hydride, and ethylene as raw materials (method 2). ).

Japanese Unexamined Patent Publication (Kokai) No. 6-51341 discloses a method of forming a light-shielding layer of diamond-like carbon by plasma CVD using methane gas as a raw material (method 3).

In Japanese Patent Laid-Open No. 4-346315, a light-shielding layer is formed by applying a paint in which an organic or inorganic pigment is dispersed in an acrylic resin, a resin such as polyimide, polyamide, or an epoxy resin using a spinner. A method is disclosed (method 4).

[0010]

However, the above-mentioned methods 1 to
In the method of forming the light-shielding layer using the vacuum film forming process represented by No. 3, an expensive device must be used,
In addition, the manufacturing process is complicated, and there is a drawback that it is not suitable for mass production.

On the other hand, the method utilizing the conventional non-vacuum film forming process represented by the method 4 has the drawbacks that the film thickness becomes nonuniform and the light-shielding property is not always sufficiently obtained.

Thus, the present invention does not require the use of an expensive device, has a simple manufacturing process, is suitable for mass production, and has a good film thickness uniformity and a high light-shielding property. An object of the present invention is to provide a method for manufacturing a spatial light modulator and a spatial light modulator that can form layers.

[0013]

The invention according to claim 1 has a photoconductive layer, a light-shielding layer, a light-reflecting layer, and a liquid crystal layer, and two laminated structures are arranged in this order with respect to these layers. With the transparent substrate with the transparent electrode inside,
In a method of manufacturing a spatial light modulator having a sandwiching structure,
The formation of the light-shielding layer comprises (A) an alkali-soluble binder, a photopolymerization initiator, an addition-polymerizable monomer having an ethylenically unsaturated double bond, and at least two kinds of colorants, the light-shielding photosensitive property. Resin composition having a hue equal to or close to black and a film thickness of 1 to 3 μm
When the light-shielding photosensitive resin composition is formed, the transmittance in the visible light region is 2 or less, and the ratio of the transmittance in the visible light region to the transmittance in the ultraviolet light region is 1: 1 to 20: 1. A step of forming a precursory light-shielding layer (light-shielding layer before exposure and curing) containing a light-shielding photosensitive resin composition in a sheet shape in advance, and (B) the precursory light-shielding layer in an adjacent space (mainly in the spatial light modulator). , A step of contacting with a layer to be a photoconductive layer), and (C) a step of laminating the precursor light shielding layer to an adjacent layer by heat.
(D) exposing the precursor light-shielding layer to form a light-shielding layer,
It is characterized by having.

The present invention does not use a vacuum process. Moreover, the precursory light-shielding layer serving as the light-shielding layer is formed in advance and is bonded to the adjacent layer by heat, so that the layer has a uniform thickness. Furthermore, due to the above-mentioned specific characteristics of the light-shielding photosensitive resin composition, the light-shielding property is also excellent. This specific feature and the meaning of “hue equal to or close to black” will be described in detail later.

In the invention of claim 2, the step (A) is carried out by applying the light-shielding photosensitive resin composition onto a temporary support, and after the bonding in the step (C), the temporary support is provided. It further has a process of peeling.

By doing so, the precursory light shielding layer can be formed easily and suitable for lamination, which is preferable.

The invention of claim 3 has a photoconductive layer, a light-shielding layer, a light-reflecting layer, and a liquid crystal layer, and these layers are laminated structures arranged in this order by two transparent substrates with transparent electrodes. In the spatial light modulator having a structure in which the transparent electrode is placed inside, the light-shielding layer has an alkali-soluble binder, a photopolymerization initiator, and an addition polymerizable monomer having an ethylenically unsaturated double bond, And two or more colorants,
A light-shielding photosensitive resin composition having at least
Hue equal to or close to black, and film thickness 1
When the light-shielding photosensitive resin composition having a thickness of 3 μm is formed, the transmittance in the visible light region is 2 or less, and the ratio of the transmittance in the visible light region to the transmittance in the ultraviolet region is 1: 1 to 20: 1. It is characterized by containing the exposed composition of the light-shielding photosensitive resin composition.

Such a spatial light modulator can be manufactured by utilizing the above-mentioned excellent manufacturing method, and exhibits an excellent light-shielding property.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to embodiments.

One form of the spatial light modulator of the present invention is schematically shown in FIG. This spatial light modulator 1 includes transparent electrodes 16 and 1
Two transparent glasses 10 and 11 each having 7 inside
And a laminated structure sandwiched therebetween. In the laminated structure, the photoconductive layer 12, the light shielding layer 13, the light reflecting layer 14, and the liquid crystal layer 15 are sequentially arranged from the transparent electrode 16 side.
Their essential functions themselves are similar to those described in the section of the prior art and are well known to those skilled in the art, including the operation of the spatial light modulator. The spatial light modulator 1 includes a power source 18
AC bias is applied from.

Since the spatial light modulator of the present invention as described above is characterized by the composition of the light-shielding layer and the manufacturing method, first, the composition of the light-shielding layer will be described. Any other material, form, or manufacturing method that can be used in the art can be adopted as the other elements, and a typical example will be mentioned later when the manufacturing method of the spatial light modulator of the present invention is described.

In the present invention, the light-shielding layer comprises an alkali-soluble binder, a photopolymerization initiator, an addition-polymerizable monomer having an ethylenically unsaturated double bond, and two or more colorants.
A light-shielding photosensitive resin composition having at least
Hue equal to or close to black, and film thickness 1
When the light-shielding photosensitive resin composition having a thickness of 3 μm is formed, the transmittance in the visible light region is 2 or less, and the ratio of the transmittance in the visible light region to the transmittance in the ultraviolet region is 1: 1 to 20: 1. The composition which has been exposed to the light-shielding photosensitive resin composition (i.e.,
Exposed composition).

As the alkali-soluble binder which is an essential component of the light-shielding layer, a polymer having a carboxylic acid group in its side chain, for example, JP-A-59-44615 and JP-B-54.
-34327, JP-B-58-12577, JP-B-5
4-25957, JP-A-59-53836 and JP-A-59-71048, a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and croton. Examples thereof include acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and the like, and cellulose derivatives having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are also useful. Particularly preferred is a copolymer of benzyl (meth) acrylate and (meth) acrylic acid described in U.S. Pat. No. 4,139,391, or a multicomponent copolymer of benzyl (meth) acrylate, (meth) acrylic acid and other monomers. Can be mentioned. Although the above-mentioned ones are exemplified by water-insoluble binders, examples of water-soluble polymers include polyvinylpyrrolidone, polyethylene oxide, and polyvinyl alcohol. In addition to the above, in order to improve various performances, for example, the strength of a cured film, an alkali-insoluble polymer can be added in a range that does not adversely affect the developability and the like. These polymers include alcohol-soluble nylon or epoxy resin. The solid content of the binder in the light-shielding photosensitive resin composition solid content is 10 to 95% by weight, and more preferably 20 to 90% by weight. If it is less than 10% by weight, the tackiness of the photosensitive resin layer is too high, and if it exceeds 95% by weight, the strength and photosensitivity of the formed image are poor.

The photopolymerization initiator which is another essential component of the light-shielding layer is described in the vicinal polyketaldonyl compound disclosed in US Pat. No. 2,367,660 and the specification of US Pat. No. 2,448,828. Acryloin ether compounds described in US Pat. No. 2,722,512, α-hydrocarbon-substituted aromatic acyloin compounds described in US Pat. Nos. 3,046,127 and 295175.
No. 8, a polynuclear quinone compound, a combination of a triarylimidazole dimer and p-aminoketone described in US Pat. No. 3,549,367, JP-B-51-
Benzothiazole compounds and trihalomethyl-s-triazine compounds described in Japanese Patent No. 48516, US Pat. No. 42.
Trihalomethyl-described in 39850
Examples thereof include s-triazine compounds and trihalomethyloxadiazole compounds described in U.S. Pat. No. 4,212,976. Particularly preferably, trihalomethyl-s-triazine, trihalomethyloxadiazole,
It is a triaryl imidazole dimer. The solid content of the photopolymerization initiator in the photopolymerizable composition is 0.5 to 2
It is 0% by weight, more preferably 1 to 15% by weight.
If it is less than 0.5% by weight, the photosensitivity and the image strength are low, and
Even if it exceeds the weight%, no good cost for performance is observed.

The addition-polymerizable monomer having an ethylenically unsaturated double bond, which is another essential component of the light-shielding layer, has at least one addition-polymerizable ethylenically unsaturated group in the molecule and has a boiling point. It is a compound at 100 ° C or higher under normal pressure. For example, monofunctional acrylates and monofunctional methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate. Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate,
Pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) )ether,
Tri (acryloyloxyethyl) isocyanurate,
After addition reaction of ethylene oxide and propylene oxide to polyfunctional alcohols such as tri (acryloyloxyethyl) cyfurate, glycerin tri (meth) acrylate, trimethylolpropane and glycerin (meth)
Acrylate. Japanese Patent Publication No. 48-41708,
Urethane acrylates described in JP-B No. 50-6034 and JP-A No. 51-37193. Polyester acrylates described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490, and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid. And other polyfunctional acrylates and methacrylates. More preferred are trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate. The solid content of the addition-polymerizable monomer having an ethylenically unsaturated double bond in the light-shielding photosensitive resin composition solid is 5 to 50% by weight.
And more preferably 10 to 40% by weight. 5% by weight
If the amount is less than 50% by weight, the photosensitivity and the image strength are low.

As the two or more kinds of colorants which are other essential components of the light-shielding layer, red, green, blue, yellow, purple, magenta, cyan, black pigments and dyes are used, but preferred pigments are used. The following may be mentioned as examples.

As red, monoazo type, disazo type,
Xanthene-based, anthraquinone-based, perylene-based, perinone-based, quinacridone-based and pyranthrone-based organic or inorganic pigments. Among these, anthraquinone pigments are preferable.

Examples of green include triphenylmethane-based, phthalocyanine-based, nitroso-based, indamine-based, monoazo-based and anthraquinone-based organic or inorganic pigments. Of these, phthalocyanine pigments are preferable.

Blue is a triphenylmethane-based, phthalocyanine-based, anthraquinone-based, triarylmethane-based, disazo-based or indigoid-based organic or inorganic pigment. Of these, phthalocyanine pigments are preferable.

As yellow, monoazo type, disazo type,
Anthraquinone-based, isoindolinone-based, quinophthalone-based, benzimidazolone-based and dioxime-based organic or inorganic pigments are used. Of these, isoindolinone pigments are preferred.

Examples of purple include xanthene-based, triphenylmethane-based, anthraquinone-based, monoazo-based, dioxazine-based, quinacridone-based, indigoid-based and perylene-based organic or inorganic pigments. Of these, dioxazine-based pigments are preferable.

As black, a carbon-based pigment is preferable. Preferred examples of these include carmine 6B
(C.I. 12490), phthalocyanine green (C.I. 74260), phthalocyanine blue (C.I.
I. 74160), Mitsubishi Carbon Black MA-10
0, perylene black (BASF K0084, K00
86), Cyanine Black, # 1201 Rionol Yellow (CI 21090), Rionol Yellow GR
O (CI 21090), Shimla Fast Yellow 8GF (CI 21105), Benzidine Yellow 4T-564D (CI 21095), Shimla Fast Red 4015 (CI 12355), Lionol Red 7B4401. (C.I. 15850), Fastgen Blue TGR-L (C.I. 74160),
Lionol Blue SM (C.I.26150), Mitsubishi Carbon Black MA-100, Mitsubishi Carbon Black #
40, Victoria Pure Blue (C.I. 4259
5), auramine O (CI 41000), carotene brilliant flavin (CI basic 13), rhodamine 6GCP (CI 45160), rhodamine B (CI 45170), safranine OK 70:10.
0 (C.I. 50240), Erioglaucin X (C.I.
I. 42080), first black HB (C.I.
26150), C.I. I. Pigment Red 97, C.I.
I. Pigment Red 122, C.I. I. Pigment
Red 149, C.I. I. Pigment Red 168,
C. I. Pigment Red 177, C.I. I. Pigment Red 180, C.I. I. Pigment Red 19
2, C.I. I. Pigment Red 215, C.I. I. Pigment Green 7, C.I. I. Pigment Green 3
6, 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 22, C.I.
I. Pigment Blue 60, C.I. I. Pigment Blue 64, C.I. I. Pigment Yellow 139, C.I.
I. Pigment Yellow 83, C.I. I. Pigment
Violet 23 etc. can be mentioned. Other than these, metal powder, white pigment, fluorescent pigment, etc. are also used. Two or more kinds of these colorants are mixed and used so that the hue becomes black.

The combination and mixing ratio of these colorants in the light-shielding photosensitive resin composition are such that the light-shielding photosensitive resin composition has a hue equal to, or close to, black and a light-shielding photosensitive resin composition. When the layer thickness is 1 to 3 μm, the transmittance in the visible light region is 2 or less, and the ratio of the transmittance in the visible light region to the transmittance in the ultraviolet light region is 1: 1 to 20: 1. To be selected.

In the present invention, "is hue equal to black,
Alternatively, “near” is defined as an achromatic color point defined by the CIE colorimetric method in a light source (F10 light source or the like) used for a display device such as a liquid crystal display panel being black, and the achromatic color point x, The value of Δx and Δy, which is the difference from the y value, is Δ
It is defined as being in the range of x ≦ 0.1 and Δy ≦ 0.1. If the hue is other than the above, the display contrast of the liquid crystal display panel will be insufficient.

The "transmittance of the light-shielding photosensitive resin composition in the visible light region" in the present invention is represented by the CIE colorimetric method 3.
It is defined by the Y value which is one of the stimulus values, and 0.01 ≦ Y ≦ 2
Is preferably within the range. When the Y value exceeds 2, the light transmittance is too high and the performance as a light shielding layer is insufficient. The transmittance in the ultraviolet light region is 350 n of the light source used during exposure.
It is defined as the transmittance (%) at an emission peak wavelength of m or more and 400 nm or less. When an ultra-high pressure mercury lamp is used as a light source, the transmittance is 365 nm. When an ultra-high pressure mercury lamp is used as a light source, in order to photo-cure to the deep part of the film of the light-shielding layer with high optical density, the ratio of the transmittance in the visible light region and the transmittance in the ultraviolet light region, that is, the ratio of the Y value and the 365 nm transmittance is used. Is 1:
It is essential that it be 1 to 20: 1. The ratio is 2
If it exceeds 0: 1, the light-shielding layer is not sufficiently hardened to the deep portion, and a light-shielding layer having a sufficient film thickness cannot be obtained. Also, this ratio is 1: 1
If it is less than the above range, only a film having an insufficient light-shielding property can be produced in a practical film thickness range.

As a preferable combination of colorants, a combination of a pigment mixture having a red color and a blue color having a complementary color relationship with a pigment mixture having a yellow color and a purple color having a complementary color relationship with each other, or a black pigment added to the above mixture is used. It is the combination which added. It is possible to obtain a light-shielding layer with a Y value of 2 or less by combining the complementary colors of red and blue, but this combination has a large absorption in the ultraviolet region, and the ratio of the Y value and the 365 nm transmittance exceeds 20: 1. Therefore, it is difficult to photo-cure to the deep part of the light shielding layer. In addition, in the case of combining the complementary colors of yellow and purple, the ratio of the Y value and the 365 nm transmittance can be suppressed to 20: 1 or less, but the light shielding layer having the Y value of 2 or less must be provided unless the thickness of the light shielding layer exceeds 3 μm. Can't get

Alternatively, by adding a blue pigment to the combination of the complementary colors of yellow and purple, the Y value is 2 or less,
Moreover, it is possible to obtain a light-shielding layer having a ratio of Y value and 365 nm transmittance of 20: 1 or less. Also in this case, it is possible to reduce the Y value by adding the black pigment in the range where the ratio of the above Y value and the 365 nm transmittance does not exceed 20: 1.

Thus, only by combining the pigments as described above, the Y value is 2 or less and the ratio of the Y value and the 365 nm transmittance is 2 within the range of the light-shielding layer thickness of 1 to 3 μm.
A light shielding layer of 0: 1 or less is obtained. Further, the Y value is reduced without significantly changing the thickness of the light shielding layer (improving the light shielding property).
To do so, use a black pigment such as carbon with the above Y value and 365
It is possible by adding in a range where the ratio of nm transmittance does not exceed 20: 1. The solid content of the colorant in the light-shielding photosensitive resin composition solid is preferably 1 to 50% by weight.

In addition to the above components, it is preferable to add a thermal polymerization inhibitor. Examples thereof include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-).
Butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, phenothiazine and the like.

Further, known additives such as a plasticizer, a surfactant and a solvent can be added to the composition of the present invention as required.

The thickness of the light-shielding layer formed of the light-shielding photosensitive resin composition of the present invention is preferably 1 μm or more and 3 μm or less. If it is less than 1 μm, the pigment concentration in the light-shielding layer becomes high and the developability deteriorates. If it exceeds 3 μm, the developability deteriorates,
Problems such as deterioration of image forming reproducibility occur. The film thickness of the light shielding layer can be arbitrarily set within the above range. Especially when making color filters, it is desirable that the finished color filters have good flatness. Therefore, in this case, set the same thickness as the other colored layers (red, blue, green, etc.). Is desirable.

By using the above light-shielding photosensitive resin composition as a raw material for the light-shielding layer, excellent light-shielding properties are exhibited. The composition must be exposed to light and cured to finally form a light-shielding layer, which will be described later. Next, a method for manufacturing the spatial light modulator of the present invention will be described. In the manufacturing method,
Although the processes are peculiar to the present invention, as described above, typical examples of the other processes are given below.

First, a transparent substrate such as a glass substrate or a transparent plastic substrate is prepared. The thickness is usually 1.8-
It is about 20 mm. Examples of usable glass include alkali glass, non-alkali glass, silica glass, and the like, and more specifically, trade name Tempax, trade name Corning 7059 (manufactured by Corning Incorporated), trade name Neoceram N-0 ( Manufactured by Nippon Electric Glass Co., Ltd., and the like. Examples of transparent plastics that can be used include polycarbonate and the like.

The substrate may be provided with a passivation film such as SiO 2 for the purpose of preventing the alkaline component from being eluted. Further, it is preferable to apply an antireflection coating to the outer surface of the substrate.

Next, a transparent electrode is formed on the transparent substrate. Specifically, SnO ₂ , ITO or the like is subjected to EB vapor deposition or sputter vapor deposition. The thickness is generally determined so that the amount of transmitted light due to light interference becomes maximum at the sensitivity peak wavelength of the photoconductor of the photoconductive layer. Usually, it is 600 to 700 nm.

After that, the transparent electrode is patterned by using photolithography or the like so that a voltage can be applied in a desired manner.

Next, a photoconductive layer is formed on the transparent electrode.
Hydrogenated amorphous silicon, BSO (Bi ₁₂ SiO ₂₀ ), amorphous SeTe, amorphous As ₂ Se ₃ , and amorphous S are used as the photoconductor forming the photoconductive layer.
Examples thereof include resin dispersions of e and ZnO, CdS resin dispersions, organic photoconductors (phthalocyanine-based, bisazo-based pigments, arylamine-based, etc.).

The film forming method and the thickness after the film forming may be selected according to the material. For example, in the case of hydrogenated amorphous silicon, it is formed by plasma CVD to a thickness of preferably 2 to 30 μm, more preferably 5 to 20 μm.

Next, a light shielding layer is formed on the photoconductive layer. The formation includes a step (A) of forming a precursory light shielding layer containing the light shielding photosensitive resin composition in a sheet shape in advance, and the precursory light shielding layer to be an adjacent layer in the spatial light modulator (currently). In the embodiment described, a step (B) of contacting the photoconductive layer), a step (C) of bonding the precursor light shielding layer to the adjacent layer by heat, and a step of exposing the precursor light shielding layer to expose the light shielding layer. This is performed through the forming step (D).

The step (A) may be carried out by any method, but preferably, the light-shielding photosensitive resin composition is first coated on a temporary support to form a precursor light-shielding layer on the temporary support, carry out. In the practice, the light-shielding photosensitive resin composition is applied using a spinner, a whiler, a roller coater, a curtain coater, a knife coater, a wire bar coater, an extruder, etc., and dried to form an unexposed light-shielding photosensitive resin layer. To form a precursor light-shielding layer.

The material of the temporary support is not limited, but, for example,
Polyethylene terephthalate and the like can be preferably used.

In step (B), the precursory light shielding layer is brought into contact with the photoconductive layer. In the step (C), heat is applied to bond (laminate) the precursory light shielding layer to the photoconductive layer. by this,
The film thickness can be made uniform. Further, it is preferable to apply pressure. The heating and pressurizing conditions may be appropriately selected, but the heating is near or above the melting temperature of the light-shielding photosensitive composition. Pressurization is usually 1.0 to 3.0 kg / cm ² .

In a preferred embodiment in which the precursor light-shielding layer is provided on the temporary support, a general-purpose laminator can be used. In this aspect, the temporary support is then peeled off. In short, the precursor light-shielding layer is transferred from the temporary support to the photoconductive layer.

It should be noted that, between the temporary support and the light-shielding layer, or on the light-shielding layer, it is transferred onto the photoconductive layer integrally with the light-shielding layer, and the function of the spatial light modulator is improved or put to practical use. Any layer may be provided to keep it within the range that does not hinder it. Such a layer can have a function of improving the peelability between the temporary support and the light shielding layer.

The thickness of the light shielding layer is preferably 1 to 3 μm. In step (D), the precursor light-shielding layer is exposed to form a light-shielding layer. The light source for exposure may be selected according to the photosensitivity of the composition of the light-shielding layer, such as an ultra-high pressure mercury lamp, a xenon lamp,
Known light sources such as a carbon arc lamp and an argon laser can be used. The step (D) may be performed at any stage of the manufacturing process of the spatial light modulator as long as it can be performed.

The light-shielding layer which can be formed as described above has a high light-shielding property and has a high uniformity of film thickness even in a large area. Also, the adhesion to the photoconductive layer is high. In addition, the resistivity is usually 1
It shows 0 ⁹ to 10 ¹² Ωcm, which is sufficiently large. Its patterning is easy and highly safe.

Then, a light reflecting layer is formed on the light shielding layer.
The light reflecting layer is generally a dielectric multilayer film.
For example, SiO ₂ and TiO _2, reflectivity is deposited by EB vapor deposition alternately with a thickness of 1/4 wavelength increments in wavelength of the light used for the reading light so that the maximum.

Further, on the light reflection layer, a counter transparent substrate with a transparent electrode is attached with a space other than the peripheral portion, and a liquid crystal is introduced into the space, but before that, a state where no electric field is applied is applied. In order to obtain the desired alignment in the liquid crystal, the alignment treatment is applied to both the light reflection layer side and the transparent electrode side.

As the counter transparent substrate with the transparent electrode, the same transparent substrate with the transparent electrode can be used. However, when the transparent substrate is glass, its thickness is usually about 1.1 to 2 mm.

The method and conditions of the alignment treatment differ depending on the operation mode of the liquid crystal. For example, if the operation mode is the pseudo vertical alignment field effect birefringence mode, an organic alignment film of a compound such as polyimide, for example, STN (super-tw
Organic alignment film for isted nematic), product name: 7511L
(Hitachi Chemical Co., Ltd.) is provided and it is rubbed. Alternatively, SiO is obliquely deposited and surface-treated with a silane coupling agent.

The alignment treatment method and conditions on the light reflecting layer side and the transparent electrode side may be the same or different.

The pretilt angle is preferably in the range of 80 ° to 89.5 °. After performing the alignment treatment as described above, a space other than the peripheral portion is provided on the light reflection layer,
Attach the opposing transparent substrate with transparent electrodes. A specific example of the method will be described below. First, an adhesive containing spacers such as spherical silica or resin is formed by screen printing on the periphery of the opposing transparent substrate. At this time, spacers may be scattered on the display portion of the spatial light modulator. The diameter or thickness of the spacer is usually 2 to 8 μm.

Examples of the adhesive include a one- or two-component thermosetting epoxy resin and a one-component ultraviolet curable resin. Next, the transparent substrate on the photoconductive layer side is attached to the opposing transparent substrate with the light reflecting layer side facing inward, and the adhesive is cured.

Normally, in the seal using an adhesive, one hole is formed as a liquid crystal injection port, but one or more holes are present on the side opposite to the hole for venting air. You may do it.

Then, liquid crystal is vacuum-injected into the above-mentioned space from the injection port. After the injection, all pores are sealed.

Liquid crystal materials are typically azomethine, azo, azoxy, ester, biphenyl,
Examples thereof include phenylcyclohexane type and bicyclohexane type. The liquid crystal material to be used may be appropriately selected from any type including these in accordance with the operation mode of the liquid crystal, and for example, if the operation mode of the liquid crystal is the pseudo vertical alignment field effect birefringence mode, A liquid crystal material having a negative Δε is used. Specifically, the product name N-35
(Manufactured by Chisso Corporation) and trade name ZLI-2806, ZLI-
4518 (manufactured by Merck Ltd.) and the like can be preferably used.

The spatial light modulator according to the present invention can be manufactured as described above.

[0068]

EXAMPLES The present invention will be described in more detail with reference to examples. In the following, "part" means "part by weight". Example 1 Production Example First, a transparent glass substrate (trade name: Tempax) having a thickness of 4 mm is prepared. Next, SnO ₂ was added to the glass substrate by E
A transparent electrode was formed by B vapor deposition. The thickness is
750 angstroms.

After that, the transparent electrode was patterned using photolithography well known in the art.

Next, a photoconductive layer was formed on the transparent electrode.
Specifically, hydrogenated amorphous silicon is plasma C
The film was formed by the VD method. The thickness was 10 μm.

Then, a light shielding layer was formed on the photoconductive layer as follows. A 100 μm thick polyethylene terephthalate film temporary support was coated with a coating solution having the following formulation H1 and dried to form a thermoplastic resin layer having a dry film thickness of 20 μm.

Thermoplastic resin layer formulation Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer molar composition ratio = 55 / 28.3 / 11.7 / 4.5, weight average molecular weight = 80000) 15.0 parts BPE-500 (Shin-Nakamura Chemical Co., Ltd. multifunctional acrylate) 7.0 parts F177P (Dainippon Ink and Chemicals fluorinated surfactant) 0.3 parts Methanol 30.0 parts Methyl ethyl ketone 19.0 Part 1-Methoxy-2-propanol 10.0 parts Next, a coating solution having the following formulation B1 was applied onto the thermoplastic resin layer and dried to provide an intermediate layer having a dry film thickness of 1.6 μm.

Polyvinyl alcohol (PVA205 manufactured by Kuraray Co., Ltd., saponification rate = 80%) 130 parts Polyvinylpyrrolidone (PVP, K-30 manufactured by GAF Corporation) 60 parts Distilled water 2110 parts Methanol 1750 parts In the schematic sectional view of FIG. As shown, the thermoplastic resin layer 2
2 and an intermediate layer 23 on a temporary support 21 is coated with a coating solution having the following formulation and dried to give a dry film thickness of 2 μm.
The light-shielding photosensitive resin layer 24 of No. 1 was formed, and a polypropylene (thickness 12 μm) covering sheet 25 was pressure-bonded onto the resin layer 24 to prepare a multilayer film F. In addition,
A laminate of the thermoplastic resin layer 22, the intermediate layer 23, and the light-shielding photosensitive resin layer 24 is hereinafter referred to as a transfer body 20.

Benzyl methacrylate / methacrylic acid copolymer (molar ratio = 70/30, intrinsic viscosity = 0.12) 34.30 parts Dipentaerythritol hexaacrylate 36.14 parts 2,4-bis (trichloromethyl) -6 -[4- (N, N-diethoxycarbomethyl) -3-bromophenyl] -s-triazine 1.78 parts Pigment Red 177 0 parts Pigment Blue 15: 6 6.02 parts Pigment Yellow 139 4.51 parts Pigment Violet 23 3.72 parts Carbon black 13.29 parts Hydroquinone monomethyl ether 0.02 parts F177P (Surfactant manufactured by Dainippon Ink and Chemicals Incorporated) 0.23 parts Methyl cellosolve acetate 40.0 parts Methyl ethyl ketone 60.0 parts Δx 0.04 Δy 0.05 Y value 0.35 Y value: 365 nm 10: 1 The covering sheet 25 is peeled off from the film F, and the structure of the temporary support 21 and the transfer body 20 is formed as shown in FIG.
The light-shielding photosensitive resin layer in the transfer body 20 is set on the transparent substrate structure 31 provided with a photoconductive layer so that the light-shielding photosensitive resin layer is in contact with the photoconductive layer. Using a laminator (trade name: VP-II, manufactured by Taisei Laminator Co., Ltd.) that has, heating (130 ° C.), pressurization (1 kg
/ Cm ² ) and stuck together. Subsequently, as shown in FIG. 4, the temporary support 21 was peeled from the transfer body 20, and the temporary support 21 was removed. Thus, the transparent substrate structure 31 to which the transfer body 20 was transferred was obtained.

Next, the portion where the photoconductor does not exist, etc.
The obtained laminated structure was irradiated with ultraviolet light of 50 mJ / cm ² with an ultra-high pressure mercury lamp by masking the portion where the light shielding layer was unnecessary. Then, it was developed with a 1% sodium carbonate aqueous solution to remove unnecessary portions, and further dried at 150 ° C. for 1 hour to form a light shielding layer. The thickness of this layer is 3 μm, the optical density is 3,
The flatness was as good as ± 0.1 μm. The resistivity is
It was 10 ¹¹ Ωcm.

Next, SiO ₂ and TiO ₂ are formed into a thickness (94 wavelengths) for each quarter wavelength of the light used for the reading light.
The light reflection layer was formed by alternately stacking the layers at a thickness of 8,585 angstroms) by EB vapor deposition on the light shielding layer.

Further, on the light reflection layer, a counter transparent glass substrate with a transparent electrode is attached with a space other than the peripheral portion, and liquid crystal is introduced into the space, but before that, no electric field is applied. In order to obtain the desired alignment of the liquid crystal in this state, alignment treatment was performed on both the light reflection layer side and the transparent electrode side.

As the counter transparent glass substrate with the transparent electrode, the same transparent glass substrate with the transparent electrode was used.
However, the thickness is about 2 mm. Orientation treatment is Si
O ₂ was provided by oblique vapor deposition, which was surface-treated with a silane coupling agent. The alignment treatments on the light reflection layer side and the transparent electrode side were the same. The pretilt angle was 88 °.

After performing the alignment treatment as described above, the counter transparent substrate with the transparent electrode was attached on the light reflection layer with a space other than the peripheral portion. In a specific example, first, an adhesive (two-component thermosetting epoxy resin) mixed with spherical silica (diameter 6 μm) was formed by screen printing on the peripheral portion of the opposing transparent substrate. Next, the transparent glass substrate on the photoconductive layer side was attached to the opposing transparent glass substrate with the light reflection layer side facing inward, and the adhesive was cured. In addition to the liquid crystal injection port, one pore was present on the side opposite to the side where the injection port was located.

Then, from the inlet to the above space,
Liquid crystal with negative Δε (trade name: N-35, manufactured by Chisso Corporation)
Was vacuum injected. After the injection, all pores were sealed.

Thus, the spatial light modulator was manufactured.

[0082]

As described above in detail, in the method of manufacturing a spatial light modulator of the present invention according to claim 1, the light-shielding layer having a high light-shielding property can be easily formed without using an expensive device. it can. Further, the light-shielding layer formed has a sufficiently high resistivity, high adhesiveness with an adjacent layer such as a photoconductor layer, and has good film thickness uniformity even in a large area.
In addition, patterning is easy and the layer composition is highly safe.

Particularly, according to a preferred embodiment of the method for manufacturing a spatial light modulator of claim 2, the light shielding layer is easily laminated,
This is a method suitable for practical use.

The spatial light modulator of the present invention according to claim 3 is
The above-mentioned effective manufacturing method can be used and excellent light-shielding properties are exhibited.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing an embodiment of a spatial light modulator of the present invention.

FIG. 2 is a schematic cross-sectional view of a light shielding layer used in an example.

FIG. 3 is a schematic view showing one step in the manufacturing process of the spatial light modulator in the example.

FIG. 4 is a schematic view showing another step of the manufacturing process of the spatial light modulator in the example.

[Explanation of symbols]

 1 Spatial light modulator 10, 11 Transparent glass 12 Photoconductive layer 13 Light-shielding layer 14 Light-reflecting layer 15 Liquid crystal layer 16, 17 Transparent electrode 18 Power supply 24 Light-shielding photosensitive resin layer (precursor light-shielding layer)

Claims (3)

[Claims] 1. A laminated structure having a photoconductive layer, a light-shielding layer, a light-reflecting layer, and a liquid crystal layer, which are arranged in this order, and a transparent substrate with two transparent electrodes has the transparent electrodes inside. In the method for producing a spatial light modulator having a sandwiching structure in the state of being formed, the light-shielding layer is formed by (A) an alkali-soluble binder, a photopolymerization initiator, and an addition polymerization having an ethylenically unsaturated double bond. Sex monomer,
And a light-shielding photosensitive resin composition having at least two kinds of colorants, the light-shielding photosensitive resin composition having a hue equal to or close to black and a film thickness of 1 to 3 μm. Sometimes the transparency in the visible light region is 2 or less, and the ratio of the transparency in the visible light region to the transparency in the ultraviolet region is
A step of forming a precursory light-shielding layer containing a light-shielding photosensitive resin composition of 1: 1 to 20: 1 in a sheet shape in advance, and (B) the precursory light-shielding layer becomes an adjacent layer in the spatial light modulator. A step of bringing the precursor light-shielding layer into contact with the adjacent layer by heat, and a step (D) exposing the precursor light-shielding layer to form a light-shielding layer. Manufacturing method of spatial light modulator. 2. The step (A) is carried out by applying the light-shielding photosensitive resin composition onto a temporary support, and the step of peeling the temporary support after the bonding in the step (C). The method for manufacturing a spatial light modulator according to claim 1, further comprising: 3. A laminated structure having a photoconductive layer, a light-shielding layer, a light-reflecting layer and a liquid crystal layer, and these layers are arranged in this order, and a transparent substrate with two transparent electrodes has the transparent electrodes inside. In a state where the light shielding layer is sandwiched, the light shielding layer comprises an alkali-soluble binder, a photopolymerization initiator, an addition polymerizable monomer having an ethylenically unsaturated double bond, and two or more kinds. A light-shielding photosensitive resin composition having at least a colorant, which is equivalent to or close to black in hue, and has a thickness of 1 to 3 μm when forming a light-shielding photosensitive resin composition in a visible light region. It contains an exposed composition of a light-shielding photosensitive resin composition having a transmittance of 2 or less and a ratio of transmittance in the visible light region to transmittance in the ultraviolet region of 1: 1 to 20: 1. A spatial light modulator characterized by.