JPH0440424A - Manufacture of cell - Google Patents

Abstract

PURPOSE:To adhere two substrates tightly via a uniform gap and to obtain the cell of large size which is extremely thin by using a transparent substrate as one of two substrates and providing a photosetting composition layer which contains a photosetting composition or spacer particles between the two substrates, and irradiating the layer with an electromagnetic wave or particle rays in a desired pattern shape. CONSTITUTION:A transparent electrode and an orienting film may be provided on a surface and at least one of the two substrates is made transparent; and the photosetting composition layer which contains the photosetting composition or spacer particles is provided between the two substrates. Then the layer is irradiated with the electromagetic wave or particle rays in the desired pattern shape and then the unset photosetting composition at an unirradiated part is developed and removed. Consequently, the cell of large size which has a thin cell gap is obtained while adhere uniformly and tightly.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention is a method for manufacturing a cell in which two substrates are firmly adhered with a uniform gap between them, and is particularly applicable to large-sized and ultra-thin cells. Concerning cell manufacturing method.

In particular, it relates to a method for manufacturing cells that are also useful for ferroelectric liquid crystal cells.

(Prior Art) In recent years, display elements using nematic liquid crystals have come to be used for various purposes such as office automation terminals, pocket televisions, and various monitors.

For these purposes, various devices such as (1) active matrix type devices in which each pixel is provided with a switching element such as a thin film transistor, (2) STN (super twisted nematic) devices, and (3) Clark et al. , U.S. Pat. No. 4,367,924, ferroelectric liquid crystal elements have been proposed for various display applications.

These devices have a response speed of several microseconds, have little viewing angle dependence, and are expected to be applied to still image or video displays that can be made on large screens. Cells used in these applications require very thin uniform cell gaps of about 5 microns or less in order to obtain fast response speeds and high contrast of the layers.

Moreover, it is required to maintain shock resistance.

The present invention has been devised to solve these problems.

(Objective of the present invention) An object of the present invention is to provide a method for manufacturing cells of dog size and thin cell gaps.

A photosensitive composition is sandwiched between two substrates, and electromagnetic waves or particle beams are irradiated in a pattern to provide a cell that utilizes strong adhesion between the crosslinked photosensitive composition and the substrate that occurs in the irradiated area. There is a particular thing.

An object of the present invention is to provide a ferroelectric liquid crystal cell.

The purpose is to provide cells that are uniformly and firmly bonded.

The purpose of this invention is to provide a cell manufacturing method that skillfully utilizes electromagnetic waves or particle beam scanning.

The object of the present invention is to provide the above-mentioned cell at low cost.

The objective is to develop a cell manufacturing method that is simple to process and allows easy control of the gap.

An object of the present invention is to develop a simple cell manufacturing method. The aim is to develop a method for producing cells that are dry and can be bonded. The aim is to develop a cell manufacturing method that allows the number and shape of bonding points to be changed arbitrarily depending on the purpose. The aim is to develop a method for manufacturing cells that uses a curable material and partially irradiates electromagnetic waves or particle beams from one or both sides of the material, thereby firmly adhering the irradiated parts.

(Structure of the present invention) The above-mentioned object of the present invention is to provide a photocurable composition or spacer particles between two substrates, at least one of which is transparent, and which may have a transparent electrode and an alignment film on their surfaces. A photocurable composition layer containing the above is provided, and after this is irradiated with electromagnetic waves or particle beams in a desired pattern, the uncured photocurable composition in the non-irradiated areas is developed and removed. This was achieved by developing a cell manufacturing method.

(Detailed Description of the Present Invention) In the present invention, the cell gap is preferably about 20 to 0.2 microns.

The photocurable composition is sandwiched between two glass plates by a method such as impregnation or coating on one side and then lamination.

When irradiating with electromagnetic waves or particle beams, either pattern-like or random-like irradiation method may be used, depending on the purpose of the cell.

It is also preferable to perform irradiation from both sides to achieve stronger and more uniform adhesion to the glass substrate.

It is also possible to irradiate electromagnetic waves or particle beams in a pulsed manner.

Various types of substrates can be used in the present invention.

It is preferable to use a material that is transparent and can be provided with a transparent electrode, such as glass or plastic.

As the glass, soda lime glass, neutral borosilicate glass, alkali-free glass, quartz glass, etc. can be used.

It is preferable that the surface is flat, and in some cases, surface treatment such as touch polishing may be performed to reduce minute irregularities and undulations on the surface.

Furthermore, in order to prevent elution of alkali ions, especially on the soda lime glass substrate, 8
It is preferable to provide the 102 film with a thickness of about several hundred microns.

As the brass tink substrate, one with low birefringence is preferable.

For example, polycarbonate, TAC, etc. can be used. Other plastics with suitable birefringence values, such as PE
7% PBT etc. are also used.

Furthermore, a color filter layer may be provided on at least one of the transparent substrates.

Various types of color filters can be used, such as those that use a polar polymer such as gelatin and mordant, and those that use printing using pigments or dyes.

In order to reduce the unevenness of these color filter layers,
Various methods have been developed and can be used. For example, the color filter layer itself may be heated and pressed using a hot roller or the like, or an inorganic or organic overcoat layer may be provided on the color filter layer as a layer or a superimposed layer.

Electrodes are provided on the substrate or color filter layer.

Various types of transparent electrodes can be used.

For example, SnO doped with 5n02, ITOIF, etc.
2 or ITOlAl, 1n doped Z n 02
Examples include %ClO%CTO.

Among these, ITO type materials having low specific resistance are preferred.

These films are coated by vapor deposition or sputtering. Among these, the sputtering method is preferred because it provides a large area, excellent low-temperature coating properties, and excellent surface smoothness.

In addition, in cases where the resistance value of transparent electrodes needs to be lowered due to higher resolution and larger screens, for example, Cu, Ni, etc. can be used on ITO.
, AI, or other metal wiring may be provided. An insulating film layer may be provided on the transparent electric bridge in order to prevent display defects due to short circuit between the transparent electrodes of the upper and lower substrates after cell formation.

As such an insulating film, 5in2. At03,
A dielectric material such as T 102 s Ca F2 may be used.

Alternatively, a ferroelectric material such as barium titanate may be used.

These insulating layers may be provided by a vapor deposition method or a sputtering method.

In the present invention, it is preferable to provide an alignment film to align the liquid crystal.

The alignment film is provided on the transparent electrode or the insulating film. In general, inorganic and organic types are used.

For example, as inorganic ones, S i 02 , A03,
An obliquely deposited film of TlO2, CaF2, etc. is preferred.

As organic materials, thin films of so-called insulating polymers such as polyimide, polyamide, polyamideimide, polyetherimide, polyvinyl alcohol, polyester, polyethersulfone, nylon, polycarbonate, and cellulose derivatives can be used.

Additives such as a sinker/mumbling agent and a long-chain furkyl compound may be added to these.

Alternatively, an LB film, a plasma polymerized film, or a conductive alignment film can also be used.

Furthermore, when using an organic alignment film, it is preferable to subject at least one of the two substrates to a rubbing treatment in order to obtain uniform alignment of the liquid crystal.

In the present invention, two substrates are bonded to a thickness of about 0.2 to 10 microns to form a cell.

For ferroelectric liquid crystal cells, the thickness is preferably about 1 to 5 microns. As described above, an alignment film or an insulating layer can be provided on these substrates at least as the uppermost layer.

Hereinafter, as a substrate, all or part of a passivation film, transparent electrode, metal wiring, color filter layer, alignment film, and insulating film may be provided on a glass or plastic plate.

The gaps between the cells are set by a photocurable composition patterned into dots or stripes with a predetermined film thickness, or by spacer particles auxiliary dispersed in the photocurable composition.

At the same time, the photocurable composition maintains a uniform cell gap by bonding two substrates, and also provides shock resistance, especially in cells for thin ferroelectric liquid crystal devices. be.

The method for producing the cell of the present invention will be briefly described.

A photosensitive composition is sandwiched between two substrates, at least one of which is transparent, to a predetermined thickness.

It may be impregnated with a photosensitive composition, or it may be applied by means such as spin cord, roll coating, dip coating, or flexo printing, and then bonded together.

At this time, in order to obtain a predetermined film thickness, it is preferable to disperse spacer particles having a uniform particle size in the photocurable composition.

After this, it is cured in a pattern. For example, electromagnetic waves or particle beams focused into a point-like beam, such as Uv
The light is scanned at regular intervals or shined through the image.

At this time, the irradiated portion of the photocurable composition is cured to such an extent that it becomes insoluble in the solvent.

After this curing treatment, the unirradiated portions of the photocurable composition are developed and removed. A solvent or alkaline water is used as the developer.

If necessary, the photocurable composition is completely cured by applying pressure, further irradiating with electromagnetic waves or particle beams, and/or heating. In this way, the two substrates are firmly bonded.

Below, various components, spacer particles, patterns of the photocurable composition, contents of the photocurable composition, solvents, electromagnetic waves, or particle beams used in the present invention will be described.

In the present invention, the cell gap is primarily set by the photocurable composition. However, by supplementarily using spacer particles, the cell gaps can be made uniform.

Particularly in the case of panels of 5 inches or more, it is preferable to use spacer particles.

Preferably, the spacer particles are mainly spherical.

Various types of fine particles have been developed in recent years, and Ichisaka products are also easily available. As mentioned above, particles with uniform particle size are preferred.

Examples include organic fine particles such as Micropearl manufactured by Blockbuster Fine Chemical Co., Ltd., Epostor manufactured by Nippon Shokubai Chemical Co., Ltd., and Tosparl manufactured by Toshiba Silicone Company.

On the other hand, the inorganic fine particles are preferably mainly spherical.

For example, Fulfit manufactured by Showa Denko Co., Ltd. and Mashidyu (silica particles) manufactured by Nippon Shokubai Kagaku Co., Ltd. are examples thereof.

Other shapes such as rod-shaped PF series made by Nippon Electric Glass Co., Ltd. can also be used.

Furthermore, if necessary, the spacer particles can be subjected to various treatments, for example, surface treatments such as silane coupling treatment to prevent agglomeration.

In the present invention, the pattern of the photocurable composition that functions as both an adhesive and a spacer between substrates is preferably dot-shaped or striped.

Alternatively, it may be a mixture of these.

Furthermore, short stripes may be provided intermittently. In order to ensure the adhesive strength between the upper and lower substrates, the density of dotted patterns should be at least 0.3 pieces/mm
In the above, those having a diameter of 0.5 microns or more are preferable.

For stripes, the arrangement density is at least 0.3
Lines/mm or more and line width of 0.5 microns or more are preferred.

When irradiating with electromagnetic waves or particle beams, various methods such as patterned, striped, random, etc. can be used.

It is also preferable to irradiate from both sides of the substrate or to irradiate while heating.

The photocurable composition used in the present invention is already well known in various fields.

One method is to use photocurable polymers, low molecules, or a mixture thereof.

In particular, it is advantageous to use a photocurable polymer, so this will be described first.

Copolymers having both photocurable groups and adhesive sites are advantageous, and these copolymers can be synthesized in several ways.

, which copolymerizes a monomer with a photocurable functional group with another monomer.

11. Copolymerization with active functional groups such as hydroxy, 7-mino, glycidyl or halogen atoms is copolymerized with a monomer having a photocurable group, and other components are introduced by polymer reaction.

Both methods such as those based on polymerization of vinyl monomers and those based on polymer reactions can be used.

From the viewpoint of handling, it is convenient to use a copolymer of a monomer having a photocurable group and a monomer.

For these reaction conditions, handling, etc., well-known ones can be referred to.

First, we will discuss i above.

Examples of the unit having a photocurable group include those having a monomer unit having an internal olefin or terminal olefin, such as an unsaturated fatty acid derivative, stilbazole, chalcone, or maleimide, as a curable group.

For example, when the unsaturated fatty acid derivative is a terminal olefin type,
(Meth)acrylate, etc., after polymerization,
Introduction by esterification or amidation is preferred over copolymerization.

When used as a monomer, an ester or 7-amide of an unsaturated fatty acid derivative, an ester or 7-amide of a quaternary chlorinated stilbazolium, a chalcone, or an ester or amide of a chalcone in which one aromatic ring is substituted with a heterocycle; Examples include those having an ester or amide having a maleimide or dimethylmaleimide moiety and a polymerizable group. A divalent group having 26 or less carbon atoms may be present between the curable group and the polymerizable group, which is carried from an ester, ether, urethane, aromatic ring, or the like.

Photocurable monomers include vinyl compounds with curable substituents, such as styrene, (meth)acrylate,
(Meth)acrylamide is a representative example.

Unsaturated fatty acid derivatives are a typical example, and will be explained first.

Typical examples of the unsaturated fatty acid moiety include cinnamic acid, α-cyanocinnamic acid, phenylpentadienoic acid, thienylpentadienoic acid, butoxycarbonyl vinyl cinnamic acid, methylfuryl acrylic acid, naphthyl acrylic acid, ethylthienyl acrylic acid, Furyl pentadienic acid, p-ethoxycarbonylcinnamic acid, α-cyanonelupic acid, hexylcrotonic acid, dimethyl maleic anhydride, maleic anhydride, cinnamylidene acetate monoethyl ester, cyanothienylpentadinic acid, p-phenylene diacrylic acid monoethyl ester, etc. There is. There are (meth)7 acrylates and (meth)acrylamides of these and vinyl monomers having a hydroxy group or an amino group.

Vinyl monomers having a dihydroxy group, a 7-mino group and a hydroxyl group, or multiple 7-mino groups are also useful.

Therefore, cinnamoyloxyethyl (meth)acrylate or amide, cinnamoyloxypropyl (meth)
Preferred curable monomers include acrylate or amide, (meth)acryloxyethyl phenylpentagenoate, (meth)acryloxybutyl-α-cyanocinnamate, and phenylene di-7 acrylate-monoethyl ester-meth 7-acrylate. .

In addition, the photocrosslinkable vinyl monomer is disclosed in West German Patent No. 21646.
25, Japanese Patent Publication No. 49-36794.38987.6039
0, +03975.107226, etc., (meth)acrylate having an ester or amide group of β-7 aryl substituted acrylic acid, styrene or (meth)acrylamide, ester or amide of vinyl cinnamic acid, (meth)acrylate having an azide group , styrene, esters of δ-7-aryl-substituted pentadienoic acids or (meth)acrylates with amide groups, (meth)acrylic 7-mides or styrene, (of chalcone with hydroxy or amine groups)
unsaturated fatty acid derivatives such as meth)acrylates or amides, (meth)7acrylates or amides from esters or 7amides of cinnamic acid with hydroxy groups, azides,
Monomers such as acid azide derivatives are available.

Furthermore, maleimide type monomers, such as monomers having a dialkyl-substituted or furkylaryl-substituted maleimide moiety, are also effective.

For example, dimethylmaleimide-N-(meth)acryloxypropyl, (meth)7cryloxyethoxyethyl-1
- Naphthyl-2-methylmaleimide, etc., and further has internal olefinic bonds such as 4-(meth)acryloxyethyloxystilbazolium tosylate, 4-N(meth)acryoxypropyloxystilbazolium iodide, etc. There are also functional groups such as stilbazolium derived from stilbazolium or similar functional groups such as stilbene, coumarin, and cyclopropenone, which can be easily substituted by those skilled in the art. These are also included.

These curable functional groups have the advantage of being able to use a sensitizer effectively and increasing the sensitivity, as the case may be, and of having good thermal stability.

The proportion of the photocurable portion as a unit with respect to the entire polymer is 5 mol percent or more and 90 mol percent or less, preferably 20 mol percent or more and 80 mol percent or less.

If it is less than 5 mol percent, sufficient curing will not proceed even if the irradiation time is extended, and if it exceeds 90 mol percent,
Although it is advantageous for polymer formation, sufficient flexibility cannot be obtained.

The molecular weight can vary widely depending on the purpose, use, and required properties.

A value of about 600 to 500,000 is convenient from the viewpoint of synthesis and handling.

It is also advantageous to have the ability to form a film.

These quantitative relationships and coating thickness depend on the type of linking group,
It is set by other tools.

Furthermore, various other monomers such as
Vinylpyrrolidone, diethylaminoethyl (meth)acrylate, diethyl 7minomethylstyrene, dimethylaminobutyl (meth)7acrylate, acetoacetoxybutyl methacrylate, acetoacetoxyethyl (meth)
Acrylate, styrene, methyl methacrylate, hydroxyethyl (meth)acrylate, hexyl methacrylate, acrylamide, butoxyethyl (meth)acrylate (meth)acrylic acid, acryloxyethyl (meth)acrylic acid, acrylamide, vinyl acetate, cellosolve (meth)acrylate, Vinyltoluene, α-Sifno 4-methoxycinnamoyloxyethyl (meth)7 acrylate, acrylonitrile, and the like can also be used.

These are used in an amount of 60 mol percent or less and 10 mol percent or more.

Monomers with active sites known as ester, carboxy, glycidyl, etc. or silane coupling agents are preferred as copolymerization partners.

Alternatively, functional groups such as a hydroxy group, a quaternary base, a dialkylamino group, and a carbamoyl group are also preferred. These introductions are carried out according to conventional methods.

By appropriately selecting the framework and amount of comonomer used, resistance, solvent resistance, light resistance, hardness, plasticity, viscosity, stability, developability,
Characteristics such as transparency can be significantly changed.

The general relationship between changes in monomers and the physical properties of the resulting polymers is known in the fields of inks, resists, paints, and printing plates, and that knowledge can be effectively used.

Next, ii etc. will be described.

The reaction of an active group such as a hydroxyl group, an amino group, a glycidyl group or a halogen atom with a group having a curable group, for example with an acid or an acid halide, is known as star manipulation.

The reaction conditions are detailed in the literature and are described in the cited patents. For example, we also have detailed information about the Maruzen (New) Experimental Chemistry Course.

He is already well versed in books about methods such as copolymerization and radical polymerization.

For example, W-R-Sorenson"Preparat
ive Methods of Potimer
Chemistry", J-E3randrup"
Polymer Handbook”Wilsy
& 5ons etc.

Copolymers are generally obtained by non-catalytic, thermal or radical polymerization reactions. 7zo compound with electron-withdrawing group,
Peroxides, redox systems, etc. are examples of preferred initiators.

These functional polymers are characterized by having different functions in their side chains, making it possible to obtain a more effective composition for adhesive materials, and to obtain good and reliable adhesion of the irradiated area. In other words, it has a curable group, so it is easily cured by radiation, light, heat, etc., and it is strongly bonded and robust.Moreover, its properties can be adjusted by selecting the comonomer. .

Furthermore, as mentioned above, since the hydrophilicity can be controlled arbitrarily, it is possible to treat, clean, or remove the uncured portion with alcohol, water, or a mixture thereof, which is preferable from the viewpoint of no or low pollution. .

Alternatively, various photocurable compositions containing low-molecular polyfunctional monomers known for use in UV-curable paints or resists can also be used.

These include, for example, quinonediazides (polymeric and non-polymeric) described in USP 4,141,733, USP 351
1611, photosensitive polycarbonate, USP 3
Diazonium salts, diazo resins, cinnamal malon II+ and their like, as described in 342601, USP
There are also photosensitive polyesters, polycarbonates, polysulfonates, etc., as described in US Pat. No. 4,139,390.

For boat fishing, a photosensitive resin composition comprising urethane di(meth)7 acrylate, a linear polymer compound, and a photosensitizer is disclosed in JP-A No. 57-55914, etc., and JP-A No. 62-2473.
Novolac epoxy resin (meth) specified in Publication No. 53
There is a photosensitive resin composition consisting of an acrylic modified resin and a photosensitizer.

In addition, in order to prevent air bubbles during heat-compression bonding and improve heat resistance and adhesion, it is also possible to use a process such as heat-compression bonding under reduced pressure, as disclosed in Japanese Patent Application Laid-Open No. 52-52703. good.

On the other hand, a liquid developable photosensitive resin composition requires fewer steps because it is impregnated or directly applied to the area to be used in its liquid state. For example, it is suitable as a bonding point for closely spaced cell reservoirs.

Further, curable compositions described in JP-A-58-24144, JP-A-59-2049, JP-A-61102652, and JP-A-62-27736 can also be used. Liquid photosensitive compositions have various advantages because they utilize prepolymers containing a large number of reactive monomers.

In addition, liquid resin compositions mainly composed of bisphenol-type epoxy resins having unsaturated groups and carboxyl groups, as disclosed in JP-A No. 62-187722, and photosensitive resin compositions that can be developed with alkaline aqueous solutions or water. JP-A No. 61-243869, No. 63-258975
A photocurable composition containing a photopolymerizable compound obtained by reacting a novolac type epoxy compound, an unsaturated monocarboxylic acid, and a polybasic acid anhydride, as disclosed in Japanese Patent Application No. 1135178. Novolak-type epoxy compound, with dibasic acid hydroxyl group (meth)
A liquid photosensitive resin composition such as a liquid photosensitive resin composition using a photopolymerizable compound obtained by sequentially reacting a 7 acrylate half-esterified product and a polybasic acid anhydride can be used.

As a photocurable compound, it is highly sensitive to electromagnetic waves, particle beams, and ultraviolet light exposure, has excellent developability with water, solvents, or in some cases alkaline aqueous solutions, and has excellent electrical and mechanical properties at the adhesive point after curing. Curable resin compositions with excellent chemical resistance and moisture resistance are effective.

As an example of this, a curable composition obtained by sequentially reacting a novolac type epoxy compound, a (meth)7 acrylate half ester having a hydroxyl group of a dibasic acid, and a polybasic acid anhydride can be used.

Examples of novolak-type epoxy compounds include phenol novolak-type epoxy resins, cresol novolak-type epoxy resins, and the like. Each of these is obtained by reacting epichlorohydrin with the phenolic hydroxyl group of a novolac type resin obtained by reacting phenol, cresol, etc. with an aldehyde in the presence of a catalyst.

A (meth)acrylate half-ester of a dibasic acid having a hydroxy group is obtained, for example, as an equimolar reaction product of a dibasic acid or its anhydride and a (meth)acrylate having a hydroxy group.

Dibasic acids or their anhydrides include succinic acid, methylsuccinic acid, methylmaleic acid, 2-chloromaleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, tetrachlorophthalic acid, hexahydrophthalic acid, and endomethylenetetrahydrophthalic acid. , chlorendic acid and 5-(2,
5-dioxotetrahydrofuryl)-3-methyl-3-
Examples include cyclohexene-1,2-dicarboxylic acid and anhydrides thereof. Having a hydroxy group (meta)
Acrylates include hydroxymethyl (meth) 7-acrylate, 2-hydroxyethyl (meth) 7-acrylate, 2-hydroxypropyl (meth) acrylate, 3-
Hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-chloropropyl (meth)acrylate, diethylene glycol mono(meth)acrylate, 2-methacryloyloxyethyl Examples include -2-hydroxypropyl phthalate, 2-hydroxy-3-phenyloxypropyl (meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tri(meth)acrylate. Furthermore, commercially available products of (meth)acrylate half esters having a hydroxyl group of dibasic acids include 70Nix M-5400, M-5500 manufactured by Toagosei Chemical Industry Co., Ltd.
Light ester HO-M manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.
P and HO-MS.

Visco-1-#2100 manufactured by Osaka Organic Chemical Industry Co., Ltd., etc. can be used. Among these, particularly preferred specific examples include equimolar reaction products of succinic anhydride and 2-hydroxyethyl (meth)acrylate, equimolar reaction products of phthalic anhydride and 2-hydroxyethyl (meth)acrylate, Examples include reaction products of succinic anhydride and 2-hydroxypropyl (meth)acrylate.

Among these, dibasic acid anhydrides are preferred, with succinic anhydride and tetrahydrophthalic anhydride being particularly preferred.

Each is reacted to obtain a photopolymerizable compound.

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

Examples of sensitizers include α-sensitizers such as benzyl and diacetyl.
Diketones, acyloins such as benzoin, acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, thioxanthone, 2゜4-diethylthioxanthone, thioxanthone 1-sulfonic acid, thioxanthone-4-sulfonic acid, etc. Thioxanthone, hensifhenone, 4゜4
'-Bis(dimethyl7mino)benzophenone, 414'
-Hensephenones such as bis(diethylamino)hensiphenone, acetophenone, ρ-dimethylaminoacetophenone, α,α′-dimethoxyacetoxyacetophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-
[4-(methylthio)phenyl]-2-morpholino-
7cetophenones such as 1-propanone and anthraquinone, quinones such as 1,4-naphthoquinone, halogen compounds such as phenacyl chloride, tribromomethylphenylsulfone, tris(tricomethyl)-S-triazine, di-t- Examples include peroxides such as butyl peroxide.

These sensitizers may be used alone or in a mixture of two or more, and are preferably used in an amount of 0.08 to 28.5 parts by weight, particularly 0.15 to 14.2 parts by weight, based on the curable composition. It is preferable to do so.

In addition to the above-mentioned compounds and sensitizers, the curable composition also contains a polymerizable compound having at least one ethylenically unsaturated double bond, a compound having at least one epoxy group, and heat for thermally reacting the epoxy group. Curing catalysts, organic solvents, thermal polymerization inhibitors, etc. can be added.

Examples of the polymerizable compound having one or more ethylenically unsaturated double bonds include acrylic acid or methacrylic acid derivatives of alcohols and amines.

Examples of the alcohol include commercially available alcohols that may have a substituent having about 1 to 250 carbon atoms. For example, methanol, ethanol, propatool, isopropanol, n-butanol, isobutanol, t-
Butanol, cyclohexyl alcohol, benzyl alcohol, 2-ethylhexanol, lauryl alcohol, stearyl alcohol, methoxyethyl alcohol,
Ethoxyethyl alcohol, butoxyethyl alcohol, polyethylene glycol methyl ether, polyethylene glycol monoethyl ether, 2-human oxygen 3-chloropropane, dimethylaminoethyl alcohol, diethylaminoethyl alcohol, glycidol,
2-trimethoxysilylethanol, ethylene chlorohydrin, 7lyl alcohol, oleyl alcohol, epoxystearyl alcohol, phenol, naphthol, etc., ethylene glycol, 1,2-propanediol, 1
．． 3-propanediol, 114-butanediol, 1
, 5-bentanediol, hexanediol, heptanediol, octanediol, nonanediol, dodecanediol, neopentyl glycol, 1,10-decanediol, 2-butene-1,4-diol, 2-n-
Butyl-2-ethylpropanediol, cyclohebutanediol, 1,4-cyclohexane dimetatool, 3-
Cyclohexene-1,1-jetanol, polyethylene glycol (diethylene glycol, triethylene glycol, etc.), polypropylene glycol (dipropylene glycol, tripropylene glycol, etc.), polystyrene oxide glycol, polytetrahydrofuran glycol, xylylene diol, bis(β-hydroxyethoxy ) Benzene, 3-chloro-1,2-propanediol, 2,2-dimethyl-1,3-propanediol,
2.2-diethyl-1,3-propanediol, 2.2
-diphenyl-1,3-propanediol, decalindiol, 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene, 2゜5-dimethyl-2,5-hexanediol, 2-ethyl-1,3 -hexanediol, 2-ethyl-2-(hydroxymethyl)-1,3-propanediol, 2-ethyl-2-methyl-1,3-propanediol, 3-hexene-2,5-diol, hydroxybenzyl alcohol , 2-methyl-1,4-butanediol, 2-methyl-2,4-bentanediol, 1-phenyl-1,2-ethanediol, 2.2.4
．． 4-tetramethyl-1,3-cyclobutanediol,
2.3,5,6-titramethyl-ρ-xylene-α,α
2-diol, +, 1,4.4-tetraphenyl-2-
Butyne-1,4-diol, 1,1'-bis-2-naphthol, dihydroxynaphthalene, +,1'methylene-di-2-naphthol, biphenol, 2,2-bis(4-
hydroxyphenyl)butane, 1,+-bis(4-hydroxyphenyl)cyclohexane, bis(hydroxyphenyl)methane, catechol, resorcinol, 2-methylresorcinol, 4-chlororesorcinol, pyrogallol, α-(1-7minoethyl)- p-hydroxypencyl alcohol, 2-amino-2-methyl-113
-propanediol, 2-amino-2-ethyl-1,3
-Propanediol, 3-7mino-1,2-propanediol, N-(3-7minoprovil)-jetanolamine, N,N-bis(2-hydroxyethyl)piperazine, 1,3-bis(hydroxymethyl) ) urea, 1,2
-bis(4-pyridyl)1,2-ethanediol, N-
n-butyljetanolamine, jetanolamine,
N-ethyljetanolamine, 3-mercapto-1,
2-propanediol, 3-piperidine-1,2-propanediol, 2-(2-pyridyl)-1,3-propanediol, α-(1-7minoethyl)-ρ-hydroxybenzyl alcohol, glycerin, trimethylol Ethane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, glucose, α-mannitol, butanetriol, 1.2.6-4 hydroxyhexane,
1.2.4-benzenetriol, triethanolamine, 2,2-bis(hydroxymethyl)-2,2',2
"-nitrilotriethanol, etc. Among the esters of acrylic acid or methacrylic acid of these alcohols, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol Trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, glycerin triacrylate, glycerin trimethacrylate, trimethylolpropane Tri7 acrylate, trimethylolpropane trimethacrylate, trimethylolethane tri7 acrylate, trimethylolethane trimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, sorbitol hexa 7 acrylate, sorbitol hexa methacrylate,
Sorbitol pentaacrylate, sorbitol pentamethacrylate and the like are preferred.

It is also possible to use (meth)acrylic acid derivatives of mono- or polyamines, such as acrylamide or methacryl 7mide. Examples of amines include ethylamine, butylamine, amylamine, hexylamine, octylamine, cyclohexylamine, 9-7 minodecalin, etc., allylamine, methalylamine, benzylamine, etc., aromatic amines such as aniline, toluidine, p-7 minostyrene, ethylenediamine, triamine, etc. Methylenediamine, tetramethylenediamine, hexamethylenediamine, octamethylenediamine, hexamethylenebis(2-
7minoprovir)amine, diethylenetriamine, triethylenetetraamine, polyethylenepolyamine, tris(2-7minoethyl)amine, 4,4'-methylenebis(cyclohexylamine), N,N'-bis(2-7
(minoethyl)-1,3-propanediamine, N,N'-
Bis(3-7minoprovil)-1,4-butanediamine, N,N'-bis(3-7minoprovil)ethylenediamine, N,N'-bis(3-7minoprovil)-1,3
-Propanediamine, 113-cyclohexanebis(methylamine), phenylenediamine, xylylenediamine, β-(4aminophenyl)ethylamine, diaminotoluene, diaminoanthracene, diaminonaphthalene, diaminostyrene, methylenedianiline, 24-bis(4- 7 minohendyl) aniline, aminophenyl ether, etc.

Furthermore, allyl compounds such as formic acid, acetic acid, propionic acid, butyric acid, lauric acid, benzoic acid, chlorobenzoic acid, malonic acid, oxalic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, terephthalic acid, hexahydrophthalic acid ,
Mono- or polyallylic esters of mono- or polycarboxylic acids such as chlorendic acid and trimellitic acid, mono- or polyallylic esters of mono- or polysulfonic acids such as benzenedisulfonic acid, naphthalenedisulfonic acid, diallylamines, N,N'-diallyloxalic acid diamide,
1,3-diallylurea, diallyl ether, triallyl isocyanurate, etc. can also be used.

Also, for example, divinylbenzene, p-7lylstyrene,
Polyvinyl compounds such as p-isopropenyl styrene, divinyl sulfone, ethylene glycol divinyl ether, glycerol trivinyl ether, divinyl phthalate, divinyl phthalate, divinyl terephthalate, etc., 2
Acrylic acid or methacrylic acid ester compounds having an ionic group such as -hydroxy-3-methacryloyloxypropyltrimethylammonium chloride and methacryloyloxyphenyltrimethylammonium chloride can also be used.

Furthermore, commercially available polymerizable monomers or oligomers, such as 70nix M5700 and M61 manufactured by Toagosei Chemical Industry Co., Ltd.
00, M8O30, M152, M2O3, M215, M
7 acrylate monomers such as 315 and M325, NK ester ABPE-4 and Ll-48 manufactured by Shin-Nakamura Chemical Co., Ltd.
A%CB-1, CBX-1, KAYARA manufactured by Nippon Kayaku Co., Ltd.
DR604, DPCA-30, DPCA-60, K
7 acrylate or methacrylate monomers such as AYAMAR PM-1, PM-2, Photomer 4061.5007 manufactured by San Nopco, Lipoxy VR6 manufactured by Showa Kobunshi Co., Ltd.
Epoxy acrylates such as 0, VR90, and 5P1509, and spirane resins having a spiroacetal structure and an acrylic or methacrylic group such as Spirac E4000X and U3000 manufactured by the same company can also be used.

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

As a compound having at least one epoxy group,
For example, glycidyl ethers of alcohols having 2 to 20 carbon atoms such as butyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether, aryl glycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, ethylene glycol diglycidyl Ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanesiol diglycidyl ether, dibromoneopentyl glycol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, diglycerol tetraglycidyl ether , polyglycidyl ethers of polyols such as polyglycerol polyglycidyl ether, 2,6-sibricidylphenylglycidyl ether, 2,6.2', 6'-tetramethyl-4,
4'-biphenyl diglycidyl ether, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol S type Glycidyl ether type epoxy compounds such as epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, halogenated phenol novolac type epoxy resins and brominated epoxy resins, alicyclic gepoxy 7-cetal, alicyclic gepoxy adipate, Cycloaliphatic epoxy compounds such as vinyl cyclohexene dioxide, unsaturated acid glycidyl esters such as glycidyl heptacrylate, glycidyl methacrylate, tetrahydroxyphthalic acid diglycidyl ester, sorbic acid glycidyl ester, oleic acid glycidyl ester and lyluic acid glycidyl ester , butyl glycidyl ester, octyl glycidyl ester, hexahydrophthalic acid diglycidyl ester and dimer acid glycidyl ester, and benzoic acid glycidyl ester, 0-phthalic acid diglycidyl ester and diglycidyl p-oxybenzoic acid. glycidyl ester type epoxy compounds such as aromatic carboxylic acid glycidyl esters such as, tetraglycidyl di7minodiphenylmethane, triglycidyl-1)-7minophenol, triglycidyl-m-aminophenol, diglycidylaniline, diglycidyltoluidine, Glycidylamine-type epoxy compounds such as tetraglycidyl-m-xylylene diamine, diglycidyltribromoaniline and tetraglycidylbisaminomethylcyclohexane; heterocyclics such as diglycidylhydantoin, glycidylglycidoxyalkylhydantoin and triglycidyl isocyanurate; Examples include epoxy compounds. Among these, 2.
6.2'6'-tetramethyl-4,4'-biphenyl diglycidyl ether, Nopola-Nk type epoxy resin, and heterocyclic epoxy compound are preferred.

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

Thermosetting catalysts for thermally reacting epoxy groups include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine (dipropyltriamine), bis(hexamethylene)triamine, 1.3.6-trisaminomethyl Polyamines such as hexane, polymethylene diamines such as trimethylhexamethylene diamine, polyether diamine, diethylaminoprobylamine, menthene diamine, infron diamine, bis(4-amino-3-methylcyclohexyl)methane and N- Aliphatic primary amines such as alicyclic polyamines such as 7-minoethylpiperazine, aromatic primary amines such as metaphenylenediamine, diaminophenylmethane, diaminophenyl sulfone and aromatic diamine eutectic mixtures, polyamine epoxy resin adducts , polyamine-ethylene oxide duct, polyamine-propylene oxide duct, cyanoethylated polyamine,
Modified amines such as ketoimine, piperidine, piperazine,
Tertiary amines such as morpholine, and amine compounds such as tertiary amines such as tetramethylguanidine, triethanolamine, benzyldimethylamine, 2,4.6-tris(dimethylaminomethyl)phenol, phthalic anhydride, Trimellitic anhydride, ethylene glycol bis(
anhydrotrimellitate), glycerin tris(7-hydrotrimellitate), pyromellitic anhydride, 3.3
Aromatic acid anhydrides such as ',4.4'-benzophenonetetracarboxylic anhydride, maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendo Cyclic aliphatic acid anhydrides such as methylenetetrahydrophthalic anhydride, fluorenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylcyclohexenetetracarboxylic anhydride, polyadipic anhydride, polyazelaic anhydride, Aliphatic acid anhydrides such as polysebacic anhydride, acid anhydrides such as chlorendic anhydride, halogenated acid anhydrides such as tetrabromophthalic anhydride, 2-methylimidazole, 2-
Ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-
cyanoethyl-2-ethyl-4-methylimidazole,
1-cyanoethyl-2-undecylimidazole, 1-
Cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium incyanurate, 2-phenylimidazolium incyanurate, 2,4-diamino-6 -[2-methylimidazolyl-(1)]-]ethyl-s-triazine 2.4
-Diamino-6-(2-ethyl-4-methylimidazolyl-(1))]-]ethyl-5-su7dine, 2,4-diamino-6-[2-undecylimidazolyl-(1)]-
]Ethyl-s-triazine 2-phenyl-4-methyl-
5-hydroxymethylimidazole, 2-phenyl-4
, 5-dihydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di(cyanoethoxymethyl)imidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride and 1,3-dibenzyl-2 Imidazol compounds such as methylimidazolium chloride, novolac type phenolic resin, cresol type phenolic resin, resorcinol type phenolic resin, phenols such as polyvinylphenol, boron trifluoride-amine complex, boron pentafluoride-amine complex and Lewis acid-amine complexes such as arsenic pentafluoride-amine complexes, dicyandiamide, o-tolyl biguanide,
Dicyandiamide derivatives such as phenylbiguanide and α-2,5-dimethylbiguanide, organic acid hydrazides such as succinic acid hydrazide, 7sibic acid hydrazide, isophthalic acid hydrazide and p-oxybenzoic acid hydrazide, diaminomaleonitrile and benzyldiaminomaleonitrile Known epoxy curing accelerators can be used, such as diaminomaleonitrile derivatives such as melamine and melamine derivatives such as N,N-diallylmelamine, amine imide derivatives, and polymercaptans.

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

Examples of organic solvents include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, cellosolves such as cellosolve and butyl cellosolve, carpitols such as calpitol and butyl cavitol, ethyl acetate, butyl acetate, and cellosolve acetate. ,
Examples include acetic acid esters such as butyl cellosolve acetate, carpitol acetate, and butyl carpitol acetate.

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

Examples of thermal polymerization inhibitors include hydroquinone, ρ-
Methoxyphenol, pt-butylcatechol, 2,
Aromatic hydroxy compounds such as 6-di-t-butyl-p-cresol, β-naphthol, and pyrogallol, quinones such as benzoquinone and p-torquinone, naphthylamine,
Examples include amines such as pyridine, p-toluidine, and fetch-7dine, aluminum salts or ammonium salts of N-nitrosophenylhydroxylamine, floranil, and nitrohenzene.

Furthermore, the curable resin composition used in the present invention includes a tackifier, an adhesion promoter, a dispersant, a plasticizer, an anti-sagging agent, a leveling agent, an antifoaming agent, a flame retardant, a brightening agent, a coloring agent, etc. Supplementary additives may be added as necessary.

Examples of tackifiers or adhesion promoters include alkylphenol/formaldehyde novolac resins, polyvinylethyl ether, polyvinyl isobutyl ether,
Polyvinyl butyral, polyisobutylene, styrene
Butadiene copolymer rubber, butyl rubber, vinyl chloride-vinyl acetate copolymer, chloride rubber, acrylic resin adhesive,
Examples include aromatic, aliphatic or alicyclic petroleum resins.

Addition of a tackifier or an adhesion promoter increases the adhesion of the photosensitive resin to the cell substrate after curing, and this effect is particularly pronounced when used in a liquid crystal cell.

Dispersants are used to improve the dispersibility, storage stability, etc. of the curable composition. The necessity of blending the plasticizer, anti-sagging agent, leveling agent, and antifoaming agent, the method of using the curable composition, and the types and amounts to be used are selected as appropriate.

Various examples of use in applications such as imaging are already available in J-
Kosar"Light 5ensistive S
systems" John Wiley & 5ons, Tsunoda "Photosensitive Resins" Printing Society, Straw material "Photosensitive Polymers" It can take any form.

As the sensitizer, which is optionally used, compounds that promote crosslinking and polymerization of unsaturated fatty acid derivatives are conveniently used.

These are well known, for example, JP-A-57-1
79836, 62-743044, USP46328
99, 4634657, 4647952, 467
0374, 4701402, 4716095, 4
753865, LISP4139390, etc.

Aromatic ketones, nitro, quinones, or amine compounds or cyanine borates or combinations thereof, 3-substituted coumarins, amino-substituted ketocoumarins, 2-7ylmethylenethiazolin or selenazoline, N-phenylthioacridone, thiapyrylium perchlorate, Quinarisin is a typical example and is used in an amount of about 1 to 10%.

Ketone-type and azide-types that act as crosslinkers
A type of sensitizer can also be used in combination.

For example, Michler's ketone, dibenzal acetone, etc. are examples.

Furthermore, depending on the purpose, various additives such as surfactants, plasticizers, dyes, pigments, stabilizers, antioxidants, sensitizers, development aids, development accelerators, latex, matting agents, or binders may be added. , used as appropriate.

For example, regarding dyes and pigments that are used as necessary,
JP 81-36872, JP 1-205149, u
sP4806451, sP4427758, etc., as well as initiators, stabilizers, etc., are described in JP-A-64-48059,
JP 1-31147, USP 4B22719, USP 48
I am also familiar with 16379 etc.

These auxiliary additives may cause the star compound to exhibit not only one type of property (dispersibility, plasticity, anti-sagging, leveling or antifoaming properties), but also multiple additive effects. For example, dispersants may also act as plasticizers, leveling agents, and antifoaming agents for liquid photopolymer compositions, and dispersants, anti-sag agents, leveling agents, and antifoaming agents may also act as plasticizers, leveling agents, and antifoaming agents for photosensitive resin compositions after photocuring. It also has an effect on the glossiness of color resin compositions, and may act as a brightening agent.

As the dispersant, for example, a fluorine-containing polymer compound, a surfactant, a modified lecithin, a non-silicon long chain carboxylic acid amine salt, an organic montmorillite, etc. are used.

When forming adhesive points using the curable composition obtained in this way, this resin composition is impregnated or applied between substrates, and then cured with electromagnetic waves or particle beams, and the cured portions bond the glass substrates. , insolubilize the unirradiated part,
Develop and elute with a solvent or aqueous solution.

At that time, it is preferable to pay sufficient attention to the amount of residual alkali and suppress it to a level that is substantially undetectable.

Further, these and the patents and documents cited above contain detailed information on various forms, additives, usage, supports, coating methods, etc.

Pine day or extenders can also be used in the curable layer.

These are used in the curable composition in an amount of about 1 to 50 wt%. Examples of binders include styrene-butadiene copolymers, silicone resins, fluid resins, acid-modified polyvinyl chloride, polyvinylidene chloride, vinyl acetate copolymers, aldehyde-modified PVA, imbutylene copolymers,
Examples include novolac, cellulose, cellulose acetate, cellulose butyrate, chlorinated rubber, gelatin, etc.
It is also possible to accelerate or increase removal after curing.

Electromagnetic waves or particle beams used for curing the curable composition include electron beams, gamma rays, X-rays, and general low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps,
Examples include xenon lamps, metal halide lamps and laser beams. 300nm to 400nm for convenience
It is preferable to use a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or a metal halide lamp that emits nearby ultraviolet rays as the light source.

The curable composition can be developed with a solvent or, optionally, an aqueous alkaline solution. The solvent was mentioned earlier. As the alkali, for example, a 0.1 to 10% by weight aqueous solution of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, ammonia, etc. can be used, but in some cases, Amines, such as primary amines such as butylamine, hexylamine, benzylamine, allylamine, secondary amines such as diethylamine and benzylethylamine, tertiary amines such as triethylamine, ethanolamine, jetanolamine, triethanolamine, 2-amino -hydroxylamine such as 1,3-propanediol,
Cyclic amines such as morpholine, pyridine, piperazine and piperidine; polyamines such as hydrazine, ethylenediamine and hexamethylenediamine; basic salts of the above amines such as sulfates, carbonates, bicarbonates, alkali metal phosphates and pyrophosphates; , tetramethylammonium hydroxide, quaternary ammonium salt hydroxide such as choline, etc. can also be used.

Further, after the point bonding, the curable resin composition may be post-cured by heat treatment if necessary.

For the heat treatment in curing before exposure and post-curing, a heating device such as a hot air circulation drying oven or a far-infrared drying oven can be used.

The present invention will be described in detail with reference to Examples below.

Synthesis Example 1.2 180 ml of dioxane, 0.1 mol of cinnamoyloxyethyl methacrylate, 0.08 mol of bivylphenol, and 0.1 mol of 2-methoxypropyl methacrylate (Example 1) and a catalytic amount of 7zobisisobutyrohale. 6 using loronitrile and passing nitrogen gas according to the usual method.
A copolymer was obtained by stirring at 5 to 78 degrees for 6.5 hours.

Conversion was approximately 85%. A similar operation was performed using the following monomer.

Acetoacetoxyethyl methacrylate 0.02 mol,
α-cyanocinnamoyloxyethyl methacrylate)
0.12 mol, cinnamoyloxypropyl methacrylate 0.04 mol, 7cetoacetoxyethyl methacrylate 0.08 mol and methyl methacrylate Ol
01 mol (Example 2).

In this way, a copolymer with a curable functional group was obtained. These are referred to as polymers 1 and 2, respectively.

These are copolymers that have both a photocurable unsaturated fatty acid derivative site and an ether site that contributes to adhesion.

Examples 1 to 2 Each of the polymers obtained in Synthesis Examples 1 and 2 having a cinnamic acid derivative moiety as a photocurable group in the side chain was added with 8% of a sensitizer (N-methylbenzoylmethylenenaphthothianphosphorus). ) was added and dissolved in a very small amount of heated DMF.

The thus obtained photocurable polymer composition was sandwiched between glass plates with a gap of 2 microns.

From a distance of 3 cm using a 400W high pressure mercury lamp,
It was irradiated for 2 minutes. It was confirmed that the exposed area did not peel off even after rinsing with a solvent (methanol/ethyl acetate mixture) and was firmly adhered.

On two 1.1 mm thick glasses patterned with TO, 5i085 degree oblique evaporation MW was applied to a film thickness of 50 parts m.
Furthermore, the above photocurable polymer composition was applied onto one of the deposited films to a thickness of 2 microns.

The other glass plate was bonded together and exposed in a dot pattern from a distance of 15 cm using a 400 W high pressure mercury lamp. The unexposed areas were washed away with a mixed solvent of methanol and ethyl acetate. The two glass plates were firmly glued together. Note that the diameter of the dotted pattern was 3 microns on average.

Ferroelectric liquid crystal CS+O23 manufactured by Chisso Corporation was injected into the cell thus prepared at 105° C., and then slowly cooled to room temperature, resulting in good alignment. Incidentally, when the cells were formed, the deposition direction of the obliquely deposited film was made to be parallel to the two glass plates.

Synthesis Example 3 50 parts of a phenol novolac type epoxy resin with an epoxy equivalent of 180 (manufactured by Dow Chemical Co., Ltd., E, N43B),
77.1 parts of equimolar reaction product of phthalic anhydride/2-hydroxyethyl acrylate (1.05 parts based on the epoxy group)
equivalent), 2-hydroxyethyl 7-acrylate 6.51 (
0.63 parts of benzyltriethylammonium chloride, and 0.089 parts of hydroquinone were dissolved in 3 parts of carpitol acetate (75°) and stirred at 80°C for 8 hours.

To this reaction product, 41.4 parts of tetrahydrophthalic anhydride (0.98 equivalents based on the epoxy group) was added, and the mixture was further stirred at 80°C for 2.5 hours to form a photocurable composition 3. A solution was obtained.

The weight average molecular weight of this photopolymerizable compound was 5180 in terms of polystyrene.

Synthesis Example 4 2-Hydroxyethyl acrylate of Synthesis Example 3 6.5
3 parts of 75° carpitol acetate was added to 72.
A solution of photocurable composition 4 was obtained in the same manner as in Synthesis Example 3 except that the amount was changed to 5 parts.

This weight average molecular weight was 27,440 in terms of polystyrene.

Synthesis Example 5 Phenol novolac type epoxy resin with epoxy equivalent weight 176 (Epiclon N-730S manufactured by Dainippon Ink Co., Ltd.) 50
parts, 78.8 parts of equimolar phthalic anhydride/2-hydroxyethyl acrylate reaction product (1 part per epoxy group)
．． 05 equivalents), 2-hydroxyethyl 7-acrylate 6.
6 parts (0.2 equivalents relative to the epoxy group), 0.65 parts of benzyltriethylammonium chloride, and 0.09 parts of hydroquinone were dissolved in 5 parts of carpitol acetate at 76°, and photocured in the same manner as in Synthesis Example 3. A solution of composition 5 was obtained.

This weight average molecular weight was 2110 in terms of polystyrene.

Synthesis Example 6 2-Hydroxyethyl acrylate of Synthesis Example 5 6.6
5 parts of carpitol acetate was added to 73.5 parts of carpitol acetate.
A solution of photocurable composition 6 was obtained in the same manner as in Synthesis Example 5 except that the amount was changed to 7 parts.

Examples 3 to 6 Photosensitive liquids M1 to M4 and thermosetting liquid N were prepared using the compounds shown in Synthesis Examples 3 to 6 according to the following formulations.

Photosensitive liquid M> 70% by weight carpitol acetate solution of photocurable composition (350 parts), Floren rAC-3 [10J (
15 parts, antifoaming agent manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.), Irgacure 907 (27.5 parts, photopolymerization initiator manufactured by Ciba Geigy) 1-benzyl-2-methylimidazole (
10 parts) Thermosetting liquid N〉 Triglycyl iso-7-nure-1- (100 parts) Dipentaerythritol hexaacrylate (36 parts) Cellosolve acetate (50 parts) Above photosensitive liquid M, thermosetting liquid N were separately kneaded using a roll mill to prepare an ink.

Next, the photosensitive liquid M and the thermosetting liquid N were kneaded to obtain a photocurable composition.

When these photosensitive resin compositions were used and irradiated in the same manner as in Example 1, the irradiated areas remained and showed strong adhesion. On the other hand, the unirradiated parts could be easily removed.

Preferred embodiments of the present invention are as follows.

(1) A method for forming a cell according to the claims, characterized in that the adhesion is performed using a photocurable composition, and the curable group is an unsaturated fatty acid derivative.

Claims (1)

[Claims] A transparent electrode and an alignment film may be provided on the surface.
A photocurable composition or a photocurable composition layer containing spacer particles is provided between two substrates, at least one of which is transparent, and is irradiated with electromagnetic waves or particle beams in a desired pattern. A cell manufacturing method characterized by developing and removing an uncured photocurable composition in an irradiated area.