JPH0227317A - Liquid crystal color display device - Google Patents

Abstract

PURPOSE:To obtain a laminated structure which is excellent and satisfactory in a protective performance such as a heat resistance, a chemical resistance, etc., by using a photosetting type resin which has brought a coating agent of a photopolymerization setting phosphagen compound for a protective film of a filter. CONSTITUTION:On a dyeing substrate 2 which works as a color filter, a protective film 1 consisting of a photosetting type resin which has brought a coating agent whose main agent is a photopolymerization setting phosphazene compound to photopolymerization setting is formed. The photopolymerization setting phosphagen compound uses that which is shown by [NP (X)p (Y)q]n. (In the expression, X and Y denote a polymerization setting radical or a non- polymerization setting radical, respectively, it will suffice that they are the same or different from each other, but at least one of them is a polymerization radical, (p) and (q) are the numbers >=0 and its sum is 2, and (n) is an integer >=3).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a liquid crystal color display device having a dyed substrate as a color filter and a protective film provided on the dyed substrate.

[Prior Art] As a means of colorizing a liquid crystal display element, one of the two substrates sandwiching the liquid crystal, 1 usually on the opposite electrode side of the pixel electrode (i.e. 1 usually on the common electrode side). , as color filters, usually red (R), green (G) and blue (
B) Each base color such as the three primary colors is finely and regularly, for example,
By providing a dyed substrate arranged in stripes, dots, mosaics, etc., and operating the transparent electrode film pattern and liquid crystal cell as light shutters corresponding to the base color arrangement of the dyed substrate, each of the three primary colors can be dyed. A method is widely used in which base color display is independently controlled and an image of a desired color is displayed by monochromatic or combined color mixture of each of the three primary colors.

In this type of liquid crystal color display device, ■I
When disposing a transparent conductive oxide film such as a TO film as a transparent electrode film by sputtering, vapor deposition, etc.,
The temperature is about 200°C, so depending on the conditions such as this high temperature or the conditions when forming the liquid crystal alignment film,
Deterioration due to peeling or cracking of the dyed substrate or loss of color of its base color; ■ Depending on the film thickness of each base color of the dyed substrate (usually the three primary colors R, G, and B), the surface of the dyed substrate or its surface may deteriorate. A step is formed between the substrate surface and the substrate surface, which causes alignment defects of the liquid crystal.
o#g! There are problems such as damage caused by chemicals such as acids, alkalis, and various cleaning solvents used when creating patterns of transparent electrode films such as the above.

Therefore, a protective film is generally provided on the dyeing substrate.

This I11 film protects the dyed substrate and solves problems such as (1) and (2) above, flattens the steps mentioned above, solves the problem (2), and also protects the dyed substrate and substrate surfaces such as glass substrates. Methods have been used to improve the adhesion of the laminated structure while improving the adhesion of transparent organic resins, (ii) metal oxides such as silicon dioxide, and (i)
ii) The use of ladder-type polysiloxanes having organic groups (see JP-A-61-3120) has been considered.

However, in the case of (i) acrylic resin, the heat resistance is poor, so the acrylic resin itself, which is a protective film, deteriorates due to heating when forming transparent electrode films and alignment films, and the dye base color of the dyeing substrate decreases in color. Otherwise, there are problems such as cracks occurring in the dyed substrate.

In addition, in the case of the silicon dioxide film described in (2) above, high temperatures are required during film formation, and therefore, there are problems such as color reduction of the dye base color and generation of cracks, as in the above case.

On the other hand, in the case of the ladder-type polysilochisane (iii) above, the color reduction of the dye base color of the dyed substrate and the occurrence of scratches are considerably suppressed. However, since it is a thermosetting protective film, if there is no curing catalyst for forming the protective film,
A high temperature of 0 to 350° C. is required, and as mentioned above, color reduction or cracking of one dye may occur.

Furthermore, when curing at low temperatures (below 150°C), a curing catalyst is required, but the amount and type of this catalyst as well as the curing temperature have a great effect on the physical properties.
Cracks often occur on themselves.

Further, when the coating film thickness is 2 square meters or more, it is extremely difficult to obtain a uniformly cured protective film that does not cause scratches, resulting in problems such as poor manufacturing efficiency and yield.

In addition, in conventional liquid crystal color display devices with a protective film, the unevenness caused by the arrangement of each base color of the dyed substrate is generally not sufficiently flattened by the provided protective film, and it is difficult to eliminate alignment defects of the liquid crystal. There were also problems, such as the fact that there were many cases where this was not achieved.

[Problems to be Solved by the Invention] The purpose of the present invention is to solve the above-mentioned problems, and to provide a material that has excellent protective properties such as heat resistance, chemical resistance, and strength, has high light transmittance, and has good insulation properties. Moreover, it is possible to obtain a fine layer structure with excellent adhesion to the dyed substrate, its substrate, the transparent electrode film corresponding to the dyed substrate, the liquid crystal layer or its alignment film, etc., and has excellent film formability. It has a protective film that has excellent properties such as being able to be formed in a short time under mild conditions. It has excellent effects such as preventing deterioration such as color reduction of the dye base color of the dyed substrate and generation of cracks during the formation of dyed substrates, etc., and also sufficiently flattening the unevenness of the dyed substrate and preventing alignment defects of liquid crystal. is,
Furthermore, it is an object of the present invention to provide a liquid crystal color display device which has the advantage that an M retaining film can be produced in a shorter time than a conventional liquid crystal color display device with a protective film.

[Means for Solving the Problems] In order to solve the above-mentioned problems in a liquid crystal color display device having a dyed substrate as a color filter, the present inventor has conducted extensive research on a protective film for the dyed substrate to be coated on the dyed substrate. As a result of repeated efforts, the above problems can be easily solved by using a specific photocurable resin or its composition obtained by photopolymerizing and curing a coating agent containing a photopolymerizable curable phosphazene compound as an i-retaining film. Based on this knowledge, we have completed the present invention.

That is, the present invention provides a liquid crystal color display device having a dyed substrate as a color filter, in which a photocurable resin is formed by photopolymerizing and curing a coating agent containing a photopolymerizable phosphazene compound as a main ingredient on the dyed substrate. A liquid crystal color display device characterized by being provided with a protective film.

It is more than that.

Hereinafter, two liquid crystal color display devices of the present invention will be described in detail with reference to the drawings.

FIG. 1 is a sectional view schematically showing an example of the liquid crystal color display device of the present invention and an example of light irradiation used when using the same.

In FIG. 1, l is a protective film, 2 is a dyeing substrate R, G, and B, and R, G, and B each represent the three primary colors used as an example of the Great Buddha of the dyeing substrate 2, that is, red, green, and blue. 3 and 3'(3a',3b') are
4 and 4' are transparent electrode films that face each other, 5 and 5' are alignment films, 6 is a liquid crystal, and 7 and 7' are polarizing films that face each other. 8 represents the irradiation light.

One of the important points in the liquid crystal color display device of the present invention is that, as illustrated in FIG. The point is that a protection W11 made of a photocurable resin obtained by polymerization and curing is provided.

Regarding other aspects of the present invention, there are no particular limitations, and a structure similar to that of a conventional liquid crystal color display device or a similar liquid crystal color display device that performs color display using the same operating principle can be adopted. ,or,
A desired liquid crystal cell configuration based on this can be adopted.

In addition, the dyeing substrate 2 used, substrates 3 and 3', transparent electrodes 115I4 and 4', orientation @5 and 5', liquid crystal 6
, and the materials of the polarizing films 7 and 7' are not particularly limited, and any desired materials such as known materials may be appropriately selected and used.

Specific examples of some of these are as follows.

The transparent electrode films 4 and 4' each include, for example, I
Optically transparent conductive oxide films such as TO films and tin oxide films,
Vapor-deposited metal thin films such as gold thin films can be suitably used, and in particular, ITO films and the like can be suitably used.

Examples of the substrates 3 and 3' include various single-layer substrates such as glass substrates and transparent plastic substrates, and multilayer substrates formed by laminating these substrates.

In addition, in the liquid crystal color display device illustrated in FIG.
As a preferred example, the substrate 3 and the substrate 3' are shown as single-layer and two-layer substrates, respectively, but the present invention is not necessarily limited to these, and a desired layer configuration can be appropriately selected. can do.

In the example shown in FIG. 1, a glass substrate, for example, is particularly preferably used as the substrate 3.

On the other hand, as the substrate 3', for example, a laminated substrate in which 3a' is a glass plate and 3b'' is a TPT (thin layer transistor) is particularly preferably used.

The dyeing substrate 2 is made of a water-soluble organic resin such as polyvinyl alcohol, gelatin, etc., depending on the material of the substrate 3 to be used and the type of dye to be disposed as a large Buddha, on the entire surface of the substrate 3 or on a predetermined portion of the surface. A suitable adhesive layer may be formed thereon, and a predetermined daibutsu may be provided thereon in a predetermined arrangement pattern, for example by dyeing with dyes of the three primary colors of red, green and blue or a composition thereof; Alternatively, if the dye (pigment) or its composition used has sufficient adhesion to the substrate to which it is applied, the dye (pigment) or its composition is applied directly onto the surface of the substrate 3. Similarly to the above, the large Buddha statues may be arranged in a predetermined pattern.

As a specific example of the method for forming the dyed substrate 2 in the latter case, for example, a glass substrate is used as the substrate 3, and a thin film of, for example, titanium dioxide or silicon dioxide is formed on the surface of the glass substrate in a pattern forming a predetermined filter arrangement. Another example is a method of dyeing red, green, and blue with predetermined Daibutsu dyes (pigments) such as the three primary colors.

The liquid crystal 6 may be, for example, various low-molecular liquid crystals, polymer liquid crystals that form various liquid crystal phases such as nematic phase, smectic A phase, smectic C phase, cholesteric S phase, chiral smectic C phase, or these. Examples include mixtures or compositions.

In the liquid crystal color display device of the present invention, as the protective film 1,
It can be obtained in the same manner as a normal liquid crystal color display device, except for using a photocurable resin or a composition thereof obtained by photopolymerizing and curing a coating agent containing a photopolymerizable curable phosphazene compound as a main ingredient. Mainly, this protective film 1 and a suitable method for manufacturing it will be explained in detail.

In the liquid crystal color display device of the present invention, the protection! 11
can be formed using a coating agent containing one or more types of photopolymerizable curable phosphazene compounds described below.

In addition, in order to promote photopolymerization and curing, it is usually preferable to use this coating agent with a suitable photopolymerization initiator mixed therein.

The coating agent may optionally contain a photopolymerizable monomer such as a photopolymerizable curable phosphazene compound and a photocopolymerizable durable polyfunctional acrylic monomer or methacrylic monomer, or oligomers or methacrylic monomers thereof, as desired. Other photopolymerizable curable components such as prepolymers, photosensitizers, diluents such as solvents, or various other additives may be appropriately blended or added for use.

By using these photopolymerizable curable components, photosensitizers, solvents, or additives, it is possible to further improve the workability for forming a protective film and the mechanical and thermal properties of the resulting protective film. I can do it.

As a photopolymerizable curable phosphazene compound, the general formula % formula % (1) (However, X and Y in formula 1 are each a polymerizable curable group or a non-polymerizable curable group, and they may be the same. and may be different from each other, at least one of which is a polymerizable curable group, p and q are each a number of 0 or more, their total is 2, and n is an integer of 3 or more). Compounds that can be used can be used.

The polymerization-curable group in the general formula CI) is not particularly limited as long as it is a group having an unsaturated bond that can be polymerized by irradiation with light having polymerization-curing ability such as ultraviolet rays, but examples include acrylic groups, methacrylic groups, vinyl group, allyl group, etc., specifically, for example, the following general formula (II
Examples include groups represented by any of a) to (IIf).

CH2= CR' COO-Y -0-(■a) CH2
=CRI C0NH-Y-0-(II b)CH2=C
RI C0NH-(II c) (n f) (However, RI in the formula represents a hydrogen atom or a methyl group, Y represents a linear or branched fullkylene group having 1 to 12 carbon atoms, and l(2 or , J-1/R3 are each independently a hydrogen atom or a carbon lI [representing a 1-4 linear or branched alkyl group] rm specific example of a group represented by formula (II a) Examples include 2-acryloyloxyethoxy group, 3-acryloyloxypropoxy group, 4-acryloyloxybutoxy group, ?-acryloyloxy-1-methylethoxy group, 2-acryloyloxy-1-ethylethoxy group, 3-acryloyl Oxy-1-methylpropoxy group, 5-acryloyloxypentyloxy group, 6-acryloyloxyhexyloxy group, 5-acryloyloxy-1-methylpentyloxy group, 6-acryloyloxy-4-methylhegycyloxy group, 3- Acryloyloxy-2-tert
-butylpropoxy group, 3-acryloyloxy-2゜2-dimethyl-1-propylpropoxy group, 3-acryloyloxy-2-methylpropoxy group, 3-acryloyloxy-2-ethylpropoxy group, 3-acryloyloxy-2 , 2-dimethylbutoxy group, 8-acryloyloxyoctyloxy group, lO-acryloyloxydecyloxy group, 12-7 acryloyloxydodecyloxy group, ? -methacryloyloxyethoxy group, 3-
Methacryloyloxypropoxy group, 4-methacryloyloxybutoxy group, 2-methacryloyloxy-1-
Methyl ethoxy group, 2-methacryloyloxy-1-ethylethoxy group, 3-methacryloyloxy-1-methylpropoxy group, 5-methacryloyloxypentyloxy group, 6-methacryloylhexyloxy group, 5-methacryloyloxy-1-methylpentyl Oxy group, 6
-methacryloyloxy-4-methylhexyloxy group, 3-methacryloyloxy-2-tert-butylpropoxy group, 3-methacryloyloxy-2,2-dimethyl-1-propylpropoxy group, 3-methacryloyloxy-2- Methylpropoxy group, 3-methacryloyloxy-2-ethylpropoxy group, 3-methacryloyloxy-2,2-dimethylbutoxy group, 8-methacryloyloxyoctyloxy group, 10-methacryloyloxydecyloxy group, 12-methacryloyldodecyloxy group etc. can be mentioned.

Specific examples of the group represented by the formula (n b) include 2-7 acryloylaminoethoxy group, 3-acryloylaminopropoxy group, 4-acryloylaminobutoxy group, 2-acryloylamino-1-methyl Ethoxy group, 2-acryloylamino-1-ethylnioxy group, 3-acryloylamino-1-methylpropoxy group,
5-acryloylaminopentyloxy group, 6-acryloylaminohexyloxy group, 5-acryloylamino-1-methylpentyloxy group, 6-acryloylamino-4-methylhexyloxy group, 3-acryloylamino-2-tert-butyl Propoxy group, 3-acryloylamino-2゜2-dimethyl-1-propylpropoxy group, 3-acryloylamino-2-methylpropoxy group.

3-acryloylamino-2-ethylpropoxy group, 3
-acryloylamino-2,2-dimethylbutoxy group,
8-acryloylaminooctyloxy group, lO-acryloylamino-7decyloxy group, 12-acryloylaminododecyloxy group, 2-methacryloylaminoethoxy group, 3-methacryloylaminopropoxy group, 4
-methacryloylaminobutoxy group, 2-methacryloylamino-1-methylethoxy group, 2-methacryloylamino-1-ethylethoxy group, 3-methacryloylamino-1-methylpropyloxy group, 5-methacryloylaminopentyloxy group, 6 -methacryloylaminohexyloxy group, 5-methacryloylamino-1-methylpentyloxy group, 6-methacryloylamino-4
-Methylhexyloxy group, 3-methacryloylamino-2-tert-butylpropoxy group, 3-methacryloylamino-2,2-dimethyl-1-propylpropoxy group, 3-methacryloylamino-2-methylpropoxy group, 3-methacryloyl Amino-2-ethylpropoxy group, 3-methacryloylamino-2,2-dimethylbutoxy group, 8-methacryloylaminooctyloxy group, 10-methacryloylaminodecyloxy group, 12
-methacryloyl aminododecyloxy group, etc.

Specific examples of the group represented by the formula (IIc) include an acryloylamino group and a methacryloylamino group.

Specific examples of the group represented by the formula (nd) include allyloxy group, l-methyl-7lyloxy group,
2-methyl-allyloxy group, 2,2-dimethyl-allyloxy group, l, 2゜2-trimethylallyloxy group,
Examples include 1.2-dimethylallyloxy group, l-ethylallyloxy group, 1-butylallyloxy group, and l-propylaryloxy group.

Specific examples of the group represented by the formula (II e) include 4-allylphenoxy group, 37allylphenoxy group, 2-allylphenoxy group, 4-(2-methylallyl)phenoxy group, 3-(2- Mention may be made of the methylallyl)phenoxy group and the 2-(2-methylallyl)phenoxy group.

Specific examples of the group represented by the formula (II f) include 4-allyloxycarbonylphenoxy group, 3
-allyloxycarbonylphenoxy group, 2-allyloxycarbonylphenoxy group, 4-(2-methylallyloxycarbonyl)phenoxy group, 3-(2-methylallyloxycarbonyl)phenoxy group and 2-(2-
Mention may be made of the methylallyloxycarbonyl) phenoxy group.

On the other hand, examples of the non-polymerizable curable group include groups represented by the following general formula (m a) or (mb).

11i4 Q- (I[ra) [However, Q in the formula is an oxygen atom, a sulfur atom, or -
NH- group; R4 is a linear or branched alkyl group having 1 to 18 carbon atoms or a halogenated alkyl group;
or represents a halogen atom, R5 represents a linear or branched alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group, or a halogen atom, and k represents an integer of θ to 5; (mb), R5 substituted with the benzene ring may be the same or different.] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. I can do it.

Specific examples of the group represented by the formula (Ha) include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, octyloxy group, decyloxy group, dodecyloxy group, hegycyloxy group. group, octyloxy group, impropoxy group, l-
Methylpropoxy group, 2-methylpropoxy group, 2,2
-dimethylethoxy group, 3-methylbutoxy group, 2-methylbutoxy group e4-methylpentyloxy group, l-methylbutoxy group, -methylpentyloxy group, l-methylhebutyloxy group, methylthio group, ethylthio group,
Propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, hexylthio group, octylthio group, 2-methylethylthio group, 1-methylpropylthio group, 2-methylpropylthio group, 2, 2-dimethylethylthio group, 3-
Methylbutylthio group, 2-methylbutylthio group, 4-methylpentylthio group, l-methylbutylthio group, ■-methylpentylthio group, l-methylhebutylthio group, methylamine group, ethylamino group, propylamino group group, butylamino group, pentylamino group, hexylamino group, octylamino group, decylamino group, dodecylamino group,
hexylamino group, octylamino group, 2-methylethylamino group, l-methylpropylamino group, 2-methylpropylamino group, 2,2-dimethylethylamino group,
3-methylbutylamino group, 2-methylbutylamino group, 4-methylpentylamino group, l-methylbutylamino group, l-methylpentylamino group, ■-methylhebutylamino group, chloromethoxy group, dichloromethoxy group ,
Examples include 2-chloroethoxy group, l-chloroethoxy group, 3-chloropropoxy group, 2-chlorobutoxy group, 5-chloropentyloxy group, and 6-chlorohexyloxy group.

Specific examples of the group represented by the formula (mb) include phenoxy group, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, dimethylphenoxy group, trimethylphenoxy group, and ethylphenoxy group. , propylphenoxy group, butylphenoxy group, chlorophenoxy group, dichlorophenoxy group, fluorophenoxy group, chloromethylphenoxy group, phenylthio group, 2-methylphenylthio group, 3-methylphenylthio group, 4-methylphenylthio group, dimethyl Phenylthio group, trimethylphenylthio group, ethylphenylthio group, propylphenylthio group, butylphenylthio group,
Chlorophenylthio group, dichlorophenylthio group, fluorophenylthio group, chloromethylphenylthio group, phenylamino group, 2-methylphenylamino group, 3-methylphenylamino group, 4-methylphenylamino group,
Examples include dimethylphenylamino group, trimethylphenylamino group, ethylphenylamino group, propylphenylamino group, butylphenylamino group, chlorophenylamino group, dichlorophenylamino group, fluorophenylamino group, chloromethylphenylamino group, etc. .

In the photopolymerizable curable phosphazene compound represented by the general formula (I), n is an integer of 3 or more, but n is 3 to 3.
18 are preferred, and 3 and 4 cyclic compounds, or a mixture thereof, are particularly preferred.

The photopolymerizable phosphazene compound described above can be produced according to a known method.

For example, hexachlorocyclotriphosphazene and 2-
By reacting with hydroxyethyl methacrylate, a phosphazene compound in which part or all of the chlorine of hexachlorotriphosphazene is substituted with a 2-hydroxyethyl methacrylate residue can be obtained. Here, it is preferable that all chlorine be replaced, but some chlorine may remain.

In this reaction, it is advantageous to use a tertiary amine in order to promote the dehydrochlorination reaction.

Examples of the tertiary amine include trimethylamine, triethylamine, triisopropylamine, tri-n-propylamine, tri-n-butylamine, and pyridine, among which pyridine is preferred.

Moreover, this reaction is usually carried out in an organic solvent.

Examples of the organic solvent used include benzene, toluene, xylene, chloroform, cyclohexane, methylene chloride, and tetrahydrofuran, which may be used alone or in combination of two or more.

In addition, in the present invention, the chlorophosphazene compound, which is the starting material for producing the phosphazene compound, is a trimer (hexachlorocyclotriphosphazene), a tetramer (octachlorocyclotetraphosphazene), or a dichlorophosphazene. , it is preferred to use oligomers thereof, since the phosphazene compounds obtained using such trimers, telomers or oligomers are
This is because the crosslink density in the protective film 1 (photopolymerized cured product of a phosphazene compound) can be easily controlled.

Specific examples of photocopolymerizable polyfunctional acrylic monomers that may be blended into the coating agent as desired include: 1, 1,3-butanediol diacrylate;

4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol diacrylate, hydroxypivalin Examples include difunctional compounds such as acid ester neopentyl glycol diacrylate, and trifunctional or higher functional polyfunctional compounds such as trimethylolpropane triacrylate, pentaerythritol acrylate, and dipentaerythritol hexaacrylate.

Specific examples of photocopolymerizable polyfunctional methacrylic monomers include 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1°6-hexanesiol dimethacrylate, ethylene glycol dimethacrylate, Difunctional compounds such as diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, polyethylene glycol dimethacrylate, hydroxypivalic acid ester neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol Examples include polyfunctional compounds having three or more chambers, such as methacrylate, dipentaerythritol hexamethacrylate, and the like.

The proportion of these photocopolymerizable multichamber acrylic monomers and methacrylic monomers used as components of the coating agent is usually 0 to 100 parts by weight per 100 parts by weight of the photopolymerizable curable phosphazene compound used. It is appropriate to keep it within this range.

The solvent used as a component of the coating agent, if desired, can be appropriately selected and used depending on the type of dyeing substrate to be used.

Specific examples of this solvent include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as chloroform and methylene chloride, methanol, ethanol, Examples include alcohols such as propatool and butamele, organic solvents such as ethers such as tetrahydrofuran and dioxane, and cellosolves such as ethyl cellosolve and butyl cellosolve. Each of these may be used alone, or
Two or more types may be mixed and used.

Among these, ketones, alcohols, or mixed solvents thereof are preferred, and methyl isobutyl ketone, isopropyl alcohol, or a mixed solvent with butyl alcohol is particularly preferred.

There is no particular limitation on the mixing ratio of these diluents and the phosphazene compound, but the weight ratio is usually 1.
=9 to 9:1. In particular, a composition in which an organic solvent and a phosphazene compound are mixed in a ratio of 9=1 to 5:5 has a viscosity in a good range and is suitable from the viewpoint of workability.

As a component of the coating agent, photopolymerization initiators that are usually used include, for example, when using a photopolymerization curing method using ultraviolet rays or visible light, -hydroxycyclohexylphenyl ketone, dibenzoyl, benzoin methyl ether. , benzoin ethyl ether, p
-chlorobenzophenone, p-methoxybenzophenone, 2゜2-dimethoxy-2-phenylacetophenone,
2-Methyl-[4-(methylthio)phenyl]=2-morpholino-1-propane, benzoyl peroxide, di-tert-butyl peroxide, camphoraquinone, and the like can be suitably used.

These photopolymerization initiators may be used alone or in combination of two or more, and their usage is 0.5 parts by weight per 100 parts by weight of the commonly used photopolymerizable curable compound.
-6 parts by weight.

Examples of the photosensitizer used as a component of the coating agent, if desired, include p-dimethylaminobenzoic acid esters.

Further, various additives that may be used as desired as components of the coating agent include, for example, plasticizers such as p-dimethylaminobenzoic acid, antioxidants, and the like.

In addition, the usage ratio of these photosensitizers and various additives is per 100 parts by weight of the photopolymerizable curable compound used.
It is appropriate that the total amount is usually within the range of 1 to 10 parts by weight.

In the liquid crystal color display device of the present invention, the protective film l can be formed as follows.

That is, in the present invention, the coating agent made of only the photopolymerizable curable phosphazene compound prepared as described above or the coating material made of the composition containing the photopolymerizable curable phosphazene compound is applied to the predetermined coating material. After coating a substrate by a conventionally known method, such as a spinner method, a spray method, a roll coater method, or a dipping method, if a solvent is used, the solvent is removed.

Next, the photopolymerizable phosphazene compound is cured by irradiation with ultraviolet rays, visible light, electron beams, X-rays, gamma rays, etc., and protected! Form ll.

Among these curing methods, a method of curing by photopolymerization by irradiating ultraviolet rays is preferred.

The calculated light amount of the irradiation light at this time is 1 t, ooo to 5.
000mj/crn'.

The ambient temperature in this photopolymerization curing treatment is usually about room temperature.

Note that, if desired, heat treatment and thermosetting treatment can also be used in combination.

The thickness of the protective film l cannot be uniformly defined because it varies depending on the thickness of the dyed substrate, etc., but it is usually 0. i
It is appropriate to set it within the range of p and m to 15 mm.

The protective film 1 thus formed has excellent protective properties such as heat resistance and chemical resistance, high light transmittance, and excellent insulation properties.

The dyeing substrate 2, its substrate 3, the transparent electrode film 4 corresponding to the dyeing substrate 2, the liquid crystal layer 6 or its alignment film 5, etc. have good adhesion, and a laminated structure with excellent adhesion can be obtained. In addition, it has excellent properties such as excellent film forming properties and can be formed in a short time under mild conditions.
In particular, deterioration such as color reduction and generation of cracks in the dyed substrate 2 during the formation of transparent electrodes WJ4, alignment [5, etc.] is prevented, and the unevenness of the dyed substrate 2 is sufficiently flattened to align the liquid crystal 6. It has excellent effects such as preventing defects and improving the adhesion of the laminated structure, and also has the advantage of being able to create a protective film in a shorter time than conventional LCD color display devices with a protective film. It is possible to realize a liquid crystal color display device having the following.

After forming the protective film 1 in this manner, the transparent electrode film 4 is provided using a known method as described above, and further, if desired, the orientation 111j5 is formed, and then the liquid crystal 6 A liquid crystal color display device having a desired structure, such as a liquid crystal color display device having the structure illustrated in FIG. 1, can be obtained by sandwiching the liquid crystal color display device between a laminated structure consisting of opposing substrates 3' and the like.

[Examples] (Production Example 1) Production of curable phosphazene compound (A) In a one-liter flask equipped with a thermometer, a stirring device, a dropping funnel, and a condenser, 58.0 g of hexachlorocyclotriphosphazene (hereinafter abbreviated as 3PNO) was added. g (0,167 mol),
50 layers of Tolu 1F and 158 g (2.0 mol) of pyridine were added, and stirring was started.

Next, 2-hydroxyethyl methacrylate (hereinafter referred to as HE
14.3 g (1.1 mol) of MA) was gradually added dropwise from the dropping funnel.

Heat the reaction to 60°C in a hot bath and continue the reaction with stirring.
Time went.

Next, the precipitated crystals and catalyst were separated by filtration, the solvent in the obtained filtrate was removed by distillation under reduced pressure, and the residue was sufficiently dried to obtain 138 g of a pale yellow liquid. The yield was 91%.

(Production Example 2) Production of curable phosphazene compound (B) 100 layers of tetrahydrofuran and 11.5 g (0.5 mol) of metallic sodium were charged into a 1 fL flask equipped with a thermometer, stirring device, dropping funnel, and condenser. did. In this reaction solution, 2.2° 2-trifluoroethanol 5
5.5 g (0.55 mol) was added dropwise, and the reaction was carried out under reflux until the sodium disappeared.

Next, a solution of 3P N C39,Eig (0,111 mol) dissolved in 100 ml of toluene was added dropwise to the above reaction solution, and the reaction was carried out under reflux for 2 hours.Then, the temperature of the reaction solution was brought to room temperature. Cooled to .

191 g (1.23 mol) of HEMA was gradually added dropwise to the colander from a dropping funnel.

The mixture was heated to 60° C. in a hot bath, and the reaction was heated and stirred for 8 hours.

Next, the precipitated crystals and catalyst were separated by filtration, the solvent in the obtained filtrate was removed by distillation under reduced pressure, and the residue was sufficiently dried to obtain 88 g of a pale yellow liquid.

The yield was 93%.

Composition of 2 lambda cloth solution (a) Curable phosphazene compound (A) 75 parts by weight Polyfunctional acrylic monomer 25 parts by weight m2-Methyl [
4-(Methylthio)phenyl]-2-morph Rino 1
-3 parts by weight of propanone 3 parts by weight of p-dimethylaminobenzoic acid ethyl ester Solvent 400 parts by weight of dicarpitol mixed solvent Composition of coating liquid (b) Curable phosphazene compound (B) 50 parts by weight Polyfunctional crylic monomer sowia2- Methyl-[
4-(methylthio)phenylgo-2-morpholino-1
- 3 parts by weight of propanone 3 parts by weight of p-dimethylaminobenzoic acid ethyl ester Solvent: 400 parts by weight of cellosolve acetate mixed solvent (Example 1) Stripes in three colors of R, G, and B were printed on a glass substrate by a printing method. A patterned dyed substrate was formed. Thereafter, the coating liquid (a) was applied by a printing method, heat treated at 60° C. for 30 seconds, and then UV irradiated (1 to 3 seconds) to form a protective film.

According to the measurement with a surface roughness meter, there was no height difference of 150 or more. Further, the film thickness from the glass substrate was 0.71 mm.

A transparent electrode was formed on this by sputtering to form a film of 500 mm thick.

Next, a polyimide forming solution was applied as an alignment control film onto the transparent electrode using a spinner, and heated at 150° C. for 30 minutes to form a polyimide film with a thickness of 0.2 mm. Thereafter, this polyimide film was subjected to a rubbing treatment.

This substrate and a counter substrate were bonded together to form a cell, and 1M of liquid crystal (ZLI-1848, manufactured by MERCK) was injected to form a liquid crystal element.

When this liquid crystal element was observed with a crossed Nicol polarizing microscope, no alignment defects were found.

Further, even when polarizing films were attached to both sides of this element and a fluorescent lamp was irradiated from the opposite side, color shift and color mixing did not occur even when the driving operation was performed. Further, no fading was observed at all.

(Example 2) A color filter was prepared in the same manner as in Example 1, and coating liquid (b) was applied thereon using a spinner.

After heat treatment at 60° C. for 30 seconds, a protective film was formed by irradiating ultraviolet rays (1 to 3 seconds).

According to the measurement with a surface roughness meter, there was no height difference of 170 or more. Further, the film thickness from the glass substrate was 0.65 mm. Thereafter, a liquid crystal element was produced in exactly the same manner as in Example 1, but no liquid crystal alignment defects were found. Even when the driving operation was performed, no color shift or color mixing occurred. Further, no fading was observed at all.

[Effects of the Invention] According to the present invention, protection properties such as heat resistance, chemical resistance, strength, etc.
It has extremely high light transmittance, excellent insulation properties, and has good adhesion to the dyeing substrate, its substrate, the transparent electrode film corresponding to the dyeing substrate, and the liquid crystal layer or its alignment film. , has a protective film that has excellent properties such as being able to obtain a laminated structure with excellent adhesion, and having excellent film forming properties and being able to form a film in a short time under mild conditions, Said protection! I prevents deterioration such as peeling of the dyed substrate, color bleeding, color reduction of the dyed substrate during formation of transparent electrode films, alignment films, etc., generation of cracks, etc., and prevents unevenness of the dyed substrate sufficiently. It has excellent effects such as flattening the liquid crystal, preventing alignment defects in the liquid crystal, and improving the adhesion of the laminated structure.Furthermore, the protective film can be removed in a shorter time than in conventional protective film-equipped LCD color display devices. It is possible to provide a liquid crystal color display device having advantages such as being able to fabricate.

[Brief explanation of the drawing]

FIG. 1 is a sectional view schematically showing an example of a liquid crystal color display device of the present invention and an example of light irradiation used when using the same. l...Protective film, 2.φ.Staining substrate, R, G. B...Three primary colors used as an example of the color of the dyeing substrate 2, 3.3' (3a, 3b')z'' substrates facing each other, 4.4'...Transparent electrode films facing each other, 5
．． 5'.m-alignment film, 6...liquid crystal, 7.7'-...polarizing films facing each other, 8...irradiation light. Figure 1

Claims (1)

[Claims] (1) In a liquid crystal color display device that has a dyed substrate as a color filter, a protective film made of a photocurable resin made by photopolymerizing and curing a coating agent whose main ingredient is a photopolymerizable phosphazene compound is applied on the dyed substrate. A liquid crystal color display device characterized by: