JPH01144021A - Colored fine spherical body and liquid crystal display panel using said spherical body - Google Patents

Abstract

PURPOSE:To obtain a high-performance liquid crystal display panel by forming colored layers on the outside peripheral faces of fine spherical bodies of a crosslinked high polymer dyed by a treatment with an acid. CONSTITUTION:This display panel is constituted by having a pair of substrates 1, 1 with electrodes which are formed of transparent glass plates, etc., and are disposed to have a prescribed spacing so as to dispose the electrode surfaces 10 provided on the inner surfaces to face each other, a sealing material 4 which is packed in the peripheral part between the two substrates 1 and 1 and closes the spacing in the peripheral part between the substrates 1 and 1, spacers 2 which are interposed between the substrates 1 and 1 and control the spacing between the substrates 1 and 1 and a liquid crystal compsn. 3 which is packed in the spacing between the substrates 1 and 1. Plural pieces of the colored fine spherical bodies 2 as spacer are interposed between substrates 1, 1 except the peripheral part of the substrate 1 in the state of tight contact. These bodies 2 are formed by drying the crosslinked high polymer fin spherical bodies treated with acid. The high quality liquid cryptal display panel which has low transmittance on the dark filed in the state of non impression of voltage to the panel and has the excellent display contrast is thereby obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to colored microspheres whose surfaces are colored, and a liquid crystal display panel that provides high performance and high quality display using the colored microspheres.

(Prior Art) In general, a liquid crystal display panel requires two light-transmitting glass substrates to be held at a constant gap. In order to achieve this, a spacer made of microspheres with a constant diameter has conventionally been interposed between the glass substrates, and both glass substrates have been fixed in close contact with the spacer.

In addition, while the liquid crystal composition exhibits an optical change when a voltage is applied, the spacer does not exhibit an electro-optical change, and when the liquid crystal display panel is displayed, dots appear in the liquid crystal layer in the dark area. There is a problem in that the existing spacer is visually recognized as a bright spot. In particular, in negative-type black/white displays or LCD projectors that illuminate the LCD panel from the back side and enlarge and project the image displayed on the LCD panel onto the screen using a projection lens, the spacer portion is always white. There are visible flaws. In the case of a transmissive liquid crystal display element that is illuminated from the back, the entire element is black when no voltage is applied, so even extreme brightness and dots can be seen relatively clearly, resulting in the problem of a significant drop in display contrast. be.

In order to solve this problem, for example, Japanese Patent Laid-Open No. 57-18
9117 discloses the use of particulate colored spacers, and JP-A-62-38427 discloses the use of dyed particulate spacers or opaque particulate spacers, Furthermore, Japanese Patent Application Laid-Open No. 62-66228 discloses the use of a colored oxide spacer.

(Problems to be Solved by the Invention) However, each of the colored spacers currently on the market is slightly colored (dyed), and uncolored particles are mixed among the colored particles. Even if each colored (dyed) spacer was used as a spacer for a liquid crystal display panel, the above problems were not solved.

Moreover, when each of the above particulate spacers is interposed between a pair of substrates and both panels are pressed and fixed so that the gap between the side substrates is maintained constant, the average center of the many spacers interposed between the substrates is There is a drawback that the spacing accuracy of the substrates is reduced due to variations in diameter and the like.

In other words, when interposing a large number of granular spacers with a predetermined center particle diameter and standard deviation between the side substrates, the spacers shown in the above publications have poor deformability, so the variation in the center particle diameter of the spacers directly affects the distance between the substrates. This leads to precision and therefore creating a large number of LCD display panels.
Due to variations in the gap between the side substrates of the liquid crystal display panel,
A liquid crystal display panel with high substrate gap accuracy could not be obtained.

Moreover, among the large number of spacers, spacers with a particularly small particle size tend to move within the space between the side substrates and aggregate around the electrodes, and since the surface hardness of each spacer is high, There was a risk that spacers larger than the center particle size would be crushed.

The present invention solves the above-mentioned drawbacks, and its purpose is to:
It can be reliably colored to prevent dark and uncolored objects, and it can almost eliminate visible light transmittance, eliminating visibility in dark areas and providing high-contrast, high-performance liquid crystal display panels. The object of the present invention is to provide colored microspheres and a liquid crystal display panel using the colored microspheres.

Still another object of the present invention is to provide colored microspheres that can improve the gap accuracy between the substrates and prevent the spacer from moving within the space between the side substrates, and to provide a liquid crystal display panel using the colored microspheres. There is a particular thing.

(Means for Solving the Problems) The colored microspheres of the present invention are made by dyeing crosslinked polymer microspheres treated with acid, and a colored layer is formed on the outer peripheral surface of the crosslinked polymer microspheres. This achieves the above objective.

The liquid crystal display panel of the present invention includes a pair of substrates with electrodes, at least one of which is transparent, and which are disposed with a predetermined gap such that electrode surfaces provided on the side faces face each other, and a sealant that is filled in the peripheral portion of the substrate to close the peripheral gap between the substrates; a spacer that is interposed between the side substrates and regulates the gap between the side substrates; a liquid crystal display panel filled with a liquid crystal composition, wherein the spacer is formed by dyeing crosslinked polymer microspheres treated with acid, and a colored layer is formed on the outer peripheral surface of the crosslinked polymer microspheres. colored microspheres, thereby achieving the above object.

The present invention will be explained in detail below.

FIG. 1 shows a sectional view of essential parts of a liquid crystal display panel according to the present invention.

The liquid crystal display panel includes a pair of electrode-attached substrates 1.1 formed of transparent glass plates or the like and disposed with a predetermined gap such that electrode surfaces 10 provided on the inner surfaces thereof face each other, and a sealing material 4 filled in the peripheral portion between the substrates 1.1 to close the peripheral gap between the substrates 1.1; and the side substrate 1.1.
A spacer 2 is interposed between the side substrates 1.1 to regulate the gap between the side substrates 1.1, and a liquid crystal composition 3 is filled in the space between the side substrates 1.1.

The sealing material 4 is made of an epoxy resin, an ultraviolet curing resin, etc. containing uncolored crosslinked polymer microspheres 4a as spacers, and is applied to the periphery of at least one of the substrates 1, and then the side substrate 1.1 is pressure-bonded. Then, by curing the resin of the sealing material 4, the peripheral portion of the side substrate L1 can be closed with a predetermined gap. Further, a large number of colored microspheres 2 as spacers are interposed between the side substrates 1.1 excluding the peripheral portion of the substrate 1 in close contact with the inner surface of the substrate 1. The colored microspheres 2 are formed by dyeing crosslinked polymer microspheres treated with acid.

Next, a method for manufacturing the colored microspheres 2 will be explained. The colored microspheres 2 are produced by polymerizing a monomer having an ethylenically unsaturated group to create polymer microspheres, then treating the polymer microspheres with an acid, and then dyeing them.

The monomer having an ethylenically unsaturated group is composed only of a monomer having two or more ethylenically unsaturated groups, or composed only of a monomer having one ethylenically unsaturated group. Alternatively, it can be composed of a monomer having two or more ethylenically unsaturated groups and a monomer having one ethylenically unsaturated group copolymerizable therewith. In particular, the monomer having two or more ethylenically unsaturated groups is
It is preferable to use at least 10% by weight, especially at least 10% by weight. When the amount of the monomer having two or more ethylenically unsaturated groups added is less than 5% by weight based on the total amount of the monomer having two or more ethylenically unsaturated groups, the resulting polymer microspheres The hardness is low, and polymer microspheres may not be dyed in a deep color.

Examples of the monomer having two or more ethylenically unsaturated groups include the monomers shown in (1) to (4) below.

■X methylol alkyl (meth)acrylate (however,
X and y are integers that satisfy the condition of X≧y≧2). Specifically, tetramethylolmethanetetra(meth)acrylate, tetramethylolmethanetri(meth)acrylate, tetramethylolmethanedi(meth)acrylate, trimethylolpropanetri(meth)acrylate,
dipentaerythritol hexa(meth)acrylate,
Examples include dipentaerythritol penta(meth)acrylate and glycerol tri(di)(meth)acrylate.

■Polyoxyalkylene glycol di(meth)acrylate. Specifically, polyethylene glycol di(meth)
Examples include acrylate, polypropylene glycol di(meth)acrylate, etc.

■Triaryl(iso)cyanurate, triaryltrimelite, etc.

■Divinylbenzene, diaryl phthalate, diarylacrylamide, etc.

Examples of monomers having one ethylenically unsaturated group that can be copolymerized with the above-mentioned monomers having two or more ethylenically unsaturated groups include styrene, vinyltoluene, acrylonitrile, and alkyl (meth)acrylates. Examples include esters, vinyl ester L (meth), acrylic acid, hydroxyalkyl (meth)acrylate, (meth)acrylamide, N-methylol (meth)acrylamide, NN-dimethylaminopropylacrylamide, and the like.

Polymer microspheres can be produced by polymerizing each of the above monomers in the presence of a radical catalyst. This polymerization is preferably carried out at a temperature below the boiling point of the dispersion medium and each monomer. As the radical catalyst that can be used, organic peroxides and radical-generating catalysts in general such as azo compound rings are preferably used. Examples of the organic peroxide include benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, and the like. As an azo compound, for example, 2.2'
Examples thereof include 6J azobisisobutyronitrile, 2,2'Q azobis(2,4dimethylvaleronitrile), and the like.

Next, the polymer microspheres thus obtained are treated with acid under predetermined treatment conditions. Acid treatment conditions range from room temperature to
It can be carried out at 200°C and at a bath ratio of 1:2 to 1:50. Examples of acid treatment agents include concentrated sulfuric acid, fuming sulfuric acid, sulfur dioxide, sulfurous acid, sulfites, bisulfite, sulfonyl chloride, chlorosulfuric acid, fluorosulfuric acid, and aminosulfonic acid, and at least one selected from these groups. More than one type can be used.

By treating the polymer microspheres with acid in this way, the acid causes an addition reaction with the unreacted ethylenically unsaturated groups remaining in the polymer microspheres, and/or a substitution reaction with the acid on the polymer microspheres. As a result, the acid becomes chemically bonded to the polymer microspheres. In particular, by producing polymer microspheres using a large amount of a monomer having two or more ethylenically unsaturated groups, the above acid can be added to the ethylenically unsaturated groups remaining in the polymer microspheres using sulfonic acid. As an ester, it can be reacted under relatively mild processing conditions. Furthermore, when polymer microspheres are produced using a monomer having an aromatic nucleus, sulfonic acid groups can be introduced by a sulfonation reaction of the aromatic nucleus of the polymer microspheres.

Next, the polymer microspheres treated with acid as described above are dyed. The dyeing conditions include a dye concentration of 0.5 to 5.
wt%, acetic acid vinegar and acid soda to pH 2-6 of the staining solution.
Adjust the bath ratio to 1:30 to 1:10 and the treatment temperature to 60 to 1.
The treatment can be carried out at 20° C. for a treatment time of 30 minutes to 15 hours. As the dye used, for example, a basic dye that can chemically bond with the acid bonded to the polymer microspheres is preferably used. This basic dye is primarily a hydrochloride of an aromatic base containing a chromophore. Basic groups include amino group (-NH2), alkylamino group (-N (CH3
)Z), etc. It does not contain acidic groups and the dye ions become cations in an aqueous solution. Specific examples include triphenylmethane type, anthraquinone type, azo type, methine type, and oxazine type.

Through this dyeing process, the basic dye is ionically bonded to the sulfonic acid groups in the polymer microspheres. Thereafter, colored microspheres 2 are obtained by filtering and washing. This operation removes residual dye and inorganic salts produced as by-products of the dyeing process. Therefore, the colored microspheres 2 can be obtained in a pure form that does not contain any impurities as well as alkali metals. In addition, since the dye is chemically bonded to the polymer microspheres, even a small amount of dye can be uniformly and deeply colored, and
It also has excellent solvent resistance.

The colored microspheres 2 obtained as described above are filled between a pair of substrates 1.1 as shown in FIG.
．． 1 is fixed in a pressed state toward the colored microsphere 2 side. The average center diameter (Dn) of the colored microspheres 2 is 0.5 to 10% larger than the average center diameter (Dn) of the crosslinked polymer microspheres before treatment, and the coloring microspheres 2 are formed on the outer peripheral surface of the microspheres 2. Since the colored layer 2a is slightly softer than the center layer 2b, as shown in FIG. ．．
The pressurized stress can be distributed to all the colored microspheres 2 filled between 1 and 2. Moreover, the central layer 2b of the colored microspheres 2
Since it is formed of crosslinked polymer microspheres, the pressing force of the substrate 1 can be supported from the inner surface by the center layer 2b. Further, since the colored layer 2a is formed to be relatively soft compared to the center layer 2b, it is difficult to slip on the inner surface of the substrate l.

For example, when the colored microspheres 2 have a center diameter of 5 to 10 μm, the thickness of the colored layer 2b can be approximately 0.1 to 0.5 μm, and a sufficient light shielding effect can be obtained with this thickness.

Although the colored layer 2a is formed only on the surface of the colored microspheres 2, the colored layer 2a can also be formed inside the colored microspheres 2. Furthermore, it is preferable to color the colored layer 2a black from the viewpoint of lowering the light transmittance, but it can also be colored with a color that easily absorbs visible light, such as dark blue, dark green, or dark brown.

(Example) The present invention will be explained below based on examples.

Disaster ■ Soil <Production of colored microspheres> In a 52 separable flask equipped with a stirrer and a reflux condenser, prepare a 2.51 solution of 5% polyvinyl alcohol, and add 625 g of divinylbenzene and dipentaerythritol hexane. A monomer solution in which 625 g of acrylate and 18.8 g of benzoyl peroxide were uniformly dissolved and mixed was charged, and the temperature was raised to 80°C with stirring.
The polymerization reaction was carried out for a period of time, and then the temperature was raised to 95°C and the polymerization reaction was carried out for 1 hour. Next, the mother liquor is separated and washed, and 6
Crosslinked polymer microspheres of ~15 μm were obtained. By classifying the crosslinked polymer microspheres, crosslinked polymer microspheres having a desired average center diameter were obtained.

Next, 10 g of dry crosslinked polymer microspheres with an average central diameter (Dn) = 10.08 um and a standard deviation (σ) = 0.28 μ- were taken, and 100 g of 95% concentrated sulfuric acid was placed in a 200 d beaker. The polymer microspheres were gradually added to the beaker while stirring with a magnetic stirrer. Acid treatment was performed by reacting at 55°C for 6 hours.

Thereafter, the acid-treated crosslinked polymer microspheres obtained were filtered and thoroughly washed with water. On the other hand, basic dye Cachilon Black SBH
(manufactured by Odugaya Kagaku ■) 6g was dissolved in 300-g water and acetic acid was added to adjust the pH to 4 to prepare a dye bath. next,
Add the acid-treated crosslinked polymer microspheres to this dye bath, and
The cells were stained with C for 6 hours.

Next, the excess dye bath was filtered off and washed with water to obtain microspheres dyed black.

When the obtained colored microspheres were observed under a microscope with a magnification of 400 times, all of the microspheres were stained black, and no uncolored microspheres were observed. Moreover, the average center diameter (Dn) of the obtained colored microspheres was 0.5 to 10% larger than the average center diameter (Dn) of the crosslinked polymer microspheres before the above treatment.

Example 1 - Production of colored microspheres> Instead of divinylbenzene and dipentaerythritol hexaacrylate used in Example 1, 187.5 g of tetramethylolmethane triacrylate and 562.5 g of tetraethylene glycol dimethacrylate were used. Example 1 except that 500 g of methacrylic acid and 500 g of methacrylic acid were used.
The operation was carried out under the same conditions as above, and the average center diameter (Dn) was 5 to 5.
Crosslinked polymer microspheres of 15 μm were obtained.

Next, take 3 g of dried microspheres classified into average central diameter (Dn) = 8.36 μm and standard deviation (σ) = 0.33, add them to 30 g of concentrated sulfuric acid, and let the mixture cool to room temperature (25°C). Acid treatment was performed for 3 hours. Next, the mixture was filtered and washed with water to obtain acid-treated crosslinked polymer microspheres. On the other hand, basic dye Cachilon Brilliant Scarlet CD-GLH (Odugaya Chemical ■
Dissolve Ig in 100 m of water and adjust the pH by adding acetic acid.
Create a dye bath adjusted to =4. The acid-treated crosslinked polymer microspheres were added to this dye bath and dyed at 95°C for 1 hour.

The filtrate became completely transparent and 100% of the dye was stained into the microspheres. After filtering, the dyed crosslinked polymer microspheres were separated into 4 to 5
The microspheres were washed twice with water and then dried to obtain colored microspheres dyed red.

When the obtained colored microspheres were observed under a microscope with a magnification of 400 times, all of the microspheres were stained red, and the presence of uncolored microspheres was not observed. Moreover, the average center diameter of the obtained colored microspheres was 0.5 to 10% larger than the average center diameter (Dn) of the crosslinked polymer microspheres before the above treatment.

1 spot (Production of colored microspheres) The same operation as in Example 1 above was carried out using 30 parts by weight of dipentaerythritol hexaacrylate and 60 parts by weight of divinylbenzene, and the average center diameter (D, ) = 6.48 μm. ,
Crosslinked polymer microspheres Log with standard deviation (σ) = 0.36
I got it. Next, 10 g of the cross-linked polymer microspheres were gradually added to a 200% beaker containing 30 g of 95% sulfuric acid under stirring, followed by heat treatment at 60°C for 3 hours. Next, the sulfuric acid was filtered off, and the microspheres were washed with water to obtain acid-treated crosslinked polymer microspheres. On the other hand, commercially available black basic dye (Catilon Black SBI+).

A dye bath was prepared by dissolving 6 g (manufactured by Udogaya Kagaku ■) in 300 d of water and adjusting the pH to 4 with acetic acid.The above acid-treated microspheres were added to this dye bath and dyed at 95°C for 5 hours. After the dye bath was filtered off, the colored microspheres were washed with water and then with acetone to remove undyed dye molecules to obtain colored crosslinked polymer microspheres.

The particle size of the thus obtained crosslinked polymer microspheres was measured using a Calder counter, and the average center diameter (D J
=6.76 (t m , standard deviation (σ) = 0.35
Met. The average center diameter of the obtained colored microspheres was determined by 4.5 mm from the average center diameter (Dn) of the crosslinked polymer microspheres before the above treatment.
It was confirmed that the amount increased by 3%.

When these colored microspheres were observed under a microscope with a magnification of 400 times,
All particles were optically uniformly dyed black, and there were no uncolored particles.

<Measurement of light transmittance of colored microspheres> 1 g of colored microspheres obtained by the above method was dispersed in 100 ml of Freon, and this was placed in a 1 mm thick x 10 mm wide x IJ3
The colored microspheres were cast onto a 0 mm glass plate, covered with glass plates of the same size so as to sandwich the colored microspheres, and then lightly pressed and fixed in two places with adhesive tape so as to span the upper and lower glass plates.

Next, this material was placed in an open chamber at 50°C to evaporate the fluorocarbons to create two samples in which colored microspheres were present in a single layer close-packed between two glass plates. . When this sample was observed under an optical microscope with a magnification of 100 times, colored microspheres were gathered in a honeycomb shape and arranged in a single layer, and it was confirmed that the sample was the desired sample.

Next, the two samples were stacked one on top of the other, and the two samples were fixed with adhesive tape so as to extend above and below the sample, thereby obtaining a sample for visible light transmittance measurement.

Four glass plates containing no colored microspheres were used as controls, and the visible light transmittance of the above samples in the range of 400 nm to 800 nm was measured using a spectrophotometer. As a result, 400 nm to 800 nm
The transmittance was 3 to 5% or less over the entire range of m.

Further, when the spectral reflectance of the above sample was measured over the entire range from 400 nm to 800 nm using magnesium oxide as a standard white plate, the reflectance was 0%.

From the above results and the results of observing the colored microspheres under a 400x optical microscope, it has been confirmed that the colored microspheres of the present invention are dyed in an extremely deep color, and can be effectively used for the intended purpose. This can be confirmed.

In addition, the colored microspheres obtained above are mixed into an epoxy resin, the resin is cured, and then the cured product is cut with a microtome to create a cut surface of the colored microspheres, and after being treated with osmic acid, An electron micrograph of the cut surface was taken at a magnification of 10,000 times. As a result, the colored microspheres were lightly colored by osmic acid up to about 3 μm from the center, but no coloring was observed in the outer periphery of 0.5 to 0.7 μm. This suggests that acid treatment staining occurs at 0.5 to 0.7 μm of the surface layer.

Fabrication of Liquid Crystal Display Panel> Substrates made of 1.1 mm thick glass plates with transparent electrodes made of ITO formed on their surfaces were placed facing each other with a gap in between. On the other hand, the average center diameter (Dn) obtained above = 6.4
8. Epoxy acrylate type U using uncolored crosslinked polymer microspheres with standard deviation (σ) = 0.36 μm as spacers.
A sealing material was prepared by incorporating it into a V-adhesive. This sealing material was applied to the peripheral areas of the two substrates by screen printing, except for the liquid crystal injection port, and then UV irradiation was applied under pressure to harden the sealing material. Before this sealing, the colored crosslinked polymer microspheres obtained above (Dn=6
．． 67, σ-〇, 35μm) dispersed in Freon,
The particles were scattered at approximately 100 particles/mm2.

Next, nematic liquid crystal was injected through the injection port, and the injection port was then sealed with an ultraviolet curing sealant to produce a desired liquid crystal display panel. Ten liquid crystal display panels were created under the same conditions as above. When the gap between the substrates of each of the 10 LCD panels was measured, the gap was 6.35.
It was μm±0.05 μm.

When the obtained liquid crystal display panel was displayed in a negative type, no colored microspheres were visible and good contrast was obtained.

A liquid crystal display panel was prepared under the same conditions as in Example 3 by spraying on the substrate a solution in which the same uncolored crosslinked polymer microspheres used for the peripheral sealing material were dispersed in Freon instead of the colored microspheres. 1
Created 0 pieces. When the gap between the substrates of 10 liquid crystal display panels was measured, the gap was 6.20μm±0.1
It was 0 μm.

This shows that by using the colored microspheres as spacers, the gap accuracy between the substrates of the liquid crystal display panel can be improved. This can be inferred from the knowledge obtained from the observation using electron micrographs mentioned above. Since the colored layer of the colored spacer has cushioning properties, when the substrate is fixed in a pressed state, the average center of the colored microspheres is It is thought that the accuracy of the substrate gap is improved because the colored layer absorbs the variation in the diameter. This inference is also supported by the following experimental facts.

That is, the colored microspheres and uncolored crosslinked polymer microspheres obtained above were dispersed in Freon (2 g/200 d) L,
Next, a sample was prepared by scattering onto a tempered glass plate at a density of about 100 particles/mm, and covering and fixing another glass plate on top of it. In addition to measuring the microspheres, the above sample was
When we observed with a magnifying glass how the particles were destroyed by applying pressure in kg/cIil increments, we found that the uncolored crosslinked polymer microspheres were crushed into pieces by the pressure, whereas the colored microspheres were crushed. I found out that it can be broken like that.

Furthermore, - liquid crystal display panels using colored microspheres prototyped by the above method and liquid crystal display panels using uncolored crosslinked polymer microspheres were selected, and heated at 40'C for 1 hour.
After ultrasonic cleaning was performed using an ultrasonic cleaner for 0 hours, dark field contrast was observed with the naked eye. As a result, the contrast of liquid crystal display panels using uncolored crosslinked polymer microspheres tended to decrease (relative to a blank), whereas the contrast of liquid crystal display panels using colored microspheres did not change. When both panels were observed under a 100x optical microscope to see how the microspheres were dispersed, it was found that in the panel using uncolored cross-linked polymer microspheres, the microspheres moved within the space between the side substrates of the liquid crystal display panel, causing the electrodes to move. It showed a tendency to aggregate in the periphery. On the other hand, in the panel using colored microspheres, there was almost no movement of the colored microspheres, and a uniformly dispersed state was maintained.

(Effects of the Invention) As described above, the colored microspheres of the present invention are made by dyeing crosslinked polymer microspheres treated with acid, and a colored layer is formed on the outer peripheral surface of the crosslinked polymer microspheres. Therefore, the outer peripheral surface can be colored uniformly and darkly. Therefore, when these colored microspheres are used as spacers for liquid crystal display panels,
A high-quality liquid crystal display panel with low transmittance in dark field when no voltage is applied to the liquid crystal display panel and excellent display contrast can be obtained.

Moreover, since the colored layer is formed on the outer peripheral surface of the colored microspheres, the center of the colored microspheres remains strong and has a high crosslinking density without being acid-treated, while only the colored layer on the outer peripheral surface is compared. It can be formed to be soft and flexible. Therefore, by using these colored microspheres as spacers for liquid crystal display panels,
When manufacturing a liquid crystal display panel, when a substrate is pressurized, the central layer of colored microspheres supports the pressing force of the substrate from the inner side, while the colored layer on the outer circumferential surface deforms, thereby supporting the pressure applied to the substrate. Pressure and stress can be distributed to all the colored microspheres, making it possible to obtain a liquid crystal display panel with better gap precision than conventional panels. Further, the colored layer of the colored microspheres is partially deformed by the pressure of the substrate, so that it comes into contact with the inner surface of the substrate over a wide area, and there is no fear that the colored microspheres will move within the gap of the liquid crystal display panel.

[Brief explanation of the drawing]

FIG. 1 is a sectional view of a main part of a liquid crystal display panel according to an embodiment of the present invention, FIG. 2 is a sectional view of colored microspheres, and FIG. 3 is an enlarged sectional view of a main part of the liquid crystal display panel. DESCRIPTION OF SYMBOLS 1... Substrate, 2... Colored microspheres, 2a... Colored layer, 2b... Center layer, 3... Liquid crystal composition, 4... Seal material, 10... Electrode surface. that's all

Claims (1)

[Scope of Claims] 1. Colored microspheres, which are made by dyeing crosslinked polymer microspheres treated with acid, and a colored layer is formed on the outer peripheral surface of the crosslinked polymer microspheres. 2. The colored microspheres according to claim 1, wherein the crosslinked polymer microspheres are obtained by polymerizing a monomer having an ethylenically unsaturated group. 3. The monomer has two or more ethylenically unsaturated groups.
The colored microspheres according to claim 2, which contain at least part by weight. 4. The monomer having two or more ethylenically unsaturated groups is x methylol alkyl y (meth)acrylate (where x and y are integers satisfying the condition x≧y≧2),
Claim 3 is at least one selected from the group consisting of polyoxyalkylene glycol di(meth)acrylate, triaryl(iso)cyanurate, triaryltrimelite, divinylbenzene, diarylphthalate, and diarylacrylamide. Colored microspheres as described. 5. The acid treatment agent is concentrated sulfuric acid, fuming sulfuric acid, sulfur trioxide, sulfite, sulfite, bisulfite, sulfonyl chloride,
The colored microspheres according to any one of claims 1 to 4, which are at least one selected from the group consisting of chlorosulfuric acid, fluorosulfuric acid, and aminosulfonic acid. 6. The colored microspheres according to any one of claims 1 to 5, wherein the dye to be dyed is a basic dye. 7. A pair of substrates with electrodes, at least one of which is transparent and arranged with a predetermined gap so that the electrode surfaces provided on the side faces face each other, and a peripheral part between the two substrates is filled. a sealing material that closes a peripheral gap between the substrates, a spacer that is interposed between the two substrates to regulate the gap between the two substrates, and a liquid crystal composition that fills the gap between the two substrates. A liquid crystal display panel comprising: a colored microsphere in which the spacer is formed by dyeing crosslinked polymer microspheres treated with an acid, and a colored layer is formed on the outer peripheral surface of the crosslinked polymer microspheres; LCD display panel.