JPH09221507A - Colored high-molecular polymer microparticle, its production, spacer for liquid crystal display, and liquid crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide colored high-molecular polymer microparticles which have excellent mechanical strengths, do not collapse when used in adjusting the gap of a liquid crystal display, and improve the display contrast of images on a liquid crystal display, a process for producing the same, a spacer for a liquid crystal display, and a liquid crystal display. SOLUTION: This microparticle contains a pigment component comprising carbon black and at least one set of organic coloring pigments other than carbon black and having different colors. This process comprises subjecting a composition obtained by dispersing a pigment component comprising carbon black and at least one set of organic coloring pigments other than carbon black and having different colors in a polymerizable monomer to suspension polymerization in the presence of a polymerization initiator in an aqueous medium. This spacer comprises colored high-molecular polymer microparticles containing a pigment component comprising carbon black and at least one set of organic coloring pigments other than carbon black and having different colors. This device is made by using this spacer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer polymer colored fine particle having an excellent light-shielding property, which can be suitably used as a spacer for a liquid crystal display element, a method for producing the same, and a liquid crystal display element using the same.

[0002]

2. Description of the Related Art Liquid crystal display devices are widely used in personal computers, portable electronic devices and the like.
It is desired to further increase the display contrast of images. Japanese Patent Application Laid-Open No. 57-189117 discloses a liquid crystal display element in which two transparent substrates with electrodes are arranged so that the electrodes face each other, and liquid crystal is sealed between the two substrates. It is disclosed that colored spacers are scattered over the entire surface to prevent a reduction in image display contrast.

With respect to the colored spacers used for such a high contrast liquid crystal display element, various kinds of polymer polymer colored fine particles and a method for producing the same have been proposed. These production methods can be divided into two types: a method of coloring the high-molecular polymer particles prepared in advance and a method of coloring in the step of preparing the high-molecular polymer particles.

The following methods have been disclosed as methods for coloring the high-molecular polymer fine particles prepared in advance. Japanese Patent Application Laid-Open No. 1-144429 discloses a method of treating high-molecular polymer particles with an acid and then coloring this, and Japanese Patent Application Laid-Open No. 1-207719 discloses high-molecular polymer particles at 200 to 700 ° C. A method for producing a flame-resistant baked product by heat treatment in a temperature range is disclosed in JP-A-1-207719, and a method for coating fine polymer particles with a conjugated polymer such as polyacetylene is disclosed in JP-A-1-200227.
Japanese Patent Laid-Open Publication Nos. 1993-242242 and 1994-1999 each disclose a method in which a metal coating layer is provided on the surface of crosslinked high-molecular polymer particles and then an oxidation treatment is performed to make the surface an oxide.

Further, Japanese Patent Laid-Open No. 4-15623 discloses that
A method of implanting black metal oxide ultrafine particles on the surface of organic high molecular polymer fine particles is disclosed in JP-A-3-101713, in which high molecular polymer fine particles containing an anionic functional group are added to an oxidant solution. A method of dispersing and adsorbing or impregnating an oxidizing agent, and then adding at least one of a hetero five-membered ring compound and an aromatic hydrocarbon to carry out chemical oxidative polymerization is disclosed in JP-B-4-27242. A method of dyeing fine particles of a water-soluble polymer obtained by polymerizing an unsaturated sulfonic acid or a salt thereof with a basic dye is disclosed.

Further, JP-A-3-351616 discloses a method of coloring fine particles of a high molecular weight polymer of amino resin with an acid dye at high temperature in the presence of a solvent.
Japanese Patent No. 331 discloses a method of coloring by mixing a dye emulsion in which an oily solvent solution of an oily dye is finely dispersed in an aqueous medium and a polymer fine particle emulsion.

[0007] As a method of coloring in the step of preparing high polymer fine particles, for example, Japanese Patent Publication No. 4-59321 discloses a filler containing a pigment treated to impart lipophilicity to a vinyl compound. In JP-A-7-2913, there is disclosed a method in which a pigment is uniformly mixed with a compound having a polyfunctional ethylenically unsaturated group containing (meth) acrylonitrile. A method of suspension polymerization of this in an aqueous medium is disclosed in JP-A-7-2913, in which a monomer, an oil-soluble dye, a dispersion stabilizer and an oil-based polymerization initiator are dissolved in a monomer. A method in which a polymer is dissolved in a solvent system in which it is insoluble and polymerization is carried out while incorporating an oil-soluble dye is disclosed in JP-A-7-2913.
A method of dissolving and dispersing a compound having a C = N ⁺ <bond in a polymerizable monomer component together with a colorant, and then polymerizing is disclosed, respectively.

[0008]

When the method of coloring pre-prepared high polymer particles is compared with the method of coloring in the step of preparing high polymer particles, the high polymer particles are The method of coloring in the step of preparing is industrially superior in that the manufacturing cost is low and the performance and quality of the product are easy to control.

However, when the method of coloring is adopted in the step of preparing the high molecular weight polymer fine particles, the high molecular weight polymer fine particles obtained have pigments or the like dispersed therein, and therefore the pigments or the like are present. Stress acts on the interface between the polymer and the polymer to easily cause interface fracture, and as a result, mechanical strength such as compressive strength tends to decrease. That is, as the fine particles of the high molecular weight polymer are colored darker, the mechanical strength is lowered.

When such polymer polymer colored fine particles having low mechanical strength are used as spacers for a liquid crystal display element, they cannot withstand the pressure applied for adjusting the gap during the assembly of the liquid crystal display element, and collapse. This may cause the gap adjustment to be disturbed. Further, the fragments of the crushed polymer-polymer colored fine particles may remain in the liquid crystal display element, inducing an inconvenient interaction with the liquid crystal as a foreign substance, and remarkably reducing the quality of the display image of the liquid crystal display element.

The present invention solves the above-mentioned problems, and its object is to have excellent mechanical strength and not to be crushed even when adjusting the gap of a liquid crystal display element.
Another object of the present invention is to provide a polymer polymer colored fine particle capable of improving the display contrast of an image of a liquid crystal display element, a method for producing the same, a spacer for a liquid crystal display element, and a liquid crystal display element.

[0012]

Means for Solving the Problems The above-mentioned object is achieved by high-polymer-polymer-colored fine particles containing a pigment component composed of carbon black and at least one set of organic coloring pigments other than carbon black and having different colors. can do.

The above-mentioned object is also a composition obtained by dispersing in a polymerizable monomer a pigment component comprising carbon black and at least one set of organic color pigments other than carbon black and having different colors. This can be achieved by a method for producing high-molecular polymer colored fine particles, in which suspension polymerization is carried out in an aqueous medium in the presence of a polymerization initiator.

The above object can be further achieved by a spacer for a liquid crystal display device comprising the above-mentioned polymer polymer colored fine particles and a liquid crystal display device using the spacer.
Hereinafter, the present invention will be described in detail.

The high molecular weight polymer fine particles of the present invention contain a pigment component comprising carbon black and at least one set of organic color pigments other than carbon black and having different colors.

The carbon black is not particularly limited, and examples thereof include acetylene black, channel black and furnace black. In the present invention, in order to improve the dispersibility of carbon black,
It is also possible to use surface-treated carbon black such as Microlith (manufactured by Ciba Geigy).

As a set of organic color pigments other than the above-mentioned carbon black and having different colors, those having relatively good transparency and excellent heat resistance, weather resistance and solvent resistance are preferable, and particularly substantially. A set of organic color pigments exhibiting a black color is preferred. In the present invention, at least one set of such a set of organic color pigments is used.

The color pigments other than the above carbon black and constituting a set of organic color pigments of different colors are not particularly limited. Azo or condensed azo organic color pigments such as red R, fast red FGR, toluidine malon, bisazo yellow, first yellow G, bisazo orange, vulcan orange, pyrazolone red; phthalocyanine blue, fast sky blue, phthalocyanine green, etc. Phthalocyanine organic color pigments; dyed lake organic color pigments such as yellow lake, rose lake, violet lake, blue lake, green lake; oxazine organic color pigments;
Examples include quinophthalone-based organic color pigments. As a set of organic color pigments other than the above carbon black and having different colors, two or more kinds of these can be appropriately selected and used.

As a combination of the above-mentioned coloring pigments other than the above-mentioned carbon black and constituting a set of different color organic pigments, at least one set of different-color organic pigments other than the above-mentioned carbon black is When used together with carbon black, the polymer polymer-colored fine particles of the present invention have a maximum transmittance of less than 3% in the entire visible range of about 450 to 600 nm, and an average transmittance of 0 in the entire visible range. A combination of 0.1 to 2.5% is preferable. More preferably, the maximum transmittance is less than 2.7%, and the average transmittance is 0.2 to
The combination is 2.0%.

The combination is not particularly limited and includes, for example, blue pigment and purple pigment, red pigment and blue pigment, yellow pigment and blue pigment and purple pigment, green pigment and blue pigment and purple pigment, red pigment and blue pigment. Examples include a combination of a pigment and a purple pigment.

From the viewpoint of light transmittance, uniformity of the film surface, etc., the above-mentioned color pigment preferably has a particle size of 1 μm or less.

In the pigment component, the blending ratio of the carbon black is 5 to 60% by weight, and the blending ratio of at least one set of organic color pigments having different colors other than the carbon black is 95 to 40. It is preferably in the weight%. The blending ratio of the above carbon black is less than 5% by weight, and the blending ratio of at least one set of organic coloring pigments other than the above carbon black and having a different color is 9%.
If it exceeds 5% by weight, the amount of addition of at least one set of organic coloring pigments other than carbon black and having a different color increases, and the mechanical strength of the polymer polymer colored fine particles of the present invention decreases extremely. There is.

If the blending ratio of the carbon black is more than 60% by weight and the blending ratio of at least one set of organic coloring pigments other than the above carbon black is different from the above, the blending ratio of the carbon black is less than 40% by weight. When the amount of addition is large, the colored particles of the high molecular weight polymer of the present invention become conductive, and it becomes difficult to use them as spacers for liquid crystal display devices. More preferably, the blending ratio of the carbon black is 10 to 40% by weight, and the blending ratio of at least one set of organic color pigments other than the carbon black and having different colors is 90 to 60% by weight.

When the pigment component is composed of only the above carbon black, the amount of carbon black added necessary for producing a sufficient black color is increased, and the polymerized polymer fine particles of the present invention become conductive. Therefore, it cannot be used as a spacer for a liquid crystal display element.

When the above-mentioned pigment component is other than the above-mentioned carbon black and consists of at least one set of organic coloring pigments of different colors, it is different from the carbon black other than the carbon black necessary for producing a sufficient black color. The addition amount of at least one set of organic color pigments increases, and the mechanical strength of the polymer polymer colored fine particles of the present invention is extremely reduced.

In the present invention, as the pigment component, at least one set of organic color pigments having different colors other than carbon black is used together with carbon black.
The high molecular weight polymer fine particles of the present invention can reduce the amount of carbon black compounded, can prevent conductivity, and can secure sufficient blackness and good physical properties. Therefore, the liquid crystal display element using the spacer for a liquid crystal display element made of the high polymer colored particles of the present invention, when the image is displayed, the spacer is not recognized as a bright spot in the dark portion of the image, The display contrast of the image becomes excellent.

The high molecular weight polymer fine particles of the present invention preferably have an average particle size of 0.1 to 5000 μm. If it is less than 0.1 μm, it tends to agglomerate and lack practicality, and if it exceeds 5000 μm, it is rarely used. More preferably, it is 0.1 to 1000 μm.

The high-molecular-weight polymer colored fine particles of the present invention preferably have a variation coefficient of particle diameter of 50% or less.
If it exceeds 50%, the particle size distribution becomes too wide, and the performance as a spacer for a liquid crystal display device may deteriorate. It is more preferably 35% or less, further preferably 25%
It is as follows.

The high-molecular-weight polymer colored fine particles of the present invention contain, in a polymerizable monomer, the above-mentioned pigment component comprising the above-mentioned carbon black and at least one set of organic coloring pigments of different colors other than the above-mentioned carbon black. The composition obtained by dispersion is obtained by suspension polymerization in an aqueous medium in the presence of a polymerization initiator.

In the suspension polymerization, first, the pigment component is uniformly dispersed in the polymerizable monomer to obtain a composition.

The above-mentioned polymerizable monomer is not particularly limited, and examples thereof include styrene-based monomers such as styrene, α-methylstyrene, p-methoxystyrene, t-butylstyrene and chlorostyrene; methyl acrylate and acryl. Acrylic acid monomers such as ethyl acrylate, butyl acrylate, stearyl acrylate, and 2-ethylhexyl acrylate;
Methyl methacrylate, propyl methacrylate, butyl methacrylate, stearyl methacrylate, methacrylic acid-
Methacrylic acid-based monomers such as 2-ethylhexyl and dodecyl methacrylate; diene-based monomers such as butadiene and isoprene; ethylene, vinyl chloride, acrylonitrile, acrylamide, methacrylamide, vinyl pyridine, N
-Vinylpyrrolidone, N-hydroxyacrylamide,
2-vinyl-2-oxazoline, 2-isopropenyl-
2-oxazoline, vinyl acetate, N-methylol acrylamide, dimethylaminoethyl acrylate, glycidyl methacrylate, allyl glycidyl ether, maleic anhydride, monomethyl fumarate and the like can be mentioned. The kind, combination, etc. of these are not particularly limited, but it is preferable to select them so that the compatibility between the obtained polymerized polymer fine particles and the binder or vehicle becomes high.

An appropriate crosslinkable compound can be used together with the above polymerizable monomer. Such compounds are not particularly limited, for example, aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene and derivatives thereof; ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate,
Diethylenic or triethylenically unsaturated carboxylic esters such as 1,3-butanediol dimethacrylate;
Divinyl compounds such as N, N-divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfonic acid; and compounds having three or more vinyl groups. These may be used alone or in combination of two or more.

The amount of the crosslinkable compound added is 0.00 based on the total amount of the crosslinkable compound and the polymerizable monomer.
5-20% by weight is preferred.

The blending amount of the above-mentioned pigment component is the polymerizable monomer 1
1 to 180 parts by weight is preferable with respect to 00 parts by weight. If the amount is less than 1 part by weight, it is difficult to color the film in a dark color. If the amount is more than 180 parts by weight, the mechanical strength of the obtained high molecular colored polymer particles may be reduced. More preferably 3 to 1
60 parts by weight.

To uniformly disperse the pigment component in the polymerizable monomer, for example, a ball mill, a bead mill,
A sand mill, attritor, sand grinder, nanomizer, etc. can be used.

If desired, a dispersant may be added to the composition obtained by dispersing the pigment component in the polymerizable monomer, in order to improve the dispersibility of the pigment component.

The dispersant is not particularly limited, and examples thereof include water-soluble polymers such as polyvinyl alcohol, starch, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, sodium polymethacrylate; barium sulfate, calcium sulfate, aluminum sulfate, calcium carbonate. , Calcium phosphate, talc, clay, diatomaceous earth, metal oxide powder and the like. The amount of the dispersant blended is 0.01 with respect to the polymerizable monomer component.
-20% by weight is preferred.

In the present invention, the above composition is then
Suspension polymerization is carried out in an aqueous solvent in the presence of a polymerization initiator to obtain the polymer polymer colored fine particles of the present invention.

As the above-mentioned polymerization initiator, those used in ordinary suspension polymerization can be used. Such a substance is not particularly limited as long as it is insoluble in an aqueous solvent and soluble in the above-mentioned polymerizable monomer, and examples thereof include benzoyl peroxide, octanoyl peroxide, orthomethoxybenzoyl peroxide, and methyl ethyl ketone peroxide. Oil-soluble peroxide type polymerization initiators such as oxide, cumene hydroperoxide and t-butyl hydroperoxide; 2,2′-
Azobisisobutyronitrile, 2,2'-azobis-
2,4-dimethylvaleronitrile, 2,2'-azobis-2,3-dimethylbutyronitrile, 2,2'-azobis-2,3,3-trimethylbutyronitrile, 2,2 '
Azobis-2-isopropylbutyronitrile, 4,4
Azobis-4-cyanovaleric acid, dimethyl-2,
An azo-based polymerization initiator such as 2'-azobisisobutyrate is exemplified.

The compounding amount of the above-mentioned polymerization initiator is preferably 0.01 to 20% by weight with respect to the polymerizable monomer. When it is less than 0.01% by weight, the polymerization rate is low, and an amount exceeding 20% by weight is unnecessary. More preferably, it is 0.1 to 10% by weight.

The aqueous medium is not particularly limited, and examples thereof include polyvinyl alcohol, polyacrylic acid, polymethacrylic acid, gelatin, methyl cellulose, polymethacrylamide, polyethylene glycol, polyethylene oxide monostearate, sorbitan tetraoleate, glycerin mono. Examples thereof include aqueous solutions of water-soluble organic compounds such as oleate and dodecylbenzenesulfonic acid, and water.

To suspend the above composition in the form of fine particles in the above aqueous medium, for example, a homogenizer or the like can be used.

The polymerization temperature of the above suspension polymerization is 20 to 100.
C is preferred. When the temperature is lower than 20 ° C., the polymerization rate is low, and when it exceeds 100 ° C., it becomes difficult to control the polymerization reaction. The polymerization time of the above suspension polymerization is preferably 1 to 50 hours. When the time is less than 1 hour, the polymerization rate is low, and the time exceeding 50 hours is unnecessary.

The high-molecular-weight polymer colored fine particles obtained by the suspension polymerization can be separated by an appropriate means such as filtration or centrifugation. The separated polymer-polymer colored fine particles are washed with water or the like, and then dried by heating or reduced pressure to obtain a product of the polymer-polymer colored fine particles.

The polymer polymer colored fine particles of the present invention can be suitably used as a spacer for a liquid crystal display device.

The high molecular weight polymer fine particles of the present invention are mixed with liquid crystal.
When used as a spacer for a display element,
The K value of the bright high-molecular polymer colored fine particles is 250 kgf /
mm ^TwoThe above is preferable. 250 kgf / mm
^TwoBetween the pair of substrates of the resulting liquid crystal display device is less than
It may be difficult to maintain the distance between and precisely and stably.

Here, the K value is a value defined by the following equation (1), which universally and quantitatively represents the hardness of a sphere. By using this K value, it is possible to quantitatively and unambiguously determine the suitable hardness of the polymer polymer colored fine particles of the present invention when the polymer polymer colored fine particles of the present invention are used as a spacer for a liquid crystal display device. Can be represented.

K = (3 / √2) · F · S ^−3/2 / R ^−1/2 (1) (In the formula, F is a load value at 10% compressive deformation of the polymer polymer fine particles. kgf), S represents compression displacement (mm), and R represents particle radius (mm).)

When the polymer polymer colored fine particles of the present invention are used as a spacer for a liquid crystal display device, the recovery rate after compression deformation of the polymer polymer colored fine particles of the present invention is 30% or more. It is preferable. If it is less than 30%, the plastic deformation is too large, which may cause an inconvenience in the step of determining the distance between the pair of substrates of the obtained liquid crystal display element.

[0050]

BEST MODE FOR CARRYING OUT THE INVENTION An embodiment of a liquid crystal display device using a spacer for a liquid crystal display device, which comprises the colored fine particles of a polymer according to the present invention, will be described with reference to the drawings.

As shown in FIG. 1, the liquid crystal display element A is disposed between the pair of substrates 7 and 9 and between the pair of substrates 7 and 9 in order to keep the gap between the pair of substrates 7 and 9 constant. Spacers 8, a nematic liquid crystal 11 enclosed between the pair of substrates 7 and 9, a sealing member 10 filled around the pair of substrates 7 and 9, and the surfaces of the substrates 7 and 9 are covered. The polarized sheets 12 and 13 are formed.

Substrates 7 and 9 are made of transparent substrates 1 and 4 made of glass on one surface of which ITO (Indium-Tin-Oxi) is provided.
de) patterning the transparent electrodes 2 and 5 made of a film,
The surfaces of the transparent electrodes 2 and 5 and the transparent substrates 1 and 4 are covered with alignment control films 3 and 6 made of a polyimide film or the like. The alignment control films 3 and 6 are subjected to alignment control processing by rubbing.

The spacer 8 is the polymer polymer colored fine particles of the present invention having a K value in the above-mentioned predetermined range and a recovery rate after compression deformation in the predetermined range.

[0054]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 Preparation of high-molecular polymer colored fine particles 60 parts by weight of tetramethylol methanetriacrylate,
20 parts by weight of divinylbenzene and acrylonitrile 20
12 parts by weight of carbon black as a black pigment component, 6 parts by weight of phthalocyanine blue (blue pigment) and 6 parts by weight of dioxane violet (purple pigment) are added to the mixture, and the mixture is mixed for 48 hours using a bead mill. To uniformly disperse the black pigment component. To this colored polymerizable monomer composition in which the black pigment component was dispersed, 2 parts by weight of benzoyl peroxide were uniformly mixed, and this was added to 850 parts by weight of a 3% by weight aqueous solution of polyvinyl alcohol and stirred well. Thereafter, a homogenizer was used to suspend the colored polymerizable monomer droplets into fine particles having a particle size of about 3 to 10 μm to obtain a suspension.

The obtained suspension was transferred to a 2 liter separable flask equipped with a thermometer, a stirrer and a reflux condenser, and heated to 85 ° C. while stirring in a nitrogen atmosphere,
The polymerization reaction was carried out for 7 hours, and the temperature was further raised to 90 ° C. and maintained for 3 hours to complete the polymerization reaction. Thereafter, the polymerization reaction liquid was cooled, and the resulting polymer-polymer colored fine particles were filtered, sufficiently washed with water, and dried to obtain a pigment-dispersed polymer-polymer colored fine particle having a particle size of 3 to 10 μm, and 120 parts by weight. I got The obtained high molecular weight colored polymer particles were classified to have an average particle size of 6.
Polymer colored fine particles having a particle diameter of 45 μm and a variation coefficient of the particle diameter of 2.88% were obtained. K of the obtained high molecular weight polymer fine particles
The value, the recovery rate after compression deformation, and the blackness were evaluated by the following methods, and the results are shown in Table 1.

Evaluation method (1) K value (i) Measuring method At room temperature, the obtained polymer polymer colored fine particles were sprinkled on a steel sheet having a smooth surface, and one polymer was selected from them. Colored fine particles were selected. Next, using a micro compression tester (PCT-200 type, manufactured by Shimadzu Corp.), the polymer polymer colored fine particles were compressed with a smooth end face of a diamond cylinder having a diameter of 50 μm. At this time, the compression load was electrically detected as an electromagnetic force, and the compression displacement was electrically detected as a displacement due to the operating transformer.

As a result, the compression displacement as shown in FIG.
The relationship of loads was calculated. From FIG. 2, the load value and the compressive displacement at 10% compressive deformation of the colored fine particles of the polymer were determined. From these values and the above equation (1), the relationship between the K value and the compression strain as shown in FIG. 3 was obtained. However, the compressive strain is a value obtained by dividing the compressive displacement by the particle diameter of the high molecular weight polymer fine particles and expressed in%. (Ii) Compression speed This was performed by a constant load speed compression method. The load was increased at a rate of 0.27 grams weight per second (grf). (Iii) Test load The maximum load was 10 grf.

(2) Recovery Rate after Compressive Deformation (i) Measuring Method At room temperature, the obtained polymer polymer colored fine particles were sprinkled on a steel plate having a smooth surface, and one polymer was selected from them. Polymer colored particles were selected. Next, using a micro compression tester (PCT-200 type, manufactured by Shimadzu Corp.), the polymer polymer colored fine particles were compressed with a smooth end face of a diamond cylinder having a diameter of 50 μm. At this time, the load was electrically detected as an electromagnetic force, and the compression displacement was electrically detected as a displacement due to the operating transformer.

As shown in FIG. 4, after compressing the colored particles of the high molecular weight polymer to the reversal load value (shown by the curve a in FIG. 4), the load was decreased on the contrary (the curve in FIG. 4). b)). At this time, the relationship between the load and the compressive displacement was measured.
However, the end point in unloading is not zero load value,
The origin load value was 0.1 g or more. The recovery rate was defined as a ratio (L ₂ / L ₁ ) of the displacement L _{1 up} to the point of reversal and the displacement difference L ₂ from the point of reversal to the point where the origin load value is taken in%.

(Ii) Measurement conditions Reverse load value 1 grf Origin load value 0.1 grf Compression rate under load and unload 0.27 grf / sec Measuring chamber temperature 20 ° C.

(3) Blackness With respect to the obtained polymer polymer colored fine particles, the degree of blackness was visually observed. Dark black ones were marked with ⊚, light black ones were marked with Δ, and extremely thin black ones were marked with x. And

Production of Liquid Crystal Display Device On a glass plate having a thickness of 0.7 mm, an indium oxide film having a thickness of about 500 Å was formed by a low temperature sputtering method.
After forming the tin oxide-based transparent conductive film, a predetermined electrode pattern was formed by photolithography. Then
After applying an aligning agent on this, a heated alignment control film was formed. Next, this glass plate was cut into a size of 5 cm × 12.5 cm to obtain a glass substrate of a liquid crystal display element.

An epoxy adhesive mixed with a glass fiber spacer was printed around the obtained glass substrate with a width of 1 mm by screen printing. After the glass substrate was placed horizontally, the colored particles of the high molecular weight polymer were scattered from above by pressurized nitrogen gas and uniformly dropped onto the glass substrate. The application time was adjusted so that the application concentration of the polymer colored fine particles on the glass substrate was about 100 particles / mm ² .

Another glass substrate was superposed on the glass substrate on which the high-molecular polymer colored fine particles were dispersed, and then a load of 1 kg / cm ² was applied by a pressing machine so that the entire glass substrate was uniformly applied. . At the same time, this one at 160 ℃
20 minutes to heat the surrounding epoxy adhesive. After the inside of the cell thus manufactured was sucked to form a vacuum, liquid crystal was injected into the inside from a hole provided in a part of the peripheral seal portion to manufacture a liquid crystal display element. As a result of measuring the gap value between the upper and lower substrates of the obtained liquid crystal display element, the gap value was 6.36 ± 0.03 μm.
Polarizing sheets were attached to both upper and lower surfaces of the liquid crystal display element so that the color tone of the reflected light applied to the obtained liquid crystal display element exhibited an olive color. At this time, the olive color was uniform and no uneven color was observed in the density. The electric resistance of the obtained liquid crystal display element, and the display contrast of the image,
It evaluated by the following method. The results are shown in Table 1.

Evaluation Method (1) Electric Resistance The resistance between the electrodes of the obtained liquid crystal display element was measured by the fine particle filling cell method. (2) Image Display Contrast The obtained liquid crystal display device is connected to a power source and turned on, and the image display contrast is visually observed. A sample having a good image display contrast is marked with ⊚, and the display contrast is normal. Those with a poor display contrast were marked with x.

Examples 2 to 4, Comparative Examples 1 and 2 High polymer polymer colored fine particles and a liquid crystal display device were prepared and evaluated in the same manner as in Example 1 except that the compounding amounts shown in Table 1 were used. did. The results are shown in Table 1.

[0068]

[Table 1]

[0069]

EFFECTS OF THE INVENTION The colored particles of the polymer according to the present invention have a dark black color and are excellent in electrical characteristics and mechanical strength due to the above-mentioned constitution. Therefore, it can be particularly preferably used as a light-shielding spacer for a liquid crystal display device, and a liquid crystal display device using the spacer for a liquid crystal display device comprising the polymer fine particles of the present invention is extremely excellent in image display contrast. It has high performance.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing one form of a liquid crystal display element of the present invention.

FIG. 2 is a graph showing the relationship between load and compressive displacement of high-molecular polymer colored particles.

FIG. 3 is a graph showing the relationship between the K value and the compression strain of high-molecular polymer colored fine particles.

FIG. 4 is a diagram illustrating a method of measuring a recovery rate of a high-molecular polymer colored fine particle after compression deformation.

[Explanation of symbols]

 1. Transparent substrate 2. Transparent electrode 3. Alignment control film 4. Transparent substrate 5. Transparent electrode 6. Alignment control film 7. Substrate 8. Spacer 9. Substrate 10. Seal member 11. Nematic liquid crystal 12. Polarizing sheet 13. Polarizing sheet

Claims (4)

[Claims] 1. Polymeric polymer colored fine particles, comprising a pigment component comprising carbon black and at least one set of organic color pigments other than carbon black and having different colors. 2. The polymerizable monomer, carbon black,
A composition obtained by dispersing a pigment component other than carbon black and comprising at least one set of organic coloring pigments of different colors may be subjected to suspension polymerization in an aqueous medium in the presence of a polymerization initiator. A method for producing colored fine particles of a polymer having a feature. 3. A liquid crystal display device comprising high molecular weight polymer fine particles containing a pigment component comprising carbon black and at least one set of organic color pigments other than carbon black and having different colors. Spacer. 4. A liquid crystal display device using the spacer for a liquid crystal display device according to claim 3.