JP3216304B2 - Colored particles - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to colored particles containing a colored component produced by irradiating a polymer obtained from a monomer containing cinnamic acid having a polymerizable double bond and / or a derivative thereof with light. .

[0002]

2. Description of the Related Art Conventionally, a liquid crystal display (hereinafter referred to as "LC
D ". In), spacer particles (hereinafter referred to as LC) are used to regulate the gap between the substrates and keep the thickness of the liquid crystal layer at an appropriate level.
The spacer particles for D are simply referred to as “spacer particles”. ) Is used. In general, such spacer particles should have sufficient strength and heat resistance to withstand the pressure and heating conditions in the LCD substrate assembly process, have a narrow particle size distribution that can uniformly maintain the substrate gap, And no impurities such as metal ions are present (preferably 10 pp per particle).
m or less), and it is required that the orientation of the liquid crystal is not disturbed. Also, more recently, from the viewpoint of improving the image quality, particularly by improving the contrast of the color liquid crystal panel,
Although colored spacer particles (hereinafter, colored spacer particles for LCD are simply referred to as “colored spacer particles”) have been used, it is strongly required that these colored spacer particles have sufficient light-shielding properties. In addition, it is also required that constituent materials such as coloring components do not peel off or fall off during manufacturing of the liquid crystal panel by liquid crystal injection or the like or during use of the liquid crystal panel. Conventionally,
The colored particles used for the colored spacer particles and the like are (A)
A method of dyeing colorless to white particles, (b) a method of obtaining spherical particles by subjecting a monomer containing a colorant to suspension polymerization or emulsion polymerization and then classifying the same, and (c) kneading a polymer and a colorant. It is manufactured by methods such as granulation and classification. However, among the conventional colored particles obtained by the method (a), the dye does not sufficiently penetrate into the inside of the particles, and the color tone is not sufficient and the light-shielding property is insufficient. Or it may dissolve in the liquid crystal and disturb the alignment of the liquid crystal.
In the method obtained by the method described above, since the coloring agent having no or poor affinity for the components constituting the base particles is dispersed at a high concentration, the brittle material often becomes brittle, and the constituent material of the coloring particles may peel or fall off. It is difficult to lower the concentration of impurities sufficiently due to the colorant,
With the conventional technique, it is extremely difficult to obtain colored particles satisfying the above requirements.

[0003]

Accordingly, the present invention is excellent in strength and heat resistance, has a sufficient degree of coloring, has no elution of components such as coloring components, and exhibits stable light-shielding performance at all times. In particular, it is an object of the present invention to provide colored particles suitable as colored spacer particles.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a cinnamic acid having a polymerizable double bond and / or a derivative thereof (hereinafter referred to as "cinnamic acid").
It is called "polymerizable cinnamic acids". )) (Hereinafter referred to as “cinnamic acid component-containing monomer”). A polymer obtained by polymerizing a monomer (hereinafter referred to as “cinnamic acid component-containing polymer”) is irradiated with light to form a coloring component. And colored particles contained in the base particles.

Hereinafter, the present invention will be described in detail. This will clarify the objects, configurations and effects of the present invention. First, as the base particles, together with the specific coloring component of the present invention, it is possible to form colored particles that have a predetermined strength and heat resistance and do not peel off or fall off during use in various applications. As long as various materials can be used, preferred base particles are made of an organic material which is swollen by the cinnamic acid component-containing monomer but does not dissolve in the monomer.

Examples of such preferred base particle materials include olefins such as ethylene and propylene; aromatic vinyl compounds such as styrene, α-methylstyrene and p-methylstyrene; methyl (meth) acrylate;
(Meth) acrylic esters such as ethyl (meth) acrylate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; vinyl esters such as vinyl acetate, vinyl propionate and vinyl butyrate; N-methyl (meth) acrylamide; N-alkyl-substituted (meth) acrylamides such as -ethyl (meth) acrylamide;
Vinyl cyanide compounds such as (meth) acrylonitrile; vinyl halide compounds such as vinyl chloride, vinylidene chloride, and tetrafluoroethylene; (meth) acrylic acid, crotonic acid, itaconic acid, vinylsulfonic acid, and (meth) allyl sulfone Acid, styrene sulfonic acid, (meth)
Sulfopropyl acrylate, vinylbenzoic acid, (meth)
Allylbenzoic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, (meth) acryloxy-3
-Unsaturated acids such as propanesulfonic acid or salts thereof; divinylbenzene, (poly) ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,4-divinyloxybutane, 1,4-diallyl (Co) polymers of polymerizable unsaturated monomers such as polyfunctional unsaturated compounds such as oxybutane, divinyl sulfone, diallyl sulfone, divinylamine and di (meth) allylamine: polyether, polyacetal, polycarbonate, polyester, Alkyd resin,
Unsaturated polyester, polyarylate, polysulfide, polysulfone, polyamide (for example, nylon-6,
Nylon-12), polyimide, polysiloxane, epoxy resin, phenol resin, urea resin, melamine resin, benzoguanamine resin, etc. (co) polyaddition or (co) polycondensation resin: natural resin such as cellulose, starch, etc .: ionomer: Organic polymer materials such as derivatives of each of the above materials can be mentioned. In addition, these base particle materials,
The particles may have a crosslinked structure.

When the base particles are used as particles when a coloring component is contained therein, the base particles can be directly produced as particles by (co) polymerization of the polymerizable unsaturated monomer. It can also be obtained by granulating and classifying a non-particulate material. These base particles may be a mixture of two or more types of particles made of different materials. If the base particles are commercially available, they can also be used.

In the (co) polymerization of the polymerizable unsaturated monomer for producing the base particles, emulsion polymerization, emulsion polymerization without using an emulsifier (so-called soap-free emulsion polymerization), suspension polymerization, dispersion polymerization , Precipitation polymerization, seed polymerization, etc., among which, soap-free emulsion polymerization and seed polymerization are preferred from the viewpoint of uniformity of particle diameter. Further, the base particles may be classified after the (co) polymerization to measure a uniform particle size.

When the base particles are obtained through a granulation step of a non-particulate material, for example, tumbling granulation, fluidized bed granulation, stirring granulation, pulverization / crushing granulation, compression granulation, extrusion Physical granulation methods such as granulation, melt granulation, mixed granulation, spray cooling granulation, spray drying granulation, precipitation / precipitation granulation, freeze drying granulation, suspension aggregation granulation, drop cooling granulation, etc. Can be appropriately selected according to the type of the base particle material to perform granulation.

From the viewpoint of using colored particles as colored spacer particles, the pressure and heating conditions in the LCD substrate assembly process differ depending on the type of LCD.
The compression resistance (ie, strength) of the colored particles is usually 30 kgf / mm ² or more per particle, preferably 50 kgf / mm ² or more.
It has a breaking strength of at least gf / mm ^2, does not break even under pressure conditions after spraying the colored particles, and has a heat resistance (ie, thermal decomposition temperature) of the colored particles of usually 100 ° C.
Or higher, preferably 150 ° C. or higher,
Therefore, it is preferable that the organic polymer material constituting the base particles has a crosslinked structure.

The base particles having a crosslinked structure as described above can be produced by (co) polymerization of a polymerizable unsaturated monomer containing the polyfunctional unsaturated compound. It can also be produced by post-crosslinking the base particles having no structure using a crosslinking agent, radiation or the like.

Next, the polymerizable cinnamic acids used for producing the coloring component are represented by the following general formula.

Embedded image

Here, X is -COOH (cinnamic acid), -CH ₂ OH
(Cinnabar alcohol), -CHO (cinnamon aldehyde),

Embedded image (If Z is H and m is 1, chalcone),

(Where Z is -OCO-CH = CH ₂ and m is 1, chalcone acrylate)

(Where Z is -OCO-C (CH ₃ ) = CH ₂ and m is 1, chalcone methacrylate), -COO-CH = CH ₂ (vinyl cinnamate), -COO-CH _2- CH = CH ₂ (allyl cinnamate), -COO-C (C
H ₃ ) = CH ₂ (methacrylic cinnamate), -COO-CH ₂ -C (CH ₃ ) = CH
₂ (methallyl cinnamate), -CH ₂ O-CH = H ₂ (cinnabar alcohol vinyl ether), -CH ₂ O-CH ₂ -CH = CH ₂ (cinnabar alcohol allyl ether), -CH ₂ OC (CH ₃ ) = CH ₂ (cinnabar alcohol methacryl ether), —CH ₂ O—CH ₂ —C (CH ₃ ) = CH ₂ (cinnabar alcohol methallyl ether) and the like, and Y and Z represent a halogen atom, an alkyl group, -H, -OH, -O-CH = CH
_{2, -O-CH 2 -CH =} CH 2, -OC (CH 3) = CH 2, -O-CH 2 -C (CH 3) =
CH ₂ , -CH ₂ O-CH = CH ₂ , -CH ₂ OC (CH ₃ ) = CH ₂ , -CH ₂ O-CH ₂ -CH
= CH ₂ , -CH ₂ O-CH ₂ -C (CH ₃ ) = CH ₂ , -OCO-CH = CH ₂ , -OCO-C (C
H ₃ ) = CH ₂ , -COO-CH = CH ₂ , -COO-C (CH ₃ ) = CH ₂ , -COO-CH ₂
-CH = CH ₂ , -COO-CH ₂ -C (CH ₃ ) = CH _{2 and the} like, and n and m
Is an integer of 0 to 5, and X and Y and / or Z may be the same or different from each other when each has a double bond, and Y and Z may be the same or different from each other And at least one of X, Y and Z is a group having a polymerizable double bond.

These polymerizable cinnamic acids can be used alone or in admixture of two or more. Particularly preferred polymerizable cinnamic acids are vinyl cinnamate and chalcone (meth) acrylate. .

The monomer containing a cinnamic acid component preferably further contains at least one polymerizable unsaturated monomer other than the polymerizable cinnamic acids.

The other polymerizable unsaturated monomers used together with the polymerizable cinnamic acids include those exemplified for the base particles.

By using such a cinnamic acid component-containing monomer, a polymer containing a cinnamic acid component having a high affinity for the base particles can be produced. And the coloring component is not easily eluted, peeled or dropped off from the base particles, and the strength of the coloring particles can be increased.

When the cinnamic acid component-containing monomer contains the other polymerizable unsaturated monomer, the proportion of the polymerizable cinnamic acids to the other polymerizable unsaturated monomer in the monomer is as follows: When the polymerizable cinnamic acids are other polymerizable unsaturated monomers 10
The amount is usually 0.1 to 1000 parts by weight, preferably 1 to 100 parts by weight, per 0 parts by weight. When the amount ratio of the polymerizable cinnamic acids is less than 0.1 part by weight, the degree of coloring of the colored particles after light irradiation may be insufficient. In some cases, polymerizable cinnamic acids may remain as a monomer, and when the obtained colored particles are dispersed in a medium such as water or an organic solvent, the monomer may be eluted into the medium. In the present invention, by adjusting the content of the polymerizable cinnamic acids in the cinnamic acid component-containing monomer, the degree of coloring of the colored particles can be set to a desired level from gray to black.

As a method for incorporating a coloring component into the base particles, there are, for example, (1) a method in which the base particles are allowed to absorb the cinnamic acid component-containing monomer under light shielding and then swollen by the cinnamic acid component-containing monomer. A method of dispersing the material particles in an appropriate dispersion medium and polymerizing (hereinafter, referred to as “swelling dispersion polymerization”), and performing light irradiation during or after the polymerization is preferable for achieving a narrow particle size distribution, In some cases, (2) the solution of the cinnamic acid component-containing polymer is absorbed into the base particles under shading, and the swollen base particles are dispersed in an appropriate dispersion medium,
A method in which light irradiation is performed during or after the solvent is removed, or (3) a cinnamic acid component-containing polymer obtained by polymerizing a cinnamic acid component-containing monomer under light shielding, and a substrate particle material, under light shielding. After kneading, granulating, and classifying, a method of irradiating with light or the like can also be employed.

In the swelling dispersion polymerization in the method (1), even if the base particles are dispersed in a dispersion medium and then the cinnamic acid component-containing monomer is absorbed, the cinnamic acid component-containing monomer is added to the base particles. After absorption, it may be dispersed in a dispersion medium, but the former is particularly preferred. In the swelling dispersion polymerization, the composition of the cinnamic acid component-containing monomer is appropriately selected according to the type of the base particles so that the particles swell but do not dissolve.

In the swelling dispersion polymerization, the shape of the base particles is preferably spherical, but in some cases, non-spherical base particles such as ellipses may be used. Also,
The average particle size and particle size distribution of the base particles are appropriately selected depending on the use of the colored particles, desired characteristics, and the like.

The dispersion medium used in the swelling dispersion polymerization includes, for example, other media such as water, alcohols, ketones, ethers, esters, and amines. It is appropriately selected depending on the base particles, the polymerization catalyst, the cinnamic acid component-containing monomer, and the like, and is usually used mainly with water and, if necessary, adding the above-mentioned other medium.

In the swelling dispersion polymerization, the amount ratio of the base particles to the dispersion medium is usually 0.001 to 100 parts by weight, preferably 0.1 to 100 parts by weight, per 100 parts by weight of the dispersion medium.
1 to 50 parts by weight.

In the swelling dispersion polymerization, when the dispersion stability of the base particles and / or the obtained colored particles in the dispersion medium is poor, a dispersion agent can be added to stabilize the dispersion.

As the dispersant, those which are generally used as so-called dispersants can be used.
It can be appropriately selected according to the seed particles, the dispersion medium, the polymerization catalyst, the cinnamic acid component-containing monomer, and the like. In particular, those that can be rapidly adsorbed to the base particles and exhibit the intended dispersion stabilizing action are preferable.

Examples of such dispersants include higher fatty acid salts such as sodium oleate, alkyl sulfates such as sodium dodecyl sulfate, alkyl sulfonates such as sodium stearyl sulfonate, and alkyl aryl salts such as sodium dodecyl benzene sulfonate. Anionic surfactants such as sulfonates, sulfosuccinates such as dioctyl sodium sulfosuccinate; alkyl polyoxyethylene ethers, alkylphenyl polyoxyethylene ethers, polyethylene glycol alkyl ethers, alkyl carbonyloxy polyethylenes, N, N-di (polyoxyethylene) alkaneamides, N, N-di (alkanol) alkaneamides, polyethylene glycol fatty acid esters, sorbitan fatty acid esters Nonionic surfactants such as fatty acid polyhydric alcohol esters such as fatty acid monoglyceride and fatty acid sucrose ester; fatty acid polyhydric alcohol polyoxyethylene ethers; higher alkyl ammonium salts such as dodecyl ammonium chloride; and quaternary compounds such as dodecyl pyridinium chloride. Quaternary N- such as quaternary N-alkylpyridinium salts and dodecylpicolinium chloride
Alkyl picolinium salts, quaternary alkyl ammonium salts such as cetyltrimethyl ammonium bromide,
Such as quaternary alkyl imidazolinium salts, quaternary polyoxyethylene alkyl diammonium salts, quaternary polyoxyethylene alkyl ammonium salts, quaternary alkoxypropyl ammonium salts, and organic or inorganic acid salts of alkyl propylene diamine. Cationic surfactants; zwitterionic surfactants such as alkylamine oxides, alkylglycines, alkylalanines, alkylbetaines, alkylimidazolines; carboxymethylcellulose, hydroxyethylcellulose,
Examples thereof include cellulose derivatives such as hydroxypropylcellulose, and polymer dispersants such as polyvinylpyrrolidone, polyvinyl alcohol, sodium polycarboxylate, and polyacrylic acid. These dispersants can be used alone or in combination of two or more.

Such a dispersing agent is used to stabilize the dispersion of the cinnamic acid component-containing monomer in the dispersion medium when the cinnamic acid component-containing monomer is absorbed by the base particles in the swelling dispersion polymerization. It is also preferable to use them. In such a case, it is preferable to sufficiently disperse the cinnamic acid component-containing monomer in the dispersion medium together with the polymerization catalyst in the presence of the dispersant, and to add the obtained dispersion to the dispersion of the base particles. . In this case, the addition of the cinnamic acid component-containing monomer dispersion can be performed continuously, intermittently, or all at once. The amount of the dispersant used is usually 30 parts by weight or less, preferably 0.1 part by weight, based on 100 parts by weight of the base particles.
-20 parts by weight.

In the swelling dispersion polymerization, the content of the cinnamic acid component-containing monomer in the base particles depends on the desired particle size of the colored particles, but is usually 0.1 to 1000 per 100 parts by weight of the base particles. Parts by weight, preferably 1-1
00 parts by weight. When the content of the cinnamic acid component-containing monomer is less than 0.1 part by weight, the swelling ratio of the base particles is low, and the degree of coloring of the colored particles is low depending on the content of the polymerizable cinnamic acids in the monomer. May be 100
If it exceeds 0 parts by weight, the cinnamic acid component-containing monomer absorbed by the base particles may remain, or the particle size distribution of the obtained colored particles may be widened. In the present invention, the particle size and degree of coloring of the colored particles can be adjusted by the content of the cinnamic acid component-containing monomer in the base particles.

In the swelling dispersion polymerization, the polymerization catalyst used for the polymerization of the cinnamic acid component-containing monomer absorbed by the base particles includes, for example, sulfur dioxide, an aqueous solution of sulfurous acid, sodium sulfite, ammonium sulfite and the like. Redox-type polymerization catalyst containing persulfate such as potassium persulfate, sodium persulfate and ammonium persulfate; benzoyl peroxide, lauroyl peroxide, di-t
-Butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, 2,2′-azobisisobutyronitrile,
Radical polymerization catalysts such as 2,2'-azobisisovaleronitrile and 2,2'-azobis (2-amidinopropane) dihydrochloride can be used alone or in combination of two or more.

The polymerization conditions in the swelling dispersion polymerization depend on the type of polymerization catalyst, monomer containing cinnamic acid, dispersion medium, etc., but the polymerization temperature is usually about 0 to 100 ° C., and the polymerization time is usually It is about 10 minutes to 48 hours.

In the swelling dispersion polymerization, the cinnamic acid component-containing monomer absorbed by the base particles is converted into an aromatic ketone such as benzophenone or Michler's ketone; an acetophenone such as acetophenone or benzoin ether; a diketone such as benzyl. Can be photopolymerized in the presence of a sensitizer such as acyl oxime esters and acyl phosphine oxides. In this case, the polymerization catalyst may or may not be used. Such photopolymerization, like the light used to generate the coloring components described below,
Irradiation with light of an appropriate wavelength from visible light to far ultraviolet light is performed, usually at a polymerization temperature of 0 to 100 ° C. until the required polymerization conversion is reached. According to the photopolymerization, simultaneously with the polymerization of the cinnamic acid component-containing monomer, colored particles having a desired degree of coloring from gray to black can be obtained.

When the colored particles are used in particular as colored spacer particles, the polymer containing the cinnamic acid component preferably has a crosslinked structure. Therefore, the colored particles having a crosslinked structure include (a) a case where only the base particles have a crosslinked structure, (b) a case where only the cinnamic acid component-containing polymer has a crosslinked structure, and (c) a case where the base particles have a crosslinked structure. Both the polymer and the cinnamic acid component-containing polymer may have a crosslinked structure, but the case (c) is particularly preferred. Further, in the colored particles, the polymer molecules constituting the base particles and the polymer molecule containing the cinnamic acid component can be mutually bonded by a so-called graft bond or the like.

When a polymer containing a cinnamic acid component having a crosslinked structure is produced by swelling dispersion polymerization, a monomer containing a cinnamic acid component containing a crosslinkable monomer is preferably used. After a polymer containing a cinnamic acid component having no crosslinked structure is produced by dispersion polymerization, post-crosslinking can also be performed.

In the swelling dispersion polymerization, the crosslinkable monomers used to introduce a crosslinked structure into the cinnamic acid component-containing polymer include divinylbenzene, diisopropenylbenzene, (poly) ethylene glycol di (meth)
Acrylate, (poly) propylene glycol di (meth) acrylate, 1,4-butanediol di (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, divinyl ether, dimethacryl ether, di (meth) allyl ether, 1,4-divinyloxybutane, 1,4-diallyloxybutane, divinyl phthalate, dimethacryl phthalate, Examples thereof include polyfunctional unsaturated compounds such as di (meth) allyl phthalate, divinyl sulfone, dimethacrylsulfone, di (meth) allyl sulfone, divinylamine, dimethacrylamine, and di (meth) allylamine. These crosslinkable monomers can be used alone or in combination of two or more.

The above-mentioned swelling-dispersion polymerization can be carried out, for example, in the same manner as in a normal seed polymerization operation. The colored particles of the present invention can be produced industrially extremely advantageously. It is. Further, in the swelling dispersion polymerization, colored particles having a uniform particle size can be easily obtained by using base particles having a narrow particle size distribution.

The light used for irradiating the polymer containing the cinnamic acid component during and / or after the swelling dispersion polymerization to form a coloring component is a light having a wavelength from visible light to far ultraviolet light. Can be used, but is preferably light having a wavelength of 100 to 800 nm, particularly preferably 180 to 700 nm. In addition, the irradiation conditions of the light, the irradiation temperature is preferably 0 ~ 100 ℃, irradiation time,
Usually, it is about 0.1 to 24 hours.

In the present invention, the mechanism for coloring the polymer containing the cinnamic acid component by light irradiation is such that the remaining double bond causes an addition reaction by the light irradiation, and the crosslinked structure in the polymer containing the cinnamic acid component is changed. Is introduced.

The average particle size and particle size distribution of the colored particles of the present invention can be determined by appropriately adjusting the average particle size and particle size distribution of the base particles in the swelling dispersion polymerization, the amount of the cinnamic acid component-containing monomer absorbed into the base particles, and the like. By selecting, the use of colored particles,
It can be set to a substantially arbitrary value according to desired characteristics and the like. Particularly when the colored particles are used as colored spacer particles, the average particle size of the colored particles is preferably 1 to 20 μm.
m, more preferably 1 to 10 μm, particularly preferably 2
８8 μm. In this case, when the colored particles are not necessarily symmetrical, the average particle diameter assumes a minor axis diameter. In addition, the particle size distribution of the colored particles can be reduced to a desired level by classifying as necessary. In particular, when the colored particles are used as colored spacer particles, the smaller the CV value (= standard deviation / average particle size) of the particle size distribution of the colored particles, the better, usually within 10%, preferably within 5%, particularly preferably 3%. Set within
By reducing the CV value of the particle size distribution of the colored particles,
The thickness of the liquid crystal layer can be kept constant.

The colored particles of the present invention do not elute the coloring components even when dispersed in water or various organic solvents and are irradiated with ultrasonic waves, and are no longer colored during the production or use of LCDs. Components and other components do not peel off or fall off. Therefore, especially when such colored particles are used as colored spacer particles, stable light-shielding performance can always be exhibited. In addition, the colored particles can keep the impurity concentration low, and can be compressed and deformed to some extent by pressurizing and heating in the LCD substrate assembly process, and can be firmly fixed to the electrode substrate, and the colored component is substantially contained in the base particles. It is uniformly distributed above and has a uniform degree of coloring. The colored particles of the present invention are also useful as a coloring agent for various rubbers, plastics, paints, and the like, a light-shielding agent, and the like.

[0040]

Next, the present invention will be described more specifically with reference to examples. Example 1 10 g of polystyrene particles having an average particle size of 4.0 μm and having a CV value of 3% or less in particle size distribution, 0.5 g of sodium dodecyl sulfate and 500 ml of water were sufficiently stirred with a homogenizer to disperse the base particles. A liquid was prepared. Separately, 200 ml of water, 40 g of divinylbenzene,
10 g of vinyl cinnamate and benzoyl peroxide 2
Ultrasonic waves were applied to the mixture consisting of g to sufficiently emulsify and disperse, thereby preparing an emulsion of a cinnamic acid component-containing monomer. To the dispersion of the base particles, while stirring at room temperature under shading, add the emulsion of the cinnamic acid component-containing monomer, and after allowing the base particles to absorb the cinnamic acid component-containing monomer over 10 hours, The temperature was raised to 70 ° C., and polymerization was performed for 10 hours. Then, the reaction dispersion was cooled to room temperature while stirring,
After irradiation with light having a wavelength of 365 nm for 4 hours and further stirring at room temperature for 5 hours, the mixture was centrifuged to precipitate particles. After that, the supernatant liquid was separated, and the washing operation of adding distilled water, sufficiently stirring with a homogenizer to uniformly disperse the particles, and centrifuging was repeated three times. Next, the obtained particles were dried at room temperature. When the particles thus obtained were observed with a scanning electron microscope, the average particle diameter was 5.
The spherical black particles had a particle size distribution of 2 μm and a CV value within 3% of the average particle size. The colored particles were washed by centrifugation in isopropyl alcohol, dried, and then pressed as colored spacer particles in an LCD substrate assembly process at 160 ° C. and 1.0 kg / cm ^2. It was kept constant at 5 μm, and was firmly fixed to the upper and lower transparent electrode substrates, and the colored particles were firmly fixed when the liquid crystal was injected, and the overall strength and heat resistance of the colored particles were excellent.

Example 2 10 g of polystyrene particles having an average particle diameter of 4.0 μm and a particle size distribution having a CV value of 3% or less, polyvinyl alcohol
(Trade name: PVA-117, manufactured by Kuraray Co., Ltd.) 1.0 g and 500 ml of water were sufficiently stirred with a homogenizer to prepare a dispersion of base particles. Separately, water 100
Ultrasonic was applied to a mixture consisting of milliliters, 40 g of divinylbenzene, 10 g of chalcone methacrylate and 2 g of benzoyl peroxide, and sufficiently emulsified and dispersed.
An emulsion of the cinnamic acid component-containing monomer was prepared.
In the dispersion of the base particles, under light shielding, while stirring at room temperature,
Adding an emulsion of the cinnamic acid component-containing monomer,
After the cinnamic acid component-containing monomer was absorbed into the base particles over 10 hours, the temperature was raised to 70 ° C. and polymerization was performed for 10 hours.
Next, the reaction dispersion was cooled to room temperature with stirring, irradiated with light having a wavelength of 600 nm for 6 hours, further stirred at room temperature for 5 hours, and then centrifuged to precipitate particles. afterwards,
After separating the supernatant, a washing operation of adding distilled water, sufficiently stirring with a homogenizer to uniformly disperse the particles, and centrifuging was repeated three times. Next, the obtained particles were dried at room temperature. When the particles thus obtained were observed with a scanning electron microscope, the average particle size was 5.2 μm.
m, spherical black particles having a CV value of 3% or less in the particle size distribution. After washing the colored particles in isopropyl alcohol by centrifugation and drying, as colored spacer particles,
160 ° C. in the LCD substrate assembly process;
When pressure was applied under the condition of 0 kg / cm ² , the distance between the transparent electrode substrates was kept constant at 5 μm, and it was firmly fixed to the upper and lower transparent electrode substrates, and the colored particles were firmly fixed even during liquid crystal injection. And the strength and heat resistance of the colored particles as a whole were also excellent.

[0042]

According to the present invention, it has excellent strength and heat resistance, has a sufficient degree of coloring, does not elute constituent components such as coloring components, etc., and always shows stable light shielding performance, etc.
Particularly, colored particles suitable as colored spacer particles are industrially extremely advantageously provided.

Continuation of front page (72) Inventor Hiroaki Nemoto 2-11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-1-315408 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08J 3/12-3/16

Claims (1)

(57) [Claims] Claims: 1. A coloring material containing a coloring component produced by irradiating a polymer obtained by polymerization of a monomer containing a cinnamic acid having a polymerizable double bond and / or a derivative thereof in a base particle. particle.