TW556020B - Spacer for liquid crystal displays, production process therefor, and liquid crystal display - Google Patents

Abstract

The present invention provides: a liquid crystal display which has excellent cell gap uniformity in response to the large sizing of the substrate, and further has high image display quality; a spacer which has excellent dry dispersibility even onto a large-sized substrate and undergoes little detachment of the fine particle, so that the provision of the above liquid crystal display can be achieved; and a process for producing such a spacer. A spacer for liquid crystal displays is used which comprises a particle body and a hydrophobic fine particle that is attached to a surface of the particle body, wherein the hydrophobic fine particle has a zero or positive electrification property in terms of triboelectrification property with an iron powder. In addition, this spacer may be an adhesive spacer wherein the above particle body is an adhesive particle.

Description

556020 A7 B7 V. Description of the invention (1) Background of the invention A. Technical scope The present invention relates to: a spacer material used in a liquid crystal display, which has superior dry dispersibility; a method for manufacturing the spacer material; and a use Liquid crystal display of the spacer. B. Background Techniques Writing this page A liquid crystal display (LCD) usually consists of two opposing electrode substrates, a spacer substance sandwiched between them, and a liquid crystal. The spacer material is used to keep the thickness of the liquid crystal layer uniform and fixed. High response speed, high contrast ratio, wide viewing angle, etc. are usually particularly important properties required for practical use of liquid crystal displays. In terms of these properties, the thickness of the liquid crystal layer, that is, the distance between the two electrode substrates, must be strictly fixed (uniformity of the gap between the members). Examples of spacers printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs for use in liquid crystal displays that meet the aforementioned requirements are as follows: silica particles, prepared by the sol-gel method (JP-A -62-269933): the aforementioned dioxide Porous sedimentary soil of silicon particles (JP-A-01-234826): and polymer particles mainly composed of styrene mono- or divinylbenzene, and monomers mainly composed of styrene- or divinylbenzene Obtained by suspension polymerization (JP — A-6 1 — 0 9 5 0 1 6) ° The spacer used in the liquid crystal display is dispersed on a substrate in a wet or dry manner. Among these methods, 'the wet method is, for example, a method in which the substrate is sprayed with a dispersion liquid', the dispersion liquid is adapted by applying a spacer material to the paper size of China National Standard (CNS) A4 (210 X 297 mm) -4- 556020 A7 __ B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (2) Dispersed in a solvent such as flon, alcohol, or water-alcohol-mixed solvent. However, this wet method has problems such as: adjustments to flons; environmental pollution and combustion due to organic solvents; and damage or pollution to the oriented mold due to solvents. In this regard, as far as the method of dispersing the spacer substance is concerned, a dry method is currently used instead of the wet method. I The drying method is a method in which a spacer is directly dispersed on a substrate using a gas such as compressed nitrogen. For example, a drying method f 'is proposed, which uses a high-speed airflow method or an electrostatic dispersion method, in which the spacer material is sprayed from a high-voltage generating nozzle onto a grounded substrate. As for the spacer material having superior dry dispersibility, for example, J P-A-10-0 1 0 5 4 2 proposes a spacer material including a particle body and fine particles attached to the surface of the particle body. The fluidity of the spacer material is improved to have improved dispersibility, and therefore, the gap uniformity of the member can be improved. In recent years, the liquid crystal display has also been used in portable terminals or mobile communicators, such as cell phones and pagers, and automobile auxiliary equipment, such as car navigation systems. Among these applications, when compared with desktop personal computers, word processors, televisions, etc., there is a problem that the spacer material is liable to move or fall due to the load involved in transportation such as vibration or impact, so the thickness of the liquid crystal layer Unable to remain uniform and fixed. In addition, in recent years, as far as the aforementioned personal computers are concerned, the display has been increasing in size endlessly, and when the display actually has a large size, 'the electrode substrate warp also exists' to make the spacer material easier > Γ. (Please First read the note on the back jR to fill in this page) The size of this paper is applicable to the Chinese National Standard (CNS) A4 (210 x 297 cm) 556020 A7 B7 V. Description of the invention (3) The liquid crystal layer cannot be moved The thickness is guaranteed to be uniform and fixed ----------- II ^ · II (Please read the precautions on the back and fill out this page) For the purpose of preventing the aforementioned spacers from moving and falling In other words, the development of adhesive spacers, wherein the adhesive spacers have a knot, so that the surface of a spacer particle is coated with an adhesive. * Known examples of the adhesive spacer material include: an adhesive spacer material prepared by the following method (high-speed airflow impact method), wherein the thermal deformation temperature is fine within a range of 25 to 180 t The resin powder is electrostatically adsorbed on the surface of the hardened spherical fine particles of an amine-based resin by the electrostatic force printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The product formed is dispersed in an air stream flowing at high speed. Hitting on the hardened spherical fine particles, and fixing the fine resin powder on the surface of the hardened spherical fine particles (JP — A — 〇1 -1 5 0 4 2 8); an adhesive spacer It is produced by the following method (agglomeration method), in which spherical fine particles such as crosslinked divinylbenzene particles or silica glass are dispersed in a solution of a hot-melt resin or epoxy resin, and formed The temperature of the dispersion is gradually lowered or a poor solvent of these resins is added dropwise to the dispersion, so that the aforementioned resin is dispersed on the surface of the spherical fine particles (JP-A — 〇1-247 1 54 JP-A — 02 — 261537, JP-A -04-036723, JP-A — 04 — 036724): and an adhesive spacer, by bonding an adhesive polymer link to the surface of a spherical fine particle It is prepared by forming an adhesive layer on the particle surface (JP-A-07-300568, JP-A-07-300587, JP-A-07333623). As of this paper size, the Chinese National Standard (CNS) A4 specification (210 X 297 mm) applies -6- 556020 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (4) How are these adhesive spacers In other words, the surface of the spherical fine particles is coated with an adhesive layer, including an adhesive resin. In addition, JP-A-09-2 4 4 0 3 2 series discloses an adhesive spacer material in which the k-wet dispersibility is improved by attaching a fine particle to the surface of an adhesive particle-. On the other hand, recently, as the ratio of liquid crystal displays used as thin film transistor-liquid crystal display detectors has increased, the area size of the substrate has begun to increase to increase productivity, so the uniformity of the gap between the members has become more and more important. The more important. Therefore, the aforementioned spacer material proposed by JP—A—10—010542 is still insufficient to meet the recent increase in the size of substrates, but the spacer material has the specific effect of increasing the uniformity of the gap of the member. Therefore, a spacer material having superior dry dispersibility (single dispersibility and continuous dispersibility) and a liquid crystal display having superior uniformity of the gap between members are required. In addition, as for the aforementioned spacer material disclosed in detail in JP — A-10-010542, the fine particles attached to the particle body may fall off by themselves, and the dropped fine particles may damage the contrast ratio and damage the liquid crystal. Image display quality of the monitor. As with the panel in the panel manufacturing step when the spacer material is dispersed, not only the dispersibility of the spacer material, but also preventing the spacer material from moving due to vibration or impact is also very important for the uniformity of the gap between the members. The aforementioned adhesive spacer material for fixing to the substrate is most important for preventing the spacer material from moving. It has the structure as disclosed in JP — A-09-2440 3 2 so that fine particles adhere to the surface of an adhesive particle (please read the note on the back first? ^ Fill in this page) »-Binding · This paper size is in accordance with Chinese National Standard (CNS) A4 specification (210 X 297 mm) 556020 A7 B7 V. Description of the invention (5) The barrier material has excellent moisture dispersion, but it is still insufficient for the recent large-size substrates. However, the spacer substance also has a specific effect of improving the uniformity of the gap of the member in the dry dispersion method because of improving the fluidity of the spacer substance. Therefore, there is a need for a spacer material having better dry dispersibility (single dispersion and continuous dispersion stability) and a liquid crystal display with superior uniformity of inter-member gaps. In addition, as for the aforementioned spacer material disclosed in detail in JP — A — 09 — 244032, the fine particles attached to the adhesive particles may fall off, and the fallen off fine particles may damage the contrast ratio and cause damage. And the image quality of the LCD monitor is not good. Description of the invention A. Purpose of the invention Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics The purpose of the present invention is to propose: a liquid crystal display with superior uniformity of component gaps relative to the large size of the substrate, and additionally a high image display Quality; a spacer material, which has superior dry dispersibility even on large substrates, and the fine particles hardly fall off, so the aforementioned liquid crystal display can be provided; and a method for producing the spacer material. B. Disclosure of the invention The present inventor has painstakingly studied the spacer material used in the liquid crystal display, wherein the dry dispersibility (monodispersity and continuous dispersion stability) of the spacer material on a large-sized substrate has been improved, and the fineness The particles hardly fall off. As a result, the inventors found that the use of thin paper sheets with specific electrification properties is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -8- 556020 A7 B7 2. Description of the invention (6) Water-based fine particles can solve the aforementioned problems. That is, the spacer substance used in the liquid crystal display of the present invention includes a particle body and hydrophobic fine particles attached to the surface of the particle body, wherein the hydrophobic fine particles have zero or Positive electrification. In addition, the method for manufacturing a spacer for use in a liquid crystal display of the present invention includes the step of attaching a hydrophobic fine particle to the surface of a particle body, wherein the hydrophobic fine particle is related to the triboelectric property of iron powder, and With zero or positive electrification. / 间隔 The aforementioned spacer material of the present invention used in a liquid crystal display may be an adhesive spacer material, wherein the aforementioned particle system is an adhesive particle. In order to obtain an adhesive spacer material, the method for manufacturing a spacer material for a liquid crystal display according to the present invention further includes, for example, coating an adhesive layer on the surface of the particle body before the hydrophobic fine particles are attached to the surface of the particle body. , To obtain a step of adhesive particles. In addition, the liquid crystal display of the present invention includes: two electrode substrates, which are arranged opposite to each other; a spacer material for the liquid crystal display, which is sandwiched between the electrode substrates to maintain a gap between the electrode substrates Distance; and a liquid crystal filled between the electrode substrates; the liquid crystal display is characterized by using the aforementioned spacer material of the present invention. These and other objects and advantages of the present invention will be fully understood from the following detailed disclosure. Brief Description of Drawings Figure 1 is a schematic cross-sectional view showing an example of the liquid crystal display of the present invention < Please read the notes on the back first '^ Fill this page) l »i Binding: This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -9-556020 2 3 4 5 6 7 8 A7 B7_ 5. Description of the invention (7) Figure. Main component comparison table Sealing material + spacer material orientation film * Polarized electrode film, spacer material in the liquid crystal plane First substrate second substrate 110 First electrode substrate 120 Second electrode substrate Detailed description of the invention First, the invention is used for liquid crystal Spacer for display. '(Spacer substance used in liquid crystal display): The particle structure of the spacer substance used in the liquid crystal display of the present invention is a particle structure including a particle body and fine particles attached to the surface of the particle body. First, this particle system is described below. This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) il · --------- M___ (Please read the notes on the back first and fill in this page) Order ·· Economic Printed by the Consumer Cooperative of the Ministry of Intellectual Property Bureau-10-556020 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy The thickness needs to remain uniform and fixed. The average particle diameter of the particle body is preferably in the range of 0.5 to 30 microns, more preferably 1 to 25 microns, and most preferably 1 to 20 microns. Particle body_Average particle diameters outside these ranges usually make the spacer material unusable as spacer material for liquid crystal displays. The coefficient of variation (CV) in the particle size of the particle body is preferably within a range of not more than 10%, more preferably not more than 8%, more preferably not more than 7%, and most preferably not more than 6% . When a liquid crystal display uses a spacer in which the particle size variation coefficient of the particle body exceeds 10%, it is difficult to keep the thickness of the liquid crystal layer uniform and fixed, so it is easy to cause uneven images. The definition or measurement of the average particle diameter and the coefficient of variation of the particle diameter in the present invention is performed using the method disclosed in the following specific examples. The charge capacity of the particle body is not particularly limited. However, the effect of the present invention is great especially when it is in the range of 2 to 2,000 // C / g. A charge in the range of 5 to _1,500 // C / g is better, and a charge in the range of 10 to 1,000 vC / g is better. Incidentally, the amount of charge of the particle body was measured in the same manner as the particles described below. As for the particle body, various types can be used, and therefore are not particularly limited. However, examples thereof include organic crosslinked polymer particles, inorganic particles, and organic-inorganic-composite particles. Among these particles, organic cross-linked polymer particles and organic-inorganic-composite particles are preferred, as they prevent electricity (please read the note on the back first and fill in this page) The size of this paper applies to Chinese national standards (CNS ) A4 size (210 X 297 mm) -11-556020 A7 ^ B7 V. Description of the invention (9) The electrode substrate, the oriented film, or the color filter is damaged, or it can easily provide a uniform gap between the electrode substrates . The shape of the particle body may be any particle shape such as a sphere, a needle, a flake, a flake, a shard, a rugby shape, a cocoon shape, or a star shape. Therefore, the shape is not particularly limited, but a sphere shape is more favorable for an f-pole substrate. A uniform and fixed gap distance is obtained, but if the particle is spherical, the particle has a fixed or nearly fixed particle diameter in all or almost all orientations. The organic crosslinked polymer particles are not particularly limited, but examples thereof include crosslinked divinylbenzene resin particles prepared by homopolymerizing or copolymerizing divinylbenzene with other vinyl monomers (JP — A— (01-1 4 4 4 2 9). The inorganic particles are not particularly limited, but examples thereof include spherical fine particles of glass, silicon dioxide, and alumina. The aforementioned organic-inorganic-composite particles are composite particles including organic and inorganic parts. In the organic-inorganic-composite particles, the proportion of the inorganic portion is not particularly limited, but in terms of inorganic oxides, it is preferably, for example, between 10 and 90% by weight relative to the organic-inorganic-composite particle system. Within the range, more preferably within a range of 25 to 85 weight percent, more preferably within a range of 30 to 80 weight percent. The proportion of the inorganic portion expressed as an inorganic oxide is the organic-inorganic-measured before and after sintering the organic-inorganic-composite particles in an oxidizing atmosphere such as air at a high temperature (eg, 1,000 ° C). Individual particle weight percentage of composite particles. When the proportion of the inorganic portion of the organic-inorganic-composite particles is lower than the foregoing range as represented by the inorganic oxide, the organic-inorganic-composite particles are in accordance with the Chinese National Standard (CNS) A4 specification (210 X 297 public love) on this paper --- 〆 ------------ ^ ___ (Please read the notes on the back and fill out this page first) · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs12 · 556020 A7 B7 V. Description of the invention (Ίο) It is quite soft, and it is necessary to increase the number of spacer substances dispersed on the electrode substrate. When the ratio is higher than the aforementioned range, the organic-inorganic-composite particles are too hard, and easily damage the oriented film or cause the thin film transistor array to break. The foregoing organic-inorganic-composite particles are not particularly limited, but examples thereof include organic-inorganic-composite particles, including an organic polymer frame and a polysiloxane frame, wherein the polysiloxane frame molecule has an organic silicon , Containing silicon atoms that are directly chemically bonded to at least one carbon atom of the organic polymer frame, wherein the amount of SiO2 that constitutes the polysiloxane frame is not less than 10 weight percent. In the organic polymer frame, a vinyl polymer is more advantageous for producing a high elasticity capable of controlling the gap. The organic-inorganic-composite particles may be colored by containing one or both of a dye and a pigment. The method for producing the organic-inorganic-composite particles is not particularly limited, but examples thereof include the following production methods, including steps of condensation, polymerization, and heat treatment. The condensation step includes a step of subjecting a silicon compound containing a radical polymerizable group to hydrolysis-condensation. In this condensation step, an alkaline catalyst such as ammonia can be used as a catalyst. The sand-polymerizable group-containing sand compound is preferably a compound having at least one general formula selected from the following general formulae (1) to (3), or a derivative thereof. General formula (1): I r \ t CH corpse C— COORb price—Si-(0Rc) 4 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back first 3Fill in this page) I · -Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-13- 55602ο A7 ^^^ _____B7 V. Description of the invention ⑴). Among them: Ra is hydrogen atom or methyl group; A bivalent organic group of 20 to 20 carbon atoms, which may have a substituent; Re is at least one monovalent group selected from a hydrogen atom, an alkane k having 1 to 5 carbon atoms, and A fluorenyl group of 5 carbon atoms; R1 is at least one monovalent group, and alkyl_ and phenyl groups having 1 to 5 carbon atoms are selected; 1 is Gu 1 or 2; and P is 0 or 1. β f " · General formula (2): (please take P 誊 this page)

(2) wherein: Rd is a hydrogen atom or a methyl group; Re is at least one monovalent group selected from a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and a fluorene having 2 to 5 carbon atoms R2 is at least one monovalent radical, selected from alkyl and phenyl groups having 1 to 5 carbon atoms; η is Gu 1 or 2; and Q is printed or typed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. through

Rf ·

CH

s R R 丨 S1

\ M (3) η This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -14- 556020 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (12) Among them: Rf is a hydrogen atom or a methyl group; Rg is a divalent organic group having 1 to 20 carbon atoms, which may have a substituent; is at least one monovalent group 'selected from a hydrogen atom, having 1 to 5 Alkyl groups of 2 carbon atoms, and fluorenyl groups having 2 to 5 carbon atoms; R3 is at least one monovalent _, selected from alkyl groups and phenyl groups having 1 to 5 carbon atoms; η is Gu 1 or 2; And r is 0 or 1. The polymerization step includes performing a radical polymerization reaction of the free-radically polymerizable group during or after the condensation step, or during the condensation step and after the plant to obtain the particles. The heat treatment step includes a step of drying and sintering a polymer particle from the polymerization step in a temperature range preferably not higher than 800 ° C, and more preferably 100 to 600 ° C. This heat treatment step is preferably performed, for example, in an atmosphere with an oxygen concentration of not higher than 10% by volume or under vacuum. The production step may further include a coloring step, in which the formed particles are colored during or after at least one step selected from the condensation step, the polymerization step, and the heat treatment step, or during and after the coloring. If necessary, the spacer material used in the liquid crystal display of the present invention can be colored, for example, by making the particle body contain at least one coloring agent selected from dyes and pigments. The color is preferably a color that is almost opaque or completely opaque 'because the color can prevent light leakage from the backlight and improve the contrast ratio in image quality. Examples of colors that are almost opaque or completely opaque include colors such as black, dark blue, navy, purple, blue, dark green, brown, and red. Especially black, dark blue and navy blue are preferred. One or two of the dye and the pigment can be accidentally simply contained in the particles. The paper size of the paper is applicable to Chinese national standards (CNS> A4 specification (210 X 297 mm)) (Please read the notes on the back first ^^ Fill in this page ) —Binding · • Teaching-• 15- 556020 A7 -------------- B7 V. Description of the invention (13) The body, or the spacer may have a structure in which the dye and Either one or two of the pigments are chemically bonded to the matrix constituting the particle body. The dye is appropriately selected and used according to the desired color, and examples include those classified according to the dyeing method, such as dispersibility Dyes, acid dyes, basic dyes, reactive dyes, and sulfur dyes. Specific examples of these dyes are described in "Handbook of Chemistry-Applied Chemistry, edited by the Japan Chemical Society" (Maruzen KK · published in 1986) Pages 1399-1427 and the "Nippon Kayaku Dye Handbook" (published by Nippon Kayaku KK · 1973). Conventional methods can be used as methods for dyeing the particle body. For example, dyeing can be described by the " Chemistry " manual- "Chemistry" (edited by the Japan Chemical Society) and "Nippon Kayaku Dye Handbook". The pigment is not particularly limited, but examples include: inorganic pigments such as carbon black, iron black, chrome vermilion, molybdenum red, and ruby , Yellow lead, chrome green, cobalt green, ultramarine blue, and iron blue; and organic pigments such as phthalocyanine, azo, and quinacridine pigments. When the average particle diameter of the pigment is greater than 0.4 microns, the pigment does not It should be introduced into the particle body. Therefore, it is better to use the dye. When the particle body is colored, a spacer having the particle body can be used as a colored spacer for a liquid crystal display. If the spacer is used in a liquid crystal display, Then it can prevent the backlight from leaking light and can improve the image quality of the liquid crystal display. The manufacturing method may further include the surface treatment step, wherein the formed particles are at least one step selected from the group consisting of a condensation step, a polymerization step and a heat treatment step. Between or after, or at the same time between and after the surface The paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) • ϋ ^ 1 ^ 1 .1 1 I ϋ ϋ ϋ II ϋ (Please read the notes on the back 0 to complete this page) Order: -Age-Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-16- 556020 A7 B7_ V. Description of the invention (M). _Li.il — — — · i I (please read the note on the back first and fill in this page) The preferred surface treatment agent for surface treatment is, for example, at least one selected from Silane compounds of the following general formulae (4) to (6): Winter * si X 4 (4) R 4 S i X 3 (δ) R 5 R 6 S i X 2 (6) f " where: X is at least One selected from a chlorine atom, a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms, and a fluorenyl group having 2 to 5 carbon atoms; each of R4 and R5 is at least one selected from the group having 1 to 2 2 Alkyl groups of carbon atoms and aryl groups having 6 to 22 carbon atoms, wherein at least one hydrogen atom of these groups is composed of at least one selected from amine group, hydrogen thio group, vinyl oxide group, cyano group, chlorine atom , And a fluorine atom group; and R6 is at least one monovalent group selected from an alkyl group and a phenyl group having 1 to 5 carbon atoms. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs to achieve particularly superior dry dispersibility, it is better to select the silicon-finished compound of the general formula (4) or the general formula (5) or (6) The silane compound wherein R4 or R5 has an amine group as a substituent. In the present invention, the particle body may be an adhesive particle having adhesiveness, adhesion, or cohesiveness (these properties are hereinafter referred to simply as "adhesiveness"). To obtain this "adhesiveness", at least a part of the surface of the particle body is covered with a thin layer having the aforementioned "adhesiveness". In this case, the adhesive particle system has a particle body and an adhesive covering the surface of the particle body. The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) -17- 556020 A7 __B7 Ministry of Economy Printed by the Intellectual Property Bureau's Consumer Cooperatives V. Invention Description (15) layer. The adhesive layer may cover part or all of the surface of the particle body. In addition, part or all of the adhesive layer may be chemically adhered to the surface of the particle itself. In this case, a structure including the adhesive particles and the following specific fine particles attached to the surface of the adhesive particles can be used as a spacer for the liquid crystal display of the present invention. Hereinafter, this spacer is referred to as an adhesive spacer. The adhesive layer is not particularly limited, but preferably contains a thermoplastic resin. The thermoplastic resin is not particularly limited, and a prerequisite is that the thermoplastic resin is used as a pressure-sensitive adhesive or an adhesive for an electrode substrate (hereinafter referred to as an adhesive). However, a specific example of the thermoplastic resin is a homopolymer or copolymer of an ethylenically unsaturated monomer. The ethylenically unsaturated monomer is not particularly limited, but examples thereof include ethylene, propylene, vinyl chloride, vinyl acetate, styrene, vinyl toluene, α-methylstyrene, and (meth) acrylate ( For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, hex (meth) acrylate Ester, lauryl (meth) acrylate, cyclohexyl (meth) acrylate). Among them, (meth) acrylic acid ester and styrene are preferable, because they have high adhesion. As for the thermoplastic resin, at least one selected from the group consisting of epoxy resin, (meth) acrylic resin and (meth) acrylic styrene resin is most advantageous for further improving the adhesion. The thermoplastic resin is not limited to the aforementioned resin. For example, polyesters such as polyethylene terephthalate and polybutylene terephthalate; various polyamides; various polycarbonates; and various epoxy resins can also be used as thermoplastic resins. (Please read the notes on the back »! Please fill in this page and write this page) Order: The paper size of the spider is applicable to China National Standard (CNS) A4 (210 X 297 mm) -18 · 556020 A7 __ B7 V. Invention Note (16) The thermoplastic resins can be used individually or in combination with each other. ---_------------ ^ ___ (Please read the note on the back 0 to complete this page) The glass transition temperature of the thermoplastic resin is preferably between 40 and 100 Within the range, more preferably 45 to 90 t, and more preferably 50 to 80 ° C. When the glass transition temperature is lower than 40 ° C, the adhesive particles V may be melted during storage or during dispersion, or may have poor dispersibility when dispersed on the electrode substrate. On the other hand, when the glass transition temperature is higher than 100 ° c, it is difficult for the thermoplastic resin in the adhesive layer to melt during heating under pressure when assembling a liquid crystal display, so the adhesion to the electrode substrate may be poor 〃 m · The melting start temperature of the thermoplastic resin is preferably in the range of 50 to 160 ° C, more preferably 60 to 150 ° C, and even more preferably 70 to 14 0 t. When the melting start temperature is lower than 50 ° C, the adhesive particles may be melted during storage, or the dispersibility on the electrode substrate may be poor. On the other hand, when the melting initiation temperature is higher than 160 ° C, it is difficult for the thermoplastic resin in the adhesive layer to melt during heating under pressure when assembling the liquid crystal display, and thus the adhesiveness to the electrode substrate is poor. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs This thermoplastic resin can be colored by containing at least one colorant selected from dyes and pigments. The color is preferably a color that hardly transmits light or does not transmit light at all, because the color prevents leakage of light from the backlight and improves the contrast ratio of the image quality. Examples of colors that hardly transmit light or completely transmit light include colors such as black, dark blue, navy, purple, blue, dark green, green, brown, and red. Black, dark blue, and navy are particularly good. The dyes and pigments that can be used for the coloring of this thermoplastic resin are not particularly limited. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -19- 556020 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 2. Description of the invention (17), but examples thereof include the aforementioned dyes and pigments that can be used to color the particle body of the adhesive particles. The thickness of the adhesive layer is not particularly limited, but is usually in the range of 0.01 to 2 microns, and preferably in the range of 0.05 to 1¼ meters. When the thickness is less than this range, the adhesion may be deteriorated. When the thickness is higher than this range, the area covered by the alignment film or color filter may be wide, so the image display quality of the liquid crystal display may be impaired. The weight ratio of the thermoplastic resin of the adhesive layer to the particles of the adhesive particles is not particularly limited, but it is higher than zero, preferably not higher than 30 percent, and more preferably between 1 and 25 percent Within the range, especially 2 to 20 percent. When the weight ratio of the thermoplastic resin is higher than 30%, the adhesive layer can widen the area covering the electrode substrate, the orientation film, or the color filter when it melts, so the image quality of the liquid crystal display may be affected damage. On the other hand, when the weight ratio of the thermoplastic resin is low, the formed adhesiveness is low. In addition, when the particle system is an adhesive particle, the particle body is also used as the spacer when the liquid crystal display is used to keep the thickness of the liquid crystal layer uniform and fixed. The average particle diameter of the particle body is preferably in the range of 0.5 to 30 microns, more preferably 1 to 25 microns, and most preferably 1 to 20 microns. When the average particle diameter of the particle body deviates from these ranges, the spacer substance may be unstable and cannot be used as an adhesive spacer substance. The average particle diameter of the adhesive particles is not particularly limited, it is caused by adding the thickness of the aforementioned adhesive layer to the aforementioned particle body, and it is preferably in the range of 0.5 to 32 μm (but not including 0.5 μm). More preferably, 1 to 2 & Zhang scales are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the notes on the back first ΪFill this page) pi •, Binding: 孰--20- 556020 A7 ----- B7 V. Description of the invention (18) 2 7 microns (but excluding 1 micron), more preferably 1 to 17 microns (but excluding 1 micron). When the spacer material of the present invention used in a liquid crystal display includes the use of an adhesive particle as the particle body, it can function as an adhesive spacer. Therefore, when used in a liquid crystal display, the spacer is fixed on the electrode substrate of the liquid crystal display to prevent it from moving and improve the image quality of the liquid crystal display. Next, a description will be given of the fine-grained pupae to be attached to the particle body. 〆 The fine particles are attached to part or all of the surface of the particle body (including the adhesive particles). When the particle system is the adhesive particle, the fine particles may be attached to the surface of the aforementioned adhesive layer, or the part of the particle body that does not cover the adhesive layer. The spacer material having this structure has a greatly improved dry dispersibility. In addition, as described above, the fine particles are hydrophobic fine particles having zero or positive electrification properties in terms of triboelectric properties with iron powder. For conventional spacers disclosed in JP — A—1 〇— 〇1 〇542 or JP—A — 0 9 — 2 44 0 3 2, those with negative electrification properties are used as the materials to be attached to the particle body. Fine particles. On the other hand, the particle body usually has negative electrification properties. Therefore, the fluidity of the spacer is improved due to the influence of the attached fine particles, and therefore has a specific effect of improving the dry dispersibility (especially, the dry dispersibility in the high-speed airflow mode. The nitrogen flow collides with the inner wall of the pipeline and comes into contact with electricity, and then disperses). However, in terms of dry dispersion on the recent large-size substrates, the pipeline is long enough to increase the nitrogen pressure, and the Chinese National Standard (CNS) A4 specification (210 X 297 mm) is applied at this paper size (please First read the notes on the back Θ and fill in this!)-Binding: Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics -21-556020 A7 ________ B7 V. Description of the Invention (19) (Please read the notes on the back d to prevent stress Therefore, as for the conventional spacer material to which the fine particles having negative electrification property are attached, the electrostatic attractive force between the particle body and the fine particles or between the adhesive particle and the fine particles is weak, and Insufficient adhesion. As a result, the fine particles themselves are liable to fall off from the particles, so the single dispersion or continuous dry dispersion stability of the spacer is insufficient. In addition, the fallen fine particles are also dispersed on the substrate, and Causes light leakage (micro-bright spots) of backlight lamps. In comparison, for the spacer material of the present invention, which is attached with fine particles of zero or positive electrification properties, The electrostatic attractive force between the particle body and the fine particles is strong enough to increase adhesion. As a result, even when the nitrogen pressure is increased when drying and dispersing in a high-speed airflow method, the fine particles can still be dropped off and dried on a large substrate. The dispersibility (single dispersibility, continuous dispersibility) is also good. In addition, the micro bright spots caused by the falling fine particles can also be greatly reduced. As a result, a liquid crystal display with high contrast ratio and high image display quality is obtained. Printed by the Consumer Cooperative of the Property Bureau. In the present invention, if a particular one of the fine particles is focused on, the state where the fine particles are attached to the particle body may be any of the following exemplary states: (1) The fine particles are not After being embedded, it is simply attached to the surface of the particle body, and the main part of the fine particles is thus exposed to the surface; (2) the fine particles are partially embedded in the particle body, and the remaining fine particles are in the particle. The state of the body surface exposed. The state of the fine particles in the overall spacer material is either (1) or (2) above, or The above state (1) and (2) are mixed. The above state (1) is particularly advantageous, because the spacer substance having this state has superior dry dispersibility. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) " -22- 556020 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (20) Especially for the adhesive particles, the aforementioned state (1) is better because it has the state The spacer is not only superior in adhesion to the substrate, but also has excellent dry dispersibility when the spacer is dispersed on the substrate in a dry state, and the spacer hardly aggregates or disperses unevenly. H The spacer The quality can be uniformly dispersed. The adhesion ratio of the fine particles attached to the particle body is not particularly limited, but the adhesion ratio is preferably, for example, within the range of 0 · 0 0 1 to 10 weight percent of the particle body, More preferred is 0. 0 1 /. To 5 weight percent, and more preferred is 0.05 to 4 weight percent. When the adhesion ratio is out of this range, the dry dispersibility is liable to decrease. With respect to the adhesive particles, when the adhesion ratio is lower than these ranges, the dry dispersion liquid is reduced, and when the adhesion ratio is higher than these ranges, the adhesiveness to the substrate is lowered. The average particle diameter of the fine particles is preferably in a range of not more than 0.5 μm, more preferably not more than 0.1 μm, and more preferably not more than 0.4 μm. When the average particle diameter is larger than these ranges, the accuracy of the gap distance of the liquid crystal layer is greatly affected, and the image quality is reduced. The fine particles used in the present invention are hydrophobic fine particles having zero or positive electrification properties in terms of triboelectric properties with iron powder. Among them, the triboelectric property with iron powder is measured based on blow-off method, in which iron powder (DSP_128, manufactured by Dowa Iron Powder Co., Ltd.) and fine particles are maintained at 20 ° C, 60% relative humidity. After 24 hours in an atmosphere, 50 g of iron powder and 0. 1 g of fine particles were mixed in a bottle, and then a blow-off electricity measuring machine (TB-200, Toshiba Chemical I paper size was applied to Chinese national standards ( CNS) A4 size (210 x 297 mm) (Please read the notes on the back 0 to complete this page) il. -23- 556020 A7 B7 V. Description of the invention (21)

Co., Ltd.) measured 0.1 g of the formed mixture. The triboelectricity of the aforementioned fine particles and iron powder is preferably in the range of +100 to +2,000 eC / g, and more preferably in the range of +100 to +1,00 ## / g. . When the triboelectricity is higher than +2, 000 β k / g, the spacer material aggregates. In addition, the term "hydrophobicity" as used in the present invention means that 50 g of water and 0.5 g of fine particles are mixed using a box-type ultrasonic disperser, and the fine particles are still floating on the water surface for 5 minutes. The fine particles are not particularly limited, but for example, at least one kind selected from inorganic fine particles and organic crosslinked fine particles is used. Among these particles, it is preferable to use the inorganic fine particles because the dry dispersibility is improved. The inorganic fine particles are not particularly limited, but are selected from, for example, metal oxides such as 8102, 81203, 1102, and? At least one of the hydroxides of 02〇3 and 31, A 1, T i & F e is more favorable for improving the dispersibility, and in addition, reducing the shedding from the particle body. Among these examples, at least one metal oxide selected from the group consisting of Si02, A1203, and Tio2 is preferred because these metal oxides have high 値 insulation properties, and therefore do not cause a short circuit, and further The dry dispersion is improved because it hardly falls off from the particle body. In addition, as for these inorganic fine particles, those obtained by a gas phase method including flame hydrolysis of metal chlorides are preferable because the inorganic fine particles have a small 値 particle size and high purity. In addition, compounds containing hydrophobic groups (for example, silicon compounds such as silazane and alkylsilane compounds) are chemically post-treated with inorganic fine particles obtained from the gas phase method to make this paper scale applicable to Chinese national standards (CNS) A4 size (210 X 297 mm) (please read the note on the back of women's clothing i I? Fill out this page); 敎 · Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economics -24- 556020 A7 B7 Ministry of Economics Wisdom Printed by the Consumer Cooperative of the Property Bureau. V. Invention Description (22) It is better that the inorganic fine particles become hydrophobic products because the products have high purity. In addition, an example of a method for imparting the inorganic fine particles with zero or positive electrification properties includes a method including a step of chemically treating the inorganic fine particles with an alkyl silane compound having an amine group, which is an electromotive compound. . Examples of such inorganic fine particles--hydrophobic fine particles having zero or positive electrification properties with respect to the triboelectric properties of iron powders--include zero & positive electrification properties with the triboelectric properties of iron powders Properties of ultrafine particles of silicon dioxide are RA200H, RA200HS, NA50H, NA50HS and REA 2 0 manufactured by Nippon aerosil Co., Ltd. These inorganic fine particles can be used individually or in combination with each other. The aforementioned organic crosslinked fine particles are not particularly limited, but examples thereof include those obtained by cross-linking polymethylmethacrylate or polystyrene with zero or positive electrification properties of the triboelectric property with iron powder. The particles are obtained by copolymerizing a small amount of an electron-donating vinyl monomer such as dimethylaminoethyl methacrylate or adding an electron-donating compound so that the particles contain the other. These organic crosslinked fine particles can be used individually or in combination with each other. The average particle diameter of the spacer material (including the particle body and the specific fine particles attached to the particle body) used in the liquid crystal display of the present invention is preferably in the range of 0.5 to 30 microns, and more preferably 1 to 25 micron, preferably 1 to 20 micron. The average particle diameter outside these ranges usually makes the spacer material unstable and cannot be used as a liquid crystal display (please read the note on the back first-fill in this page to fill in this page). (CNS) A4 specifications (210 X 297 mm) 25 · 556020 A7 _ B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention ⑵) Spacer substances. The coefficient of variation of the particle diameter of the spacer material used in the liquid crystal display of the present invention is preferably within a range of not more than 10%, more preferably not more than 8%, more preferably not more than 7%, and the best is not more than V percentage. · When the LCD uses spacers with a coefficient of variation in particle size outside this range, it is difficult to keep the thickness of the liquid crystal layer uniform and fixed, so it is easy to cause uneven images. ... $ t '· (Manufacturing method of spacer material used in liquid crystal display): The method for manufacturing the spacer material used in the liquid crystal display of the present invention is not particularly limited, but an example thereof includes a manufacturing method including The step of attaching the specific fine particles to the surface of the particle body or the adhesive particle. The manufacturing method will be described in more detail below with reference to specific examples thereof. When the particle body is not the adhesive particle, the method for producing a spacer of the present invention includes, for example, a step of attaching the fine particles to the surface of the particle body. When the particle system is an adhesive particle, in other words, when the spacer substance of the present invention is an adhesive spacer substance, the manufacturing method thereof includes, for example, steps: (1) coating the surface of the particle body with an adhesive layer to obtain Adhesive particles; and (2) attaching the fine particles to the surface of the applied adhesive layer. In addition, regardless of whether the particle body is an adhesive particle, the manufacturer (please read the note on the back 3 and fill out this page) i Binding:; · · This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 (Mm) -26- 556020 A7 _ _____ B7 V. Description of the invention (24) — JLIi --- II --- II (please read the note on the back first and fill in this page) The method is preferably included in the attachment Step one-in which the fine particles are attached-before, the step of dispersing the fine particles in advance (pre-dispersing step), because including the pre-dispersing step can make the fine particles effectively adhere to the short-term in a subsequent attaching step The particle body is on the surface of k. · First, the aforementioned coating step (1) will be described below. The specific method for coating the adhesive layer on the surface of the particle body is not particularly limited, but an example thereof includes a method in which the adhesive property is to be formed. The particle-printed particles are printed by the employee's consumer cooperative of the Intellectual Property Bureau, Ministry of Economic Affairs The particle system of the particle body is dispersed in the solution of the thermoplastic resin, and then sufficiently mixed by stirring, the solvent is removed by evaporation, and the formed product is pulverized; a method in which the particle system of the particle body of the adhesive particle is to be formed Fully dispersed in the molten thermoplastic resin by kneading, the formed mixture is cooled, and the formed bulk product is pulverized; a method in which various functional groups (such as vinyl group, epoxy group are introduced on the surface of the particle body) , Hydroxyl), polymerize a monomer, wherein the starting position of the polymerization is the functional group; or a method in which a polymer reacts with the aforementioned functional group leading to the surface of the particle body, and the polymer is connected Branches on the surface of the particle body. The coating can also be performed by other methods, for example, conventional resin coating methods such as in-situ polymerization, agglomeration, interfacial polymerization, liquid curing coating method, liquid drying method, high-speed air impact method, air-jet coating method, and Spray dry method. These conventional methods are disclosed in detail in "Surface Improvement" (Chemical Generality, edited by the Japan Chemical Society's No. 44, pp. 4-5-52, published in 1987) and "Powder Surface Improvement and High Functionalization" "Technology" This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) -27 · 556020 A7 B7 V. Description of the invention (25) ("Surface", Volume 25, No. 1, No. 1-11 19 pages and photo on the cover, published 1987). In particular, the high-speed airflow impingement method is optimal because this method includes, for example, mixing the particle body of the adhesive particles and the powder of the thermoplastic resin (thermoplastic resin powder), and separating and dispersing the formed mixture in the gas phase so that The aforementioned particle body and the aforementioned thermoplastic resin powder have a step of mechanical thermal energy, mainly including an impact force, to easily apply the thermoplastic resin on the surface of the aforementioned particle body. The average particle diameter of the aforementioned thermoplastic resin.powder-using f1 when performing the high-speed airflow impact method-is not particularly limited, but, for example, it is preferably not more than 1.5 microns, more preferably not more than 1 microns, and the best Greater than 0 · 6 microns. The mixing ratio of the thermoplastic resin powder to the particle body is preferably in the range of 0.1 to 30 weight percent, more preferably 1 to 20 weight percent, and most preferably 2 to 20 weight percent. Equipment using the high-speed airflow impingement method is not particularly limited, but examples thereof include: Hybridization System manufactured by Nara Kikai Seisakusho Co., Ltd .; Mechanofusion System manufactured by Hosokawa Mikawa Co., Ltd .; and Kawasaki Heavy Industries Co., Ltd. The manufactured Kryptron System ° The preferred average particle size of the particle body used in the coating step is the same as that of the aforementioned particle body. Next, the pre-dispersion step will be described. As described above, if the pre-dispersion step is performed, the fine particles are effectively attached to the surface of the particle body (including the adhesive particles) in a short time in the subsequent attachment step. Method for dispersing the fine particles in advance This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the note on the back first-1 pack --- jc write this page) Order: Ministry of Economic Affairs Printed by the Intellectual Property Bureau's Consumer Cooperatives • 28- 556020 A7 — ___________ B7 V. Description of Invention (26) is not particularly limited, but its preferred examples include a method in which the fine particle system uses a device that includes high-speed agitation Propeller--such as a coffee honing machine and a local-speed fluid mixer (e.g., made by Mitsui Mine Co., Ltd., trademark: Hensheru Mixer), stirring for about 5 seconds to about 10 minutes, k reduces the aggregation of the fine particles, and then disperses . Next, a description will be given of an attaching step of attaching the fine particles to the particle body (including the adhesive particles). The method for attaching the fine particles to the surface of the particle body in the attaching step is not particularly limited, but examples thereof include a method in which the particle body and the fine particles use a mixing device such as a ball mill, an automatic mortar, and coffee A honing machine, and a high-speed fluid mixer (for example, manufactured by Mitsui Mine Co., Ltd., trademark: Hensheru Mixer) are mixed. Among these mixing apparatuses, the coffee honing machine and the high-speed fluid mixer are preferable because they allow the adhesion to proceed uniformly, and in addition, they are effectively performed in a short time of about 5 seconds to about 10 minutes. This mixing can unexpectedly be performed by a method of generating a strong impact, such as the aforementioned high-speed airflow impact method. The mixing ratio of the particle body and the fine particles in the attaching step is not particularly limited, but the ratio of the fine particles to the particle body is, for example, preferably in a range of 0. 0 0 1 to 10 weight percent, more The preferred range is 0.01 to 5 weight percent, and the more preferred range is 0.05 to 4 weight percent. When the proportion of the fine particles deviates from these ranges, the dry dispersibility is low. With respect to the adhesive particles, when the proportion of the fine particles is lower than these ranges, the dry dispersibility is low, and when the proportion of the fine particles is higher than the foregoing range, the adhesiveness to the substrate is low. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back 3 and fill out this page). Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-29- 556020 A7 _______ ________ B7 V. Description of the Invention (27) (Liquid Crystal Display): Next, the liquid crystal display of the present invention will be described. As for the liquid crystal display of the present invention, the spacer k of the present invention and the conventional liquid crystal display are differently sandwiched between electrode substrates, and the distance between the electrode substrates is maintained, wherein the gap distance is between the electrode substrates The particle diameters of the spacers between the electrode substrates are the same or similar. The dry dispersibility of the aforementioned spacer material constituting the liquid crystal display of the present invention on a large substrate (not less than 5 5 0 X 6 5 0 f 'mm) is particularly excellent, especially using a device such as a dry dispersing device DI SPA — // R (Nisshin Engineering Co.,

Ltd.) using the high-speed airflow method for drying and dispersing, which can be uniformly dispersed on the large substrate in the drying mode without unevenness. The resulting liquid crystal display has a high contrast ratio and almost no gap distance. Uniformity and improved image display quality. In addition, the spacer has excellent stability in continuous drying and dispersion, which increases the production capacity of liquid crystal displays. In addition, the first fine particles do not fall off, so a liquid crystal display with high image display quality can be obtained: there are almost no micro bright spots, and the contrast ratio is high. The liquid crystal display of the present invention, for example, as shown in FIG. 1, includes a first electrode substrate 110, a second electrode substrate 120, a spacer used for the liquid crystal display, a sealing material, and a liquid crystal. The first electrode substrate 1 10 includes a first substrate 11 and a first electrode 5 and is formed on a surface of the first substrate 11. The second electrode substrate 12 includes a second substrate 12 and a second electrode 5, which are formed on the surface of the second substrate 12 and are configured to comply with the Chinese National Standard (CNS) A4 specification with the paper size ( 210 X 297 mm) ---- I ------ install --- (Please read the notes on the back ^! Fill in this page first) Order: im · Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs- 30- 556020 A7 --------- B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Description of the invention (28) The first electrode substrate 1 1 0 is opposite. The spacer used in the liquid crystal display is the aforementioned inventor, and is sandwiched between the first electrode substrate 110 and the second electrode substrate 120, while maintaining a distance between the electrode substrates. The sealing material 2 is bonded to the periphery of the first electrode substrate 110 and the second electrode substrate 120. The liquid crystal 7 is sealed between the first electrode substrate 110 and the second electrode substrate 120, and is encapsulated by the first electrode substrate 110, the second electrode substrate 120, and the sealing material 2. Within the defined space. As for the liquid crystal display of the present invention, elements other than the spacer material, such as electrode substrates, sealing materials, and liquid crystals, can be the same as those of conventional liquid crystal displays, and can be used in the same manner as conventional liquid crystal displays. The electrode substrate includes a substrate such as a glass substrate or a film substrate, and an electrode formed on a surface of the substrate. If necessary, the electrode substrate may further include an alignment layer formed on a surface of the electrode substrate to cover the surface of the electrode. Examples of the sealing material include an epoxy-adhesive sealing material. The liquid crystal may be conventional, for example, the following types: biphenyl, phenylcyclohexane, Sciuff base, azo, azooxy, benzyl ester, bitriphenyl, cyclohexylcarboxylate, biphenyl Cyclohexane, pyrimidine, dioxane, cyclohexylcyclohexane ester, cyclohexylethane, cyclohexene and fluorine. An example of a method for producing a liquid crystal display includes a method including the following continuous steps: the spacer material of the present invention as an in-plane spacer material is uniformly dispersed on one of two electrode substrates by a drying method; An electrode substrate, wherein the other electrode substrate has an adhesive sealing portion and is coated with a dispersion by, for example, a screen printing method, which conforms to the Chinese National Standard (CNS) A4 specification (210 X 297 by this paper size) (Mm) (Please read the note on the back first; fill in this page to fill in this page) Order: • Lost 31- 556020 A7 ----- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (29) Will The silicon dioxide spacer material used as the spacer material of the sealing part is dispersed in an adhesive sealing material such as epoxy resin; the composite material formed by heating at a temperature of 100 to 18 01 over a period of 1 to 60 minutes or by The composite material is irradiated with ultraviolet light of 40-300 millijoules / cm2, and the adhesive sealing material is thermally cured under appropriate high pressure; liquid crystal is injected; and the liquid is sealed for injection. The portion of the liquid crystal display is obtained. However, the present invention is not limited to a method for producing a liquid crystal display. As far as the in-plane spacer material is concerned, the aforementioned color spacer material of the present invention is preferable because the color spacer material hardly leaks the light of the back light. / The liquid crystal display of the present invention can be used for the same purpose as a user, for example, it can be used for devices such as a television, a detector, a personal computer, a word processor, a car navigation system, a PHS (Personal Mobile Phone System), and a DVD Video display. (Effects and advantages of the present invention): The spacer material used in the present invention is particularly excellent in dry dispersibility on large substrates, especially when using a dry dispersing device such as DI SPA — // R (N isshi η Engineering Co., manufactured by L td) The dry dispersibility of the device under high-speed airflow mode, and it can be evenly dispersed on the entire large substrate in the dry mode without generating unevenness. Therefore, the liquid crystal display including the spacer material has a high contrast ratio and extremely low non-uniformity in the gap distance, and also has a high image display quality. In addition, the spacer material used in the present invention has excellent stability in continuous drying and dispersion. Therefore, the improvement includes the use of spacer material (please read the precautions on the back first and fill in this page). China National Standard (CNS) A4 specification (210 X 297 mm) • 32- 556020 A7-B7 V. Description of the invention (3) Production capacity of crystal display. In addition, as for the spacer material used in the liquid crystal display of the present invention, the attached fine particles rarely fall off when they are attached. Therefore, the liquid crystal display device including the spacer material has high image display quality: micro-bright spots_less and high contrast ratio. When the spacer material used in the liquid crystal display of the present invention is an adhesive spacer material, the spacer material has high adhesion, so that the spacer material hardly moves, aggregates, or falls off. Therefore, the spacer is used. The liquid crystal display with a material barrier has high image display quality, and almost no image unevenness or image display defects. The method for manufacturing a spacer for use in a liquid crystal display of the present invention can effectively produce the aforementioned superior spacer. As described above, the liquid crystal display of the present invention has high image display quality. DETAILED DESCRIPTION OF THE PREFERRED SPECIFIC EXAMPLES The present invention will be described in more detail with reference to some examples of the preferred specific examples in comparison with non-present invention comparative examples. However, the present invention is not limited to the following examples. < Average particle diameter and particle size variation coefficient of spacer substance and particle body, and weight ratio between particle body and thermoplastic resin >: (Average particle size and coefficient of variation of particle size): The size of this paper applies Chinese national standards ( CNS) A4 specification (210 X 297 mm) ----------- install --- (please read the notes on the back β and fill in this'!) Order: Intellectual Property Bureau, Ministry of Economic Affairs, Consumer Consumption Cooperative Printed-33- 556020 A7-B7 V. Description of the invention (31) The particle body or spacer is confirmed by FT-IR analysis. In addition, the average particle diameter, standard deviation of particle diameter, and coefficient of particle size variation are measured as follows : Observe the particle body or spacer with an electron microscope; Measure individual particle diameters on 10'0 particles of the winter selected randomly from the electron micrographs of the formed particle body or spacer; and calculate the target number according to the following formula: : Η _ ZXi average particle size (X) = +, f '〆η _ \ 1/2 Σ (χ-Χι) 2 standard deviation of particle size ⑹ = ——-— I nl J, coefficient of variation of particle size ( %) = (Σ / Again) X 1〇〇 (weight between the particle body and the thermoplastic resin ): The adhesive spacer lines material of 5 g weighed (this weight is referred Ρ1), placed in a cylindrical filter paper. The solvent used to dissolve the thermoplastic resin is selected (for example: tetrahydrofuran and toluene are more favorable for (meth) acrylic resins and (meth) acrylic monostyrene resins; and toluene and xylene are more favorable for polyolefins) The thermoplastic resin covering the adhesive particles was dissolved by Soxhlet extraction, and then only the particle body was exposed. The formed particle body was dried under vacuum at 100 ° C to measure the weight of only the dried particle body (this weight is referred to as P 2). The weight ratio between the particle body and the thermoplastic resin is determined from the following formula: The size of this paper applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back first--installation-- -? Fill in this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-34- 556020 A7 __B7 V. Description of the invention (32) Weight ratio between the particle body and the thermoplastic resin (P) = (Pi-P2) / P2xl00 < Average particle diameter of the adhesive spacer material: + + According to the method of the particle body, it is measured by the foregoing formula. < Glass transition temperature of thermoplastic resin >: The solvent was distilled off from the thermoplastic resin solution extracted from the aforementioned Soxhlet using an evaporator, and then the residue was dried under vacuum at 100 ° C to obtain the thermoplastic resin. The formed thermoplastic resin was confirmed by F T-IR analysis. The glass transition temperature (T g) was measured using a differential scanning calorimeter D S C-7 manufactured by Perkin Elmer. < Whether the fine particles are attached >: The surface of the adhesive spacer is observed with an electron microscope to confirm whether the fine particles are attached. The composition of the fine particles was confirmed by X-ray microanalysis. (Example A1) A monomer mixture of 80% by weight of divinylbenzene and 20% by weight of pentaerythritol hexaacrylate was subjected to suspension polymerization. The formed polymer particles are separated from the formed slurry by decantation, and then washed with water and classified according to the particle diameter. Therefore, a particle body (1) having an average particle diameter of 4.5 microns and a coefficient of variation of the particle diameter of 5.0% is obtained. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the note on the back first-Install i I? Fill out this page) Printed by the Intellectual Property Bureau Staff Consumer Cooperatives -35 556020 A7

V. Description of the invention (33) Secondly, a coffee honer is used to pre-disperse in the form of fine particles by a mixing operation and has a positive electrification property (+1, 000 // c κ g) (RA200HS manufactured by Nippon Aerosil Co., Ltd.) , The average particle size is about 12 nm), and the S i 〇2 hydrophobic fine particles last for 15 seconds. In the nucleus, 10 g of the aforementioned particle body (1) and 0.02 g of fine particles dispersed in advance are placed in a coffee honer, and then mixed with the coffee honer for 15 seconds to make the fine particles adhere. On the surface of the particle body (1), a spacer (1) used in a liquid crystal display is obtained. Secondly, the dry dispersibility of the formed spacer material (1) is evaluated by the following method: The spacer material (1) is using DISPA — // R (manufactured by Nisshin Engmeenng Co., Ltd.) — it is a high-speed airflow Type dry dispersing device--dispersed on a 500 mm x 650 mm electrode substrate (electrode substrate 1 1 0 in Figure 1) at a dispersion density of 150 spacers / mm2, under the condition of nitrogen pressure It is 4 kg / cm2. After that, twenty-five observation zones were selected from the substrate and observed. As a result, there is only one partition with two condensed spacer masses. After that, the continuous stability of dry dispersion in the high-speed gas mode (D I SPA — " R, manufactured by Nishin Engineering Co., Ltd.) was evaluated as follows. The dispersion was performed continuously using 600 impacts to evaluate the dispersibility of the 200th impact and the 600th impact. As a result, there are no agglomerated spacer masses. Secondly, the spacer material (1) is used to produce the liquid crystal display by the following method: This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the note on the back 3 and fill out this page)-Binding : Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-36- 556020 A7 _______________ B7 V. Description of the Invention (34) As shown in Figure 1 'First, the spacer material (1) is in a high-speed air-flow drying method, using DI SPA — eR (manufactured by Nisshin Engineering Co., Ltd.) is dispersed under the nitrogen pressure of 4 kg / cm 2 in the form of an in-plane spacer 8 in a layer of 500 mm X 6½ 0 mm X · 0 · 7 mm An electrode substrate 110 is formed (an orientation film is formed thereon, and a rubbing treatment has been performed). After that, the upper and lower electrode substrates 120 and 110 are bonded via the plane-in-spacer 8, and the alignment films 4 can be arranged to face each other individually, and then the adhesive sealing material 2 is cured by heating. After that, the gap between the two electrode substrates 120 and 11 was placed under vacuum, returned to atmospheric pressure, and the thin film transistor fluorine-twisted nematic liquid crystal 7 was injected, and then the portion for sealing was used to inject the liquid crystal. The polarizing film 6 is adhered to individual external portions of the upper and lower glass substrates 12 and 11 to obtain a liquid crystal display (A1). In the liquid crystal display (A) produced using the spacer material (1) according to the foregoing method, the gap distance uniformly generates a small number of micro bright spots, and the image display quality is superior. In addition, 10,000 pieces of this type of liquid crystal display are continuously produced. As a result, the image display quality of any formed liquid crystal display is superior. The series of results of the aforementioned dry dispersibility and liquid crystal display performance are shown in Tables 1 and 2. (Example A 2) 50% by weight of styrene and 15% by weight of methacrylic paper are in accordance with China National Standard (CNS) A4 specification (210 X 297 mm) ---_----- ------- ^ ___ (Please read the notes on the back to fill in this page) ^ · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs • 37 · 556020 A7 ____ B7 V. Description of the invention (35) The ester and the monomer mixture of 3 to 5 weight percent of r-methacryloxypropyltrimethoxysilane were subjected to dispersion polymerization. The formed polymer particles are separated from the formed slurry by decantation, and then washed with water, classified according to particle size, and dried under reduced pressure at 200 ° C. Therefore, an average particle size of 4 ·% microns and a coefficient of particle size variation are obtained. 4.7 percent of the particle body (2).

The fine particles were adhered to the surface of the particle body (2) in the manner of Example A 1 to prepare a spacer material (2) for use in a liquid crystal display. The difference is that it has a positive electrification property (+ 5 0 0 β C 〆 · / g) (NA50HS, manufactured by Nippon Aerosil Co., Ltd., with an average particle diameter of about 30 nm), as the fine particles, hydrophobic fine silica particles, and the particle body (2) as the particle body . Next, the dry dispersibility of the formed spacer substance (2) was evaluated in the same manner as in Example A1. In addition, a spacer (2) was used to produce a liquid crystal display in the same manner as in Example A1. The results of the dry dispersibility and the performance series of the liquid crystal display are shown in Tables 1 and 2. (Example A 3) A solution (A-solution) prepared by mixing 6.0 g of a 20% ammonia solution and 387.3 g of water was placed in a four-necked flask, and the device was equipped with a condenser, a thermometer, and a drip inlet. . This solution was kept at 2 5 ± 2 ° C while stirring, and a solution (B-solution) was added, by mixing 6 2 g of r-methacryloxypropyltrimethoxysilane and 28 g of vinyltrimethoxy Silane, tetramer or pentamer of 5 grams of tetraethoxysilane, and 0.34 grams of 2,2'-azo-bis-one (4-methoxy-2,4) This paper is applicable to China Standard (CNS) A4 specification (210 X 297 mm) --------------Install i I (Please read the note on the back first and fill out this page) -SJ · Ministry of Economy Intellectual Property Printed by the Bureau's Consumer Cooperatives-38- 556020 A7 B7 V. Description of the Invention (36) Dimethylvaleronitrile)-prepared as a radical polymerization initiator, added from the drop inlet to carry out the r-form Co-hydrolyzed polycondensation of tetramer or pentamer of methacryloxypropyltrimethoxysarane, vinyltrimethoxysilane and tetraethoxysilane. With continuous stirring: After 20 minutes, the reaction mixture was heated to 60 ° C to 5 ° C under an atmosphere to perform free radical polymerization. After continued heating for 2 hours, the reaction mixture was cooled to room temperature to obtain a suspension of polymer particles. The suspension was subjected to solid-liquid f separation by filtration, and the formed residue was washed three times by decantation with methanol. The washed residue was filtered out, and the formed particles were sintered at 300 ° C under a nitrogen atmosphere for 2 hours to obtain the particle body (3). The formed particle body (3) is an organic-inorganic composite material, having an average particle diameter of 4.5 microns, and a coefficient of variation of the percentage of the particle diameter of 3.5 percentages, wherein the proportion of the polysiloxane frame is dioxide Relative to the particle body (3), silicon is 46.0% by weight. Secondly, the spacer material (3) used in the liquid crystal display is prepared by attaching fine particles to the surface of the particle body (3) according to the method of Example A 1. The difference is that the particle body (3) is used as Particle body. Next, the dry dispersibility of the formed spacer substance (3) was evaluated in the same manner as in Example A1. In addition, the liquid crystal display was produced using the spacer (3) in the same manner as in Example A1. The results of the dry dispersibility and the performance series of the liquid crystal display are shown in Tables 1 and 2. This paper size applies the Chinese National Standard (CNS) A4 specification (21 × 297 mm) (Please read the note on the back 3 and fill out this page) 3 ·-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-39- 556020 B7 V. Description of the invention (37) (Comparative Example A 1) The reference spacer (1) used in the liquid crystal display is obtained by attaching fine particles to the surface of the particle body (1) in the manner of Example A 1. Different parts use hydrophobic two with negative electrification properties (-1, 000+ // C / g ·) (Aerosil R97 2, manufactured by Nippon Aerosil Co., Ltd, average particle size about 16 nm) Fine particles of silica are used as fine particles. Next, the dry dispersibility of the formed control spacer (1) was evaluated in the same manner as in Example A1. In addition, a liquid crystal display was produced using the control spacer (1) in the same manner as in Example A1. The results of the dry dispersibility and the performance series of the liquid crystal display are shown in Tables 1 and 2. As shown in Table 2, when the contrast spacer (1) was used to continuously produce a liquid crystal display, the image display quality of the liquid crystal display produced at the initial stage was good. However, at about the 100th tablet, the dry dispersibility becomes worse (the number of agglomerated agglomerates increases), so that the gap distance becomes non-uniform, and color unevenness starts to be produced. In addition, many micro bright spots are generated, so the contrast ratio is greatly reduced. As a result of the analysis of the micro-bright spot, it was found that the fine particles themselves fall off from the particle body (1). (Please read the note on the back 3 to fill out this page first)-Printed on the paper printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) -40- 556020 A7 B7 V. Description of the invention (38) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Table 1. Dry dispersibility. First spraying. 200th spraying. 600th spraying. Example A 1 In a zone, there are two agglomerates without agglomeration. Example: Agglomeration without agglomeration + Agglomeration Example A2 Agglomeration without agglomeration Agglomeration with agglomerate and agglomeration in a sub-region Example A3 Agglomeration without agglomeration Agglomeration with no agglomeration Block comparison example A 1 In a sub-region, there are sixteen sub-regions. In the two agglomerated clusters, there are at least four agglomerated clusters of Ltfcl blocks (please read the Note 3 fill out this page)-installed. •-sorry · This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) • 41 _ 556020 A7 B7 V. Description of the invention (39) Table 2 Preliminary All The LCD display produced by the system continuously produces 1,000 pieces of uniformity of the gap distance. The appearance of the micro bright spots is not good. Winter A1 〇 Any one is good A2 〇 No one is good A3 〇 j A good comparison example A 1 〇 ^ ΤΤΓ Μ is about 100 / piece, the gap distance becomes uneven, in addition, a large number of micro bright spots, resulting in image display quality defects (please read the precautions on the back to fill out this page) I ·! Binding: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (Example B 1) First, mix 3 to 5 grams of crosslinked divinylbenzene pellets (average particle size of 4.5 microns, coefficient of variation of particle size = 4.0%) 1 — as the particle body and 7 g of methyl methacrylate-butyl acrylate copolymer (average particle size = 1.0 μm, glass transition temperature = 65 ° C) — as a thermoplastic resin. After that, the hybridization system N H S — 0 type (coating step) manufactured by Nara Kikai Seisakusho Co., Ltd was used to coat the surface of the particle body with the thermoplastic resin by a high-speed airflow impact method to obtain adhesive particles (1). Secondly, 2 g has a positive electrification property (+ 500 β C / g) (NA 5 0 HS 1 manufactured by Nippon Aerosil Co., Ltd. 'average particle size. The paper size applies the Chinese National Standard (CNS) A4 specification (210 χ 297 公 -42- 556020 A7 ----- B7 V. Description of the invention (40) (approximately 30 nanometers) is pre-dispersed by a coffee honing machine in the form of fine particles in a mixing operation for 15 seconds. After that, 1 0 g of the aforementioned adhesive particles (1) and 0.22 g of pre-dispersed fine particles were placed in a coffee honing machine, and mixed using a coffee honing machine for 15 seconds to attach the fine k particles to the adhesion The adhesive spacer (1) used in the liquid crystal display is obtained on the surface of the adhesive particles (1). Next, the dry dispersibility of the formed adhesive spacer (1) is evaluated using the following method, f, the adhesiveness The spacer material (1) is dispersed at a dispersion density of 150 spacer material / mm2 using DISPA — // R (manufactured by Nisshin Engineering Co., Ltd.) dispersed in an electrode substrate of 5500 mm x 650 mm ( The electrode substrate 1 1 0) in FIG. 1 is a high-speed air-flow type dry dispersion. Once set, using a nitrogen pressure of 4 kg / cm 2, on a substrate selected from the observation twenty-five partition, and observed. The results, found agglomerations

Lcfcj blocks. After that, the stability of continuous drying and dispersion (D I S P A-// R, Ni s s h i η E n g i n e r i n g C 0 ·, L t d · manufacturing) was evaluated as follows. The dispersion was carried out continuously by spraying 600 times to evaluate the dispersibility of the 2000th and 600th sprays. As a result, at the 200th spray, only two observation zones with two agglomerated spacer masses were found. At the 600th spray, there were only three observations with two agglomerated spacer masses. Partition. Secondly, the adhesive spacer (1) is used to manufacture a liquid crystal display by the following method: This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Read the note on the back first and then zero. Printed by the Consumer Cooperative of the Ministry of Intellectual Property Bureau-43 · 556020 A7 _______________B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (41) As shown in Figure 1, first, the adhesive spacer (1) is based on High-speed air-flow drying method, using DI SPA-// R (manufactured by Nisshin Engineering Co., Ltd.) under the nitrogen pressure of 4 kg / cm2, dispersed in the form of spacer material 8 in a plane of 5 50 mm X 6 5 0 ½ m X 0. · 7 mm on the lower electrode substrate 1 1 0 (orientation film has been formed on the upper layer and rubbing treatment has been performed). After that, the upper and lower electrode substrates 120 and 110 are bonded via the in-plane spacers 8, and the alignment films 4 can be placed on opposite sides of each other, and then the adhesive sealing material 2 is cured by heating. After that, the gap between the two electrode substrates 120 and 110 was placed under vacuum, and then the atmospheric pressure was restored. Therefore, the thin film transistor fluorine was injected to twist the nematic liquid crystal 7, and then the portion used to inject the liquid crystal was sealed. After that, the polarizing film 6 is adhered to the respective external portions of the upper and lower glass substrates 12 and 11 to obtain a liquid crystal display (B 1). As for the liquid crystal display (B 1) produced in the aforementioned manner using the adhesive spacer (1), the gap distance is uniform, resulting in very few micro bright spots, and the image display quality is superior. In addition, 1, 000 pieces of the liquid crystal display were continuously produced. As a result, the image display quality of any formed liquid crystal display is superior. The foregoing dry dispersion results and the performance of the liquid crystal display are shown in Tables 4 to 5. (Example B 2) Both the adhesive spacer (2) and the liquid crystal display (Β 2) are in accordance with the Chinese paper standard (CNS) A4 specification (210 X 297 male f " I • 44- (please first Read the note on the back? ^ Fill in this page) li-Binding: 556020 A7 B7 V. Description of the invention (42) Manufactured in the way of Example B 1, the difference is the type and amount of the particle body and the type of the thermoplastic resin And the amount, and the type and amount of the fine particles are listed in Table 3. The series of results are shown in Tables 4 to 5. In addition, the particles used in Example B 2 are organic-inorganic prepared by the V method. -Composite material particles: A solution (A-solution) prepared by mixing 2.5 g of a 25% aqueous ammonia solution, 0.1 g of methanol, and 141.1 g of water is placed in a condenser, a thermometer, and In a four-necked flask with a drip inlet. The solution was kept at 25 ± 2 t and stirred. Add from the drip inlet by mixing. 10 g r monomethacryloxypropyltrimethoxysilane, 15 g Vinyltrimethoxysilane, 5 grams of tetraethoxysilane, 54 grams of methanol, and 〇 · 14 grams of 2,2'-azobisbis (2,4-dimethylvaleronitrile) solution prepared as a radical polymerization initiator (B-solution) for r-methacrylic oxygen Hydrolysis-condensation of propyltrimethoxysilane. After 20 minutes of continuous stirring, the reaction mixture was heated to 70 ± 5 ° C under N 2 atmosphere to carry out radical polymerization. After heating for 2 hours, the reaction The mixture was cooled to room temperature to obtain a suspension of polymer particles. This suspension was subjected to solid-liquid separation by filtration, and the formed residue was repeatedly washed three times with methanol. After that, the formed polymer particles were at 200 ° C. Dry in a vacuum drying oven for 2 hours to obtain organic-inorganic-composite material particles. The formed composite material particles have an average particle diameter of 4.5 microns, and have a coefficient of variation in the particle diameter of 3.3 percentages. The amount of silicon dioxide in the siloxane frame is 60 · 0 weight percent. The paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Read S Ideas on the back B-Pack — fill in this page)-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -45_ 556020 A7 ----- B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ) (Comparative Example B 1) The control adhesive spacer material (1) used in the liquid crystal display was prepared by attaching fine particles to the surface of the intellectual particle (1) in the same manner as in Example B1. The difference is the hydrophobicity of silicon dioxide with a negative electrification property (-1, 000 β C / g) (Aerosil P972, manufactured by Nippon Aerosil Co., Ltd., with an average particle size of about 16 nm). Fine particles are referred to as fine particles. Secondly, the dry dispersibility of the formed control adhesive spacer (1) was evaluated in the manner of Example B1. In addition, the liquid crystal display was produced using the control adhesive spacer (1) according to the method of Example B1. The series of dry dispersibility and performance of the liquid crystal display are shown in Tables 4 to 5. As shown in Table 5, when the liquid crystal display was continuously produced using the control adhesive spacer (1), the image display quality of the liquid crystal display produced at the initial stage was good. However, at about the 100th tablet, the dry dispersibility becomes worse (the number of agglomerated agglomerates increases), and the gap distance becomes non-uniform ' In addition, many micro-bright spots' are generated to drastically reduce the contrast ratio. From the analysis results of the micro-bright spots, it is found that they are fine particles that have fallen off from the adhesive particles (1). (Please read the notes on the back I · • Install i I and fill in this page) Order:% This paper size applies to China National Standard (CNS) A4. (210 X 297 mm) -46- 556020 A7 B7 V. Description of the invention (44) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Table 3 Example B1 Example B2 Comparative Example B1 Coated particle materials Crosslinked organic-inorganic-crosslinked diethylbenzenebenzene composite materials Benzene particles (white) Particles (white) Particles (1 color) Step-Jr- Η * Body average particle size 4.5 4.5 4.5 (micron) Particle size change 4.0 3.3 4.0 Coefficient WO) .... Thermoplastic material methacrylic acid 2 -Methyl Methacrylate-Propylhexyl Ester- Methyl Acetate-Butyl Acrylate Styrene Co-butyl Acrylate Copolymer Polymer Copolymer- Average Resin Particle Size 1.0 0.4 1.0 (micron) Glass Transition Temperature 65 70 65 Degree (° c) Attach fine material * NA50HS * RA200HS R972 Step particle electrification property +500 + 1,000 -1,000 (β c / g) Average particle size about 30 about 12 about 16 '(nm) sticky Adhered or not adhered microfine attaching elements attached to the spacer particle detector Si Si Si mass average particle diameter (m) 4.7 4.8 4.7 thermoplastic resin / particle body 171,818 (weight percent) * Nippon Aerosil Co., Ltd. Manufactured. (Please read the notes on the back first! ^ Fill in this page)-Xiangim, · This paper size is applicable to China National Standard (CNS) A4 (210 χ 297 mm) -47- 556020 A7 B7 V. Description of the invention (45 ) Table 4 Dry dispersibility First spraying 200th spraying 600th spraying Example B 1 In two divisions of agglomerates with no agglomeration, in three divisions with two agglomerated agglomerates, in Example B2 with two agglomerated agglomerates In two divisions, there are two agglomerated clumps. In two divisions, there are two agglomerated clumps. In one division, there are two agglomerated clumps. Comparative Example-B 1 In two divisions, there are two agglomerated clumps. , There are at least four agglomerate clumps in all the districts, please have at least four agglomerate clumps (please read the note on the back 3 to complete this page) Production of the LCD display produced continuously produced 1,000 pieces of uniformity of the image display quality gap distance uniformity of the micro bright point Example B 1 〇dnc ΊΙΙΙΓ J \\\ Any piece is a good example B2 〇 和 J k \ N Any piece is good Comparative Example B 1 0 M J \\\ At about the 100th film, the gap distance becomes uneven, and in addition, a large number of micro bright spots are generated, which causes a defect in image display quality. Various details of the invention may be changed without departing from its spirit and scope. This paper size applies the Chinese National Standard (CNS) A4 specification (210 χ 297 mm) • -Min--48 · 556020 A7 ___B7____ V. Description of the invention (46) In addition, the description of the preferred specific examples of the invention in the previous text is for illustration only Without limiting the invention as defined by the scope of the patent application and its equivalents. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) -49-

Claims (1)

556020 k, 丨 A.One * -Yer 6. Application for Patent Scope Printed Annex I of the Intellectual Property Bureau Employee Consumer Cooperative of the Ministry of Economic Affairs Printed Annex I No. 901 05857 Patent Application Chinese Application for Patent Scope Amendment March 1993 A spacer material for a liquid crystal display includes a particle body and hydrophobic fine particles attached to a surface of the particle body, wherein the particle body is at least one selected from organic crosslinked polymer particles and organic-inorganic-composite particles. One; the hydrophobic fine particles are inorganic fine particles, which have zero or positive electrification properties in terms of the triboelectric properties with iron powder; and the ratio of the fine particles to the particle body is from 0.01 to 1 Within the range of 10% by weight. 2. As the spacer substance in the scope of the patent application, it is an adhesive spacer substance, and the particle system is an adhesive particle. 3. A method for manufacturing a spacer material used in a liquid crystal display, comprising the step of mixing hydrophobic fine particles with a particle body to make the hydrophobic fine particles adhere to the surface of the particle body, wherein the particle body is selected At least one of organic cross-linked polymer particles and organic-inorganic-composite particles; the hydrophobic fine particles are inorganic fine particles that have zero or positive electrification in terms of triboelectric properties with iron powder Nature; and the ratio of the fine particles to the particle body is in the range of 0.0001 to 10% by weight. '' 4. If the method of applying for the third item of the patent scope, it is also included in this (please read the precautions on the back before filling this page) This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 556020 A8 B8 C8 _________ D8 __ ^ __ VI. Patent application: The step of coating an adhesive layer on the surface of the particle body to obtain the adhesive particles before the hydrophobic fine particles 丨 contact the surface of the particle body. (Please read the precautions on the back before filling this page) 5. A liquid crystal display, which includes: two electrode substrates, which are configured to face each other; a spacer material for the liquid crystal display, which is sandwiched between the electrode substrates To maintain a gap distance between the electrode substrates; and a liquid crystal, which is filled between the electrode substrates; the liquid crystal display is characterized in that the spacer substance is as described in the first item of the patent application Spacer for liquid crystal displays. 6. A liquid crystal display comprising: two electrode substrates, which are arranged to face each other; a spacer material used for the liquid crystal display, which is sandwiched between the electrode substrates to maintain a gap distance between the electrode substrates And a liquid crystal, which is filled between the electrode substrates; the liquid crystal display is characterized in that the spacer material is a spacer material used in a liquid crystal display as described in item 2 of the patent application scope. Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This paper is sized for China National Standards (CNS) A4 (21〇 × 297 mm) _ 2-