JPH06503180A - Microspheres, spherical spacers for liquid crystal display elements, and liquid crystal display elements using the same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Microspheres, spherical spacers for liquid crystal display elements, and liquid crystal display elements using the same skin anal standing The present invention is used for spherical spacers for liquid crystal display elements, conductive microspheres, etc. Concerning microspheres. More specifically, spherical spacers for liquid crystal display elements and their liquid crystal The present invention relates to a liquid crystal display element using a spherical spacer for display elements and conductive microspheres.

Lt trouble TN (twisted nematic) mode liquid crystal display element using conventional spacers A typical example of a child is shown in FIG.

This liquid crystal display element includes a pair of substrates 37.39 and a gap between the pair of substrates 37.39. A spacer placed between a pair of substrates 37 and 39 to keep the top constant. 38 and nematic liquid crystal 41, and a cylinder filled around the space between the pair of substrates 37 and 39. the polarized light beam 42.43 coated on the surface of each substrate 37.390; have.

The substrate 37.39 has ITO (ITO) on one side of a transparent substrate 31.34 made of glass. A transparent electrode 32.35 made of a ndium-Tin-Oxide film or the like is patterned. Polyimide is formed on the surfaces of the transparent electrodes 32, 35 and the transparent substrates 31, 34. The alignment control film 33, 36 is formed by covering the alignment control film 33, 36 made of a metal film or the like. its orientation system The films 33 and 36 are subjected to orientation control treatment by rubbing.

The spacer 38 is made of an inorganic material containing aluminum oxide, silicon dioxide, etc. Made from synthetic resin materials including benzoguanamine, polystyrene polymers, etc. It is. A spacer made of an inorganic material is disclosed in, for example, Japanese Patent Application Laid-Open No. 63-73225. No. 1, Japanese Patent Application Laid-open No. 1-59974, etc., from synthetic resin materials. The spacer is disclosed in Japanese Patent Application Laid-Open No. 60-200228 and Japanese Patent Application Laid-Open No. 1-293316. It is disclosed in the publication number etc.

The liquid crystal display element having the above structure is usually manufactured as follows.

Spacers 38 are sprinkled on the alignment control film 33 of the one substrate 37, and the substrate 3 Apply sealing resin to the peripheral edge of 7 by printing. Next, a pair of substrates 37.39 are stacked so that the orientation control films 33 and 36 face each other and pressurized. Next, the sea A sealing member is formed by heating and curing the resin for a pair of substrates 37. 39 are fixed together. Next, a pair of substrates 37. The gear knob 39 is filled with nematic liquid crystal 41, and the hole is then closed. stop Then, polarizing sheets 42 and 43 are laminated on the outer surfaces of the transparent substrates 31 and 34, respectively.

Colored spherical spacers are used as spacers for such liquid crystal display elements. Servers are often used for the following reasons:

In a liquid crystal display element, by applying a voltage between transparent electrodes, the liquid crystal becomes optically A change occurs to form an image. However, the spacer can be optically Does not show any significant change.

Therefore, when an image is displayed, uncolored spacers are bright spots in the dark areas of the image. as a result, the image display quality is reduced. .

A colored spherical spacer made of an inorganic material is disclosed in JP-A No. 62-66228, Disclosed in JP-A-63-89408, JP-A-63-89890, etc. A colored spherical spacer made of a synthetic resin material is disclosed in Japanese Patent Application Laid-Open No. 1-20227. disclosed in JP-A-1-2007719 and JP-A-2-214781. It is.

Furthermore, spacers that do not have adhesive properties will not adhere to the transparent substrate, so as shown below However, adhesive spherical spacers are often used.

■In the process of assembling liquid crystal display cells, air is blown onto the substrate or Air is sucked from above the board. At this time, the spacer placed on the board It can scatter and disappear.

■In the process of injecting liquid crystal into the liquid crystal display cell, the spacer moves on the substrate, Unbalanced placement of spacers on the substrate may occur.

■When driving a liquid crystal display cell, spacers are used by electrical and hydrodynamic forces. can move.

■If external mechanical vibrations act on the liquid crystal display cell, the spacer may move. . The movement of the spacer inside the liquid crystal display cell reduces the gap between the substrates. This will reduce the precision of the image and the quality of the displayed image.

Spherical spacers with adhesive properties are described, for example, in Japanese Utility Model Application Publication No. 51-22453, JP-A-63-44631, JP-A-63-94224, JP-A-63-2 00126, JP 1-247154, JP 1-247155 It is disclosed in Japanese Patent Application Laid-Open No. 1-261537.

However, as a spacer for liquid crystal display elements, the conventional inorganic materials mentioned above are used. When using a spacer or a spacer made of synthetic resin material, the following It had some notable flaws.

As shown in FIG. 8, when a liquid crystal display element is manufactured using an inorganic spacer 38 In this case, this spacer 38 is too hard, so when both substrates 37 and 39 are pressurized, This damages the alignment control film 33. In the damaged portion 33a of the alignment control film 33, the liquid Since it becomes impossible to maintain the molecular arrangement of crystal 41 in the desired state, for example, the transmission type In the liquid crystal display element, the scratched portion 33a appears as a display defect.

Furthermore, since the inorganic spacer 38 is too hard to deform, the spacer 38 It will contact the inner surface of each of both substrates 37, 39 at one point. As a result, the space The sensor 38 is moved by gravity or minute vibrations in the gear knob where the liquid crystal 41 is located. It becomes easier to do. This problem is caused by laptop-type computers, which are becoming rapidly popular these days. - Sonal computers, word processors, and wall-mounted devices are similar to those used for TVs, etc. type of liquid crystal display element, whether the display surface is used vertically or diagonally. And it's very noticeable. For example, most of the spacer 38 is below the liquid crystal display element. This causes non-uniformity in the thickness of the liquid crystal layer, resulting in sharp It becomes difficult to obtain images. Also, by moving the spacer 38, the distribution Since the control film 33 is damaged, the above-mentioned image display defects occur.

On the other hand, using spacers that are too soft for liquid crystal display elements may cause the following problems. Ku.

When dispersing the spacers 38 on the surface of the substrate 37, 39, make sure the spacers 38 are completely It is impossible to spread the powder uniformly, resulting in considerable variation in the density of the spray. Then , when pressing the pair of substrates 37 and 39 in directions facing each other, the spacer 38 In areas where the distribution density is low, the pressure applied to each spacer 38 is extremely large. The spacer 38 deforms greatly because the spacer 38 becomes hard. On the other hand, if the spacer 38 is In areas where the fabric density is high, the pressure applied to each spacer 38 is small, so The spacer 38 hardly deforms. In this way, as shown in FIG. The variation in the dispersion density of the pacer 38 is caused by the This causes unevenness in the thickness of the crystal layer, and as a result, it becomes impossible to obtain a clear image.

Furthermore, when applying pressure to a pair of substrates 37.39, actually all of the substrates 37.39 are It is impossible to apply pressure uniformly to the body, and the substrate 37.39 will be different at different positions on the surface. You will be under a lot of pressure. Therefore, if the spacer 38 is too soft, In this case, the spacers 38 are deformed due to the difference in pressure that each spacer 38 receives. As a result, the thickness of the liquid crystal layer becomes uneven. Because of that The quality of the displayed image will deteriorate significantly.

By the way, in the field of electronics packaging, in order to connect a pair of fine electrodes, A conductive paste is created by mixing metal particles such as gold, silver, or nickel with a binder resin. By preparing a paste and filling this paste between a pair of fine electrodes, It is done to connect. However, these metal particles have non-uniform shapes. and has a higher specific gravity than the binder resin, so it is applied evenly to the binder resin. It was difficult to disperse.

In order to solve these drawbacks, Japanese Patent Application Laid-Open No. 59-28185 discloses that the particle size On the surface of relatively uniform particles such as glass beads, silica beads, glass fibers, etc. discloses forming conductive microspheres by providing a metal plating layer. but However, the conductive microspheres disclosed in the above publication have problems because the base material microspheres are too hard. Therefore, it is difficult to compress and deform it.

Therefore, when trying to connect between electrodes using these conductive microspheres, the conductive microspheres Since the contact area between the sphere and the electrode surface does not expand, the contact resistance value can be reduced. It becomes difficult.

In JP-A-62-185749 and JP-A-1-225776, the base material Polyphenylene sulfide particles, phenol resin particles, etc. were used as microspheres. Conductive microspheres are disclosed. However, when such synthetic resin particles are used as base microspheres, The conductive microspheres used as the material have poor deformation recovery properties after compression deformation. Therefore, the applicable When connecting between electrodes using conductive microspheres, the compressive load acting on both electrodes is When removed, a slight gear knob is formed at the interface between the conductive microspheres and the electrode surface. , resulting in poor contact.

Excuse me! Nu The microspheres of the present invention were made to eliminate the above-mentioned drawbacks, and K = (3/7 2)・F, 3-3/2・R-1/2 smile, F, S are each 10 of microsphere % load value (kgf) and compressive displacement (mm) in compressive deformation, R is the microsphere radius (mm)] at 20°C is 2SOkgf/ It is in the range of mm2 to Took g f / m m2, and the recovery rate after compression deformation is in the range of 30% to 80% at 20°C.

In a preferred embodiment, the above value is 350 kgf/mm2 to 550 kgf /mm2.

In a preferred embodiment, the recovery rate after the compression deformation is 4 at 20°C. It ranges from 0% to 70%.

In a preferred embodiment, the microspheres are divinylbenzene polymer, divinylbenzene Rubenzene-styrene copolymer, divinylbenzene-acrylic acid ester copolymer and at least one selected from the group consisting of diallyl phthalate polymers. Formed from resin.

In a preferred embodiment, the microspheres are perfectly spherical and have a diameter of 0. 1 It is in the range of ~100 μm.

In a further preferred embodiment, the microspheres have a diameter in the range of 0.5 to 50 μm. It is surrounded.

In a further preferred embodiment, the microspheres have a diameter in the range of 1.0 to 20 μm. It is surrounded.

The spherical spacer for liquid crystal display elements of the present invention has K=(3/42)・F, 3-3/ 2.R-1/2 (here, F and S are spherical spacers, respectively) - is the load value (kgf) and compression displacement (mm) at 10% compression deformation, and R is The value of K defined as the radius (mm) of the spacer is at 20°C. The range is 250 kgf/mm2 to 700 kgf/mm2, and The recovery rate after compression deformation is in the range of 30% to 80% at 20°C.

The colored spherical spacer for a liquid crystal display element of the present invention includes colored base material microspheres, Katsuni = (3/, /-2)・F, S-3/2・R-1'2 [Here, F, S are Load value (kgf) at 10% compression deformation of colored spherical spacer, compression is the displacement (mm), and R is the radius (mm) of the spacer. The value of K is between 250kgf/mm” and 700kgf/mm2 at 20°C. range, and the recovery rate after compression deformation is in the range of 30% to 80% at 20°C It is.

The adhesive spherical spacer for liquid crystal display elements of the present invention comprises a base material microsphere and a base material microsphere. and an adhesive layer provided on the surface of the crab=(3/J2)・F-3-" "R-"" C1: 10% of each of Koni, F, and Sit adhesive spherical spacers Load value (kgf) and compression displacement (mm) in compression deformation, R is the spacer The value of K defined as the radius (mm) of 250 kg at 20°C r/　mm2~700k　g　/　mm2, and after compressive deformation Recovery rates range from 30% to 80% at 20°C.

The liquid crystal display element of the present invention is manufactured using each of the above-mentioned spherical spacers.

The conductive microspheres of the present invention include the above microspheres and a conductive layer provided on the surface of the microspheres. has.

In a preferred embodiment, the conductor is an indium plated layer.

Thereby, the invention described herein may achieve the following objectives; (1) Damaging the alignment control film of the liquid crystal display element and inducing modulation of the alignment characteristics of the liquid crystal. , to provide a spherical spacer that does not degrade the quality of displayed images; (2) Disturbing the dimension of the liquid crystal layer gap of the liquid crystal display element to make the displayed image clearer To provide a spherical spacer that does not reduce the degree of (3) A spherical spacer that does not move due to gravity or minute vibrations, and its use. (4) To provide a liquid crystal display element that can display a clear image without any defects; To provide a liquid crystal display element that can be used; 5) To provide conductive microspheres having appropriate compressive deformability and deformation recovery properties; (6) To provide conductive microspheres with excellent connection reliability; FIG. 1 is a sectional view of one embodiment of the liquid crystal display element of the present invention.

FIG. 2 is a graph showing the relationship between load and compressive displacement of the spacer.

FIG. 3 is a graph showing the relationship between the value and the compressive strain of the spacer.

FIG. 4 is a diagram illustrating a method of measuring the recovery rate after compressive deformation of a spacer.

FIG. 5 is a cross-sectional view of the main part of an element obtained using conductive microspheres.

FIG. 6 is a cross-sectional view of the test piece produced in Example 13.

FIG. 7 is a cross-sectional view showing a general liquid crystal display element.

FIG. 8 is a cross-sectional view of a liquid crystal display element using a spherical spacer that is too hard.

FIG. 9 is a cross-sectional view of a liquid crystal display element using a spacer that is too soft.

(Margin below) 81] ′ Sphere, crystal hexagonal sphere spacer, 1 hexaspherical spacer, and ゛ 8 Hexagonal sphere sube i2 The microspheres of the present invention have a value in a predetermined range and a recovery rate after compression deformation in a predetermined range. This can be used as a spherical spacer for liquid crystal display devices.

Further, the colored spherical spacer for liquid crystal display elements of the present invention has a value in a predetermined range and a predetermined value. It has a recovery rate after compression deformation within a range and is colored. Liquid crystal display of the present invention Adhesive spherical spacers for display devices have a predetermined range of values and a predetermined range of compressive deformation values. It has a recovery rate and has adhesive properties when heated.

First, the values defined in the present invention will be explained.

Landau Rifshinotsu Theoretical Physics Course “Elasticity Theory” (published by Tokyo Tosho in 1972) ), page 42, when two elastic spheres with radii R and R' come into contact, h is given by the following equation.

h=F2'3[D2(1/R+l/R')]1'3...(1)D=(3 /4) [(1-σ2)/E+(1-σ")/E']...(2) Here, h is the difference between R+R' and the center of both methods, F is the compressive force, and E and E' are the two elasticities. The elastic modulus of the sphere, σ, σ゛, represents the Poisson's ratio of the elastic sphere.

On the other hand, if the ball is placed on a rigid plate and compressed from both sides, R'- E) If E', then the following equation can be obtained approximately.

F = (2" / 3) (S") (E - R") (1 - σ2) ... (3 ) Here, S represents the amount of compressive deformation. By transforming this equation, the following equation can be easily obtained.

K=E/(1-σ2)...(4) yo-), the formula expressing the K value: K=(3/v'2)・F, 3-3/2・R- 1/2...(5) is obtained.

This value is a universal and quantitative expression of the hardness of a sphere. use this value The suitable hardness of the microspheres or spacers (hereinafter referred to as spacers etc.) It becomes possible to quantitatively and unambiguously express the

And the value at 10% compressive strain is 250k g f 7mm2 ~ 700k g　f　7’m　m2 range, and spacers etc. within this range can be used. For example, when manufacturing a liquid crystal display element, the alignment control film is coated with a spacer, etc. There is no damage caused by the press, and the gap between both electrodes can be created using a pressure press. When doing so, gap control can be easily performed. More preferable 10 The value at % compression strain is 350 k g f / m m2 ~ 550 k g f It is 7mm2.

If a spacer etc. with a K value exceeding 700 kg f 7 mm2 is used, the liquid crystal display The element manufacturing process has the drawback of damaging the surface of the liquid crystal alignment control film, making the manufacturing process even more difficult. In manufactured liquid crystal display elements, space is required to prevent the liquid crystal from shrinking when the temperature drops. Since compressive deformation such as a sensor is difficult to occur, air bubbles are generated in the liquid crystal cell due to the reduced pressure.

When using a spacer etc. with a K value of less than 250 k g f / mm2, the cell Gap control becomes difficult.

By the way, it only specifies the suitable hardness of spacers, etc. used in liquid crystal display elements. However, it is not possible to completely express the mechanical properties of suitable materials such as spacers.

Another important property is the recovery rate after compression deformation, which is a value that indicates the elasticity of spacers etc. is within a predetermined range. By specifying the recovery rate after compressive deformation, This makes it possible to quantitatively and uniquely represent the elasticity or plasticity of pacers, etc. be.

In the spacer etc. of the present invention, the recovery rate after compressive deformation of the spacer etc. is 20°C The range of 30% to 80% is preferable.

A particularly preferable recovery rate after compression deformation is in the range of 40% to 70%.

If a spacer etc. with a recovery rate of over 80% is used, in the liquid crystal cell manufacturing process, When the gear between the side boards is pressed out using a pressure press and the pressure is removed, the compressive deformation occurs. The gap of the liquid crystal cell taken out may be disturbed because the spacers etc. that have been removed tend to recover elastically. It gets lost.

If a spacer etc. with a recovery rate of less than 30% is used, the space between the side substrates will be removed by pressure pressing. If excessive pressure is applied locally when extending the gear knob, the spacer etc. Since the gear knob is still compressed and deformed, the gear knob will not return to its original state at that point. This causes the gear knob to become uneven.

Next, a method for measuring the K value and the recovery rate after compression deformation will be explained.

(A) K value measurement method and conditions (i) Measurement method Spread spacers etc. on a steel plate with a smooth surface at room temperature, and Select one spacer etc. Next, a micro compression tester (PCT-200 model manufactured by Shimadzu) Seisakusho) was used to create a space with the smooth end of a diamond cylinder with a diameter of 50 μm. Compress servers etc. At this time, the compressive load is electrically detected as an electromagnetic force, and the compressive displacement is is electrically detected as the displacement caused by the operating transformer.

A relationship between compressive displacement and load as shown in FIG. 2 can be seen. From Figure 2, the space The load value and compression displacement at 10% compression deformation of the The relationship between the value and the compressive strain can be seen from the value and equation (5) as shown in FIG.

However, the compressive strain is the value obtained by dividing the compressive displacement by the particle diameter of the spacer, etc., expressed as a percentage. be.

(ii> Compression speed A constant load speed compression method was used. Load at a rate of 0.27 grams force per second (grf) increased.

(iii) Test load The maximum was 10grf.

(B) Measuring method and conditions for recovery rate after compression deformation (i>Measurement method Spread spacers etc. on a steel plate with a smooth surface at room temperature, and Select one spacer etc. Next, a micro compression tester (PCT-200 model manufactured by Shimadzu) Seisakusho) was used to create a space with the smooth end of a diamond cylinder with a diameter of 50 μm. Compress servers etc. At this time, the compressive load is electrically detected as an electromagnetic force, and the compressive displacement is is electrically detected as the displacement caused by the operating transformer.

Then, as shown in Figure 4, after compressing the spacer etc. to the reverse load value (in Figure 4 , shown by curve (a)), and conversely reduce the load (shown by curve (b) in Figure 4). . At this time, the relationship between load and compressive displacement is measured. However, the end point in the unloading type is The load value is not zero, but the origin load value is O,1g or more. Recovery rate reaches point of reversal Ratio of displacement 1 and displacement difference L2 from the point of reversal to the point where the origin load value is taken (L2/ L1) is defined as a value expressed in %.

(ii) Measurement conditions Reversal load value 1grf Origin load value 0.1grf Compression speed at loading and unloading 0.27g　r　f　/see Measurement room temperature 20°C The spacer, etc. of the present invention is made of inorganic particles as long as it satisfies the above values and recovery rate. Alternatively, any synthetic resin particles can be used. In particular, the values and times listed above Particles made of synthetic resin are preferred because the recovery rate can be easily adjusted within the above range. Often used.

The following various plastics are suitable as synthetic resins for forming spacers etc. Contains bulk materials. Polyethylene, polypropylene, polymethylpentene, polysalt vinyl chloride, polytetrafluoroethylene, polystyrene, polymethyl methacrylate polyethylene terephthalate, polybutylene terephthalate, polyamide , polyimide, polysulfone, polyphenylene oxide, polyacetal, etc. linear or cross-linked polymers; epoxy resins, phenolic resins, melamine resins, unsaturated Japanese polyester resin, divinylbenzene polymer, divinylbenzene-styrene co Polymer, divinylbenzene-acrylic acid ester copolymer, diallyl phthalate Networks of polymers, triallylisocyanurate polymers, benzoguanamine polymers, etc. A resin with a structure.

Among these resins, particularly preferred are divinylbenzene polymers and divinylbenzene polymers. Rubenzene-styrene copolymer, divinylbenzene-acrylic acid ester copolymer It is a resin having a network structure such as polyester, diallyl phthalate polymer, etc.

There are no particular limitations on the inorganic substance, and conventionally known inorganic substances can be used. Wear.

The shape of the spacer etc. is preferably spherical, for example. The diameter is preferably The diameter is preferably in the range of 0.1 to 100 μm, and the particularly preferred diameter is 0.5 to 50 μm. A more preferable diameter is 1 to 20 μm.

The colored spherical spacer for liquid crystal display elements of the present invention is colored. How to color Methods include, for example, dyes, pigment incorporation, polymerization of dye monomers, and gold on spacers. Examples include a method of forming a metal thin film and oxidizing it. For example, the coloring method may be JP-A-57-189117, JP-A-63-89890, JP-A-1-1 44021, JP 1-144429, JP 63-66228 Publication, JP-A-63-89408, JP-A-1-200227, JP-A-Hei 1-2007719, Japanese Patent Application Laid-Open No. 2-214781, etc. Therefore, the coloring methods disclosed therein can be employed in the present invention.

In the present invention, a colored spherical spacer is used as a spacer for a liquid crystal display element. The reason why it is preferable to use is as follows.

In a liquid crystal display element, by applying a voltage between transparent electrodes, the liquid crystal becomes optically A change occurs to form an image. On the other hand, when a spacer is applied, the optical Does not show any significant change.

Therefore, uncolored spacers appear as bright spots in dark areas when displaying images. There may be visible C, which may reduce the contrast of the image display. This is because that.

The adhesive spherical spacer for liquid crystal display elements of the present invention has adhesive properties when heated. Ru. The method of imparting adhesiveness to the spacer involves applying polyethylene to the surface of the base microspheres. Includes methods for applying wax layers, hot melt adhesive layers, and epoxy adhesive layers. It will be done.

Methods for imparting adhesive properties are described, for example, in Japanese Utility Model Application Publication No. 51-22435 and Japanese Patent Application Laid-Open No. 63-1989. -44631, JP-A-63-94224, JP-A-63-20012 No. 6, JP-A-1-247154, JP-A-1-247155, This method is disclosed in Japanese Patent Publication No. 2-261537, and the methods disclosed therein are applied to the present invention. It can be adopted clearly.

Use of adhesive spherical spacers as spacers for liquid crystal display elements This prevents the spacer from moving in the substrate gap as described above. Can be stopped. As a result, it actively prevents inconvenient phenomena such as damage to the alignment control film. It is possible to stop the display, improve the quality of the displayed image, and improve the precision of the gear knob between the boards. can.

The base material particles used for colored spherical spacers and adhesive spherical spacers are , the above-mentioned spacers, etc.

As described above, the spacer etc. of the present invention has a predetermined range of values and a predetermined range of compression changes. It has a good recovery rate after molding, making it suitable as a spacer for liquid crystal display elements. It has physical properties.

In other words, since the spacer has an appropriate hardness, it can be used in the manufacturing process of liquid crystal display elements. Therefore, the alignment control film will not be damaged when the substrate is pressurized.

Furthermore, since the spacer has moderate deformability, the substrate and spacer have a large surface area. They will come into contact with each other. As a result, the spacer is placed on the surface of the substrate by gravity and microscopic forces. Vibrations make it difficult to move. In addition, by moving the spacer, the orientation control film can be It can also prevent damage to the person.

The spacer develops appropriate hardness, so it presses the pair of boards in the direction that they face each other. When applying pressure, support the pressure with a spacer to keep the gap between the base materials constant. be able to. Therefore, unevenness in the thickness of the liquid crystal layer can be reduced compared to conventional methods. Ru.

Night Vigil”jL15 Next, an example of the liquid crystal display element of the present invention will be explained with reference to the drawings. Liquid crystal display of the present invention The display element has the same structure as that shown in Fig. 7, except for using the spherical spacer described above. It can be made into

That is, as shown in FIG. 1, the liquid crystal display element A includes a pair of substrates 7.9 and is arranged between a pair of substrates 7.9 to maintain a constant gap between the substrates 7.9. The area between the spacer 8 and the nematic liquid crystal 11 and the pair of substrates 7 and 9 is filled. a polarizing channel 12.1 coated on the surface of each substrate 7.9; It has 3 and.

The substrate 7.9 has a transparent substrate 1.4 made of glass with ITO (Indium Ind. A transparent electrode 2.5 made of a film such as m-Tin-Oxide is formed into a pattern. The transparent electrode 2.5 and the transparent substrate 1.4 have an alignment layer made of a polyimide film or the like on the surface of the transparent electrode 2.5 and the transparent substrate 1.4. It is constructed by covering a control membrane 3.6. The orientation control film 3.6 is formed by rubbing. Orientation control processing is performed.

The spacer 8 has a value in a predetermined range indicated by - and a rotation value after compression deformation in a predetermined range. It has a recovery rate. This spacer 8 may be a colored spacer, and/or adhesive spacers.

Therefore, according to the present invention, there is provided a liquid crystal display that can provide clear images without display image defects. It is possible to obtain elements.

conductive microspheres The conductive microspheres of the present invention include the above microspheres and a conductive layer provided on the surface of the microspheres. has. These conductive microspheres are used between fine electrodes in the electronics packaging field. Can be used for conductive connections.

In this conductive microsphere, as mentioned above, the value at 10% compressive strain is 2. The range is 50k gf/’mm” to 700k gf/mm2, and this For example, by using conductive microspheres within the range of Of elements connected by microspheres! 8! During the manufacturing process, conductive microspheres are placed on the opposing electrode surface. There is no need to injure the body, and the gap between both electrodes can be created using a pressure press. When doing this, you can easily control the gear knob. More preferable 1 The value at 0% compressive strain is 350 k g f, mm2 ~ 550 k g f / It is mm2.

If the K value exceeds 700 kgf,...’mm2, the conductive microspheres are Even if a compressive load is applied between the electrodes, the conductive microspheres do not deform easily, and as a result, the conductive The contact area between the electrically conductive microspheres and the electrode surface does not expand, reducing the contact resistance value. It becomes difficult. Also, if you forcefully apply a load to deform the conductive microspheres, the conductivity The conductive layer on the surface of the microspheres may be torn or peeled off, or the conductive layer may be damaged during the device manufacturing process. There is a risk of damaging the surface.

If the K value is less than 250kgf/mm2, the conductive microspheres are When a compressive load is applied between poles, the compressive deformation often increases, so conductive The conductive layer on the surface of the microsphere cannot follow this deformation, and as a result, the conductive layer may be torn or There is a risk that peeling will occur. In addition, the amount of compressive deformation may become excessive, resulting in poor conductivity. If the microspheres become flat, the electrodes will come into direct contact with each other, making it impossible to make a sufficient fine connection. Another problem arises:

Furthermore, in the conductive microspheres of the present invention, the recovery rate after compressive deformation of the conductive microspheres is The range is 30% to 80% at 20°C. Particularly favorable recovery after compressive deformation The rate ranges from 40% to 70%.

If the recovery rate of the conductive microspheres after compression deformation exceeds 80%, the conductive microspheres An adhesive containing dispersed spheres is sandwiched between two electrodes and bonded under pressure, and after the adhesive hardens, When the pressure is removed, the compressively deformed conductive microspheres easily recover elastically, so the adhesive layer becomes the electrode. There is a risk of it being peeled off from the surface.

If the recovery rate is less than 30%, apply the adhesive containing the conductive microspheres to two electrodes. Elements manufactured by filling the gap and bonding under pressure, and then removing the pressure after the adhesive hardens. The adhesive layer repeatedly contracts and expands in an environment of repeated heating and cooling, but it is not conductive. Since the microspheres remain compressed and deformed, they do not touch the electrode surface when the adhesive layer expands. This will cause the gear knob to become loose between the two, causing poor contact.

The conductive microspheres of the present invention are free as long as they satisfy the value and recovery rate within the above ranges. Either made from organic materials or synthetic resins. I can be there.

The microspheres that form these conductive microspheres are the same as the spacers mentioned above. can be used. A preferred resin for forming microspheres is divinylbenzene polymerization. divinylbenzene-styrene copolymer, divinylbenzene-acrylic acid ester It is a resin having a network structure such as a polyester copolymer or a diallyl phthalate polymer.

The particle size range of the microspheres is preferably 0.1 to 100 μm, and the particularly preferable diameter is The diameter is 0.5 to 50 μm, and a more preferable diameter is 1 to 20 μm.

Moreover, the thickness of the conductive layer is preferably in the range of 0.02 to 5 μm. The thickness of the conductive layer is 0 ．． If it is less than 0.2 μm, it will be difficult to obtain the desired conductivity, and if it exceeds 5 μm, microspheres will form. Due to the difference in thermal expansion coefficient between the conductive layer and the conductive layer, the conductive layer easily peels off from the surface of the microsphere. .

Metals used for the conductive layer include, for example, nickel, gold, silver, copper, cobalt and tin. , indium, etc., or alloys containing these as main components. Especially injiu is preferred.

Examples of methods for forming a metal layer on the surface of the microspheres include electroless plating (chemical plating). (Also called the scientific plating method); metal fine powder alone or mixed with a binder. Method for coating microspheres with the paste obtained; vacuum evaporation, ion-bubbling This includes physical vapor deposition methods such as rating and ion sputtering.

The following describes how to form a metal layer using electroless plating, using total displacement plating as an example. Explained below.

This method consists of the following etching process, activating process, chemistry process, and chemistries. The plating process is divided into a plating process and a total displacement plating process.

The coating and ching process forms the plating layer into microspheres by forming unevenness on the surface of the microspheres. This is the process of adhering it to the body, and the etching solution is, for example, a caustic soda solution. liquid, concentrated hydrochloric acid, concentrated sulfuric acid or chromic anhydride.

The activation process forms a catalyst layer on the surface of the notched microspheres. This is also a step for activating the catalyst layer. After activation of the catalyst layer The precipitation of metallic nickel in the chemical nickel agate process described above is promoted. microsphere The catalyst layer containing Pd2'' and Sn'' on the surface of is treated with concentrated sulfuric acid or concentrated hydrochloric acid. Only n2" is dissolved and removed to metallize Pd2". metallized palladium , activated and sensitized with a palladium activator such as a concentrated solution of caustic soda.

Chemistry 2. In the Kermenoki process, metal nitrogen is added to the surface of the microspheres on which the catalyst layer has been formed. This is the process of forming a nickel layer, for example, by mixing nickel chloride with sodium hypophosphite. nickel is reduced on the surface of the microspheres.

In the total displacement plating process, the nickel-coated microspheres are coated with gold and cyanide. Place the gold in an aqueous solution of potassium chloride and heat the microspheres to dissolve the gel. Let it precipitate.

In addition, when the conductive layer is formed from an indium plating layer, the thickness of the conductive layer is The range of the thickness is particularly preferably 0.02 to 5 μm. The thickness of the conductive layer is less than 0.02μm If it is less than 5 μm, it is difficult to obtain the desired conductivity, and if it exceeds 5 μm, the conductive microspheres may be difficult to obtain. When sandwiched between a pair of electrodes and pressurizing both electrodes, the elastic properties of conductive microspheres effect is no longer expressed. If the thickness of the conductive layer exceeds 5 μm, the conductive microspheres will aggregate together. Gathering is more likely to occur.

Examples of methods for forming an indium plating layer on the surface of microspheres include the method F below. I can give it to you.

■Method of forming an indium plating layer using electroless plating method Another metal (for example, copper) that has a higher ionization tendency than indium is applied to the surface of the microspheres in advance. After forming a thin film of (e.g.), this metal is replaced with indium as shown in This is the method of

3Cu+2 In””→3Cu”+21 n↓■Reduction method, Ki method A reducing agent is added to an aqueous solution of indium salt to transform indium into microspheres through a reduction reaction. This is a plating method that forms an indium plating layer by depositing it on the surface. .

Alternatively, after forming a thin film of another metal such as nickel on the surface of the microspheres, It is also possible to deposit indium on this surface through a reduction reaction to form a thin film. Ru.

■Mechanical and physical method for forming indium plating layer After mixing microspheres and indium particles, hybridization or By using the mechano-hydraulic method, indium particles are collided with the surface of microspheres. Indium is thinned by rubbing indium fine particles on the surface of microspheres. A film is formed on the surface of the fine particles. Alternatively, mix microspheres and indium particles. By heating this, the indium is melted and imprinted on the surface of the microspheres. It may also be coated with a thin film of indium.

A device can be manufactured using the conductive microspheres obtained in this way.

This element can be manufactured, for example, as follows.

That is, as shown in FIG. 5, conductive microspheres 29 are placed in an insulating binder 28. Apply the uniformly dispersed material onto one electrode 24 using screen printing or a dispenser. Apply to. Alternatively, only the conductive microspheres 29 can be electrified without using the binder 28. Placed on pole 24. In the latter case, the conductive microspheres 29 are dispersed from above the electrodes 24. Alternatively, the conductive microspheres 29 may be charged and electrostatically attached to the electrodes 24. You may wear it.

Next, the other electrode 25 is placed on top of the electrode 24. In this state, both electric Pressurize poles 24.25. Here, no particularly large pressing force is required. Conductivity The pressure may be sufficient to maintain contact between the microsphere 29 and the surfaces of the electrodes 24 and 25. next , a laminate in which conductive microspheres 29 are sandwiched between a pair of electrodes 24 and 25 is heated.

Press heating is preferred as the heating method. In this way, an element like the one shown in Figure 5 can be created. Child B is obtained.

The electrodes used in the above device include, for example, an ITO thin film on a glass plate. formed electrodes, electrodes with aluminum thin films formed on glass plates, plastic Electrodes made by pasting copper notes on a film and etching them; Contains electrodes made by printing silver paste and carbon black on a film. Ru. In this way, by using conductive microspheres, it is possible to improve the Predetermined locations can be electrically connected.

The conductive microspheres of the present invention can be appropriately compressed and deformed, so they have conductive properties. When connecting electrodes using microspheres17, contact between the conductive microspheres and the electrode surface The contact resistance value can be reduced by expanding the area. Furthermore, the change after compression deformation Because the shape recovery property is also moderate, it is suitable for the process of connecting between electrodes using conductive microspheres. When the compressive load acting on both electrodes is removed, the conductive microspheres and the electrode surface There will be no gap formed at the interface between the two and no contact failure will occur.

As described above, the conductive fine particles of the present invention have appropriate compressive deformability and deformation recovery properties. Therefore, when used between two electrodes, it has excellent anisotropic conductive performance and connection reliability. It is suitable for the following applications.

■Transfer material for electrical connection between upper and lower substrate electrodes in liquid crystal display elements fee.

■C0G (chip-on-glass) between LSI and glass wiring board in liquid crystal display elements ) Connection materials.

■Electrical relationship between glass wiring board and flexible printed circuit in liquid crystal display element connection material.

■COG (chip-on-glass) between a plate-like substrate or a film-like substrate and an LSI Or COF (chip-on-film) connection material.

(Margin below) New Year's Day.

The present invention will be explained in detail below based on examples.

The test method is as follows.

(A) Measurement of particle size Coulter Counter 7B/C-1000 type particle size measuring machine (''-Luther Ele (manufactured by Cutronics).

CB) Spacer compression test The test was carried out using a micro compression tester (manufactured by Shimadzu Manufacturing Co., Ltd.).

(C) Measuring the gap between the upper and lower substrates of the if crystal cell Liquid crystal cell gap measuring device (optional) The test was carried out using a newly manufactured TFM-12OAFT model).

(D) Display performance of liquid crystal display element Place the top of the liquid crystal cell so that the color of the light reflected from the liquid crystal cell is olive-colored. Attach polarizing sheets to both sides of the bottom.

At this time, color unevenness was observed in the background color of the polarizing sheet. In addition, power is supplied to the liquid crystal display element. I connected it, turned it on, and observed the image for 1 degree.

X1l lift After suspension polymerization of tetramethylolmethanetetraacrylate, it is flattened by classification. A spacer with an average particle diameter of 703 μm and a standard deviation of 0.2771 m was obtained.

When this spacer was subjected to a compression test, the value was 55 at 10% compression strain and lt6. It was 0kgf/mm2. Also, compressive deformation when the reverse load value is 1 grf The subsequent recovery rate was 65%.

Approximately 500 angstroms of straw was deposited on a glass plate with a thickness of 0.7 mm by low-temperature sputtering. After forming an indium oxide-tin oxide transparent conductive film with a thickness of A predetermined electrode pattern was formed by lithography. Next, apply an alignment agent on top of this. After coating, it was heated to form an alignment control film. Next, this glass plate is 5 cm x It was cut into a size of 12.5 cm to obtain a glass substrate for a liquid crystal display element.

Mix glass fiber spacers by screen printing around this glass substrate. The epoxy adhesive was printed with a width of 1 mm.

After placing the glass substrate horizontally, the spacer is blown from above using pressurized nitrogen gas. It was scattered and dropped uniformly onto a glass substrate. spacer on glass substrate The spraying time was adjusted so that the spraying concentration was about 100 particles/m2.

After superimposing another glass substrate on the above glass substrate on which spacers are scattered, A press machine applies a load of 1 kg*/crn2 evenly to the entire glass substrate. added to. At the same time, heat this thing at a temperature of 160°C for 20 minutes to remove the surrounding epoxy. The glue was cured.

After creating a vacuum by suctioning the inside of the cell created in this way, the surrounding seal area is Liquid crystal was injected into the inside through holes provided in some parts. Liquid crystal cell created in this way As a result of measuring the gap between the upper and lower boards, the gear knob value was 6.98±0.0 It was in the range of 3 μm.

This liquid crystal cell is designed so that the color tone of the light reflected from the liquid crystal cell is olive-colored. Polarizing sheets were pasted on both the top and bottom sides. At this time, this olive color is uniform and concentrated. No color unevenness was observed. Connect the power supply to the liquid crystal display element created in this way. As a result, sufficient display performance was obtained.

5 pieces per plate 75% by weight of tetramethylolmethanetetraacrylate and 2% of divinylbenzene After suspension polymerization of 5% by weight, the average particle diameter was 7.05μm, standard deviation o , a 25 μm spacer was obtained.

The value of this spacer at 10% compressive strain was 450 kgf/mrn2. . Further, the recovery rate of the spacer after compression deformation was 54%.

A gear valve for a liquid crystal cell made in the same manner as in Example 1 except for using this spacer. The value was in the range of 6.88±0.03 μm. Also, implementation F! Same as AI 1 There was no color unevenness in the density when the polarization sorting was pasted on the liquid crystal cell, and it turned on. The display condition was also good.

Tomoe Superintendent Tomoe 50% by weight of tetramethylolmethanetetraacrylate and 5% of divinylbenzene After suspension polymerization of 0% by weight, the particles were classified to have an average particle size of 702 μm and a standard deviation of 0. A 26 μm spacer was obtained.

The value of this spacer at 10% compressive strain was 390 kgf/mm2.

Further, the recovery rate of the spacer after compression deformation was 50%.

A gear valve for a liquid crystal cell made in the same manner as in Example 1 except for using this spacer. The value was in the range of 683±0.04μ. In addition, in the same manner as in Example 1, There was no color unevenness in the density when the polarizing sheet was attached to the crystal cell, and it was The display condition was also good.

Arashi Hill E 25% by weight of tetramethylolmethanetetraacrylate and 7% of divinylbenzene After suspension polymerization of 5% by weight, the average particle size was 7.03 μm and the standard deviation was 0 by classification. ．． A 28μ eyebrow spacer was obtained.

The value of this spacer at 10% compressive strain is 380 kgf/m　m2. Ta. Further, the recovery rate of the spacer after compression deformation was 45%.

The gap of a liquid crystal cell made in the same manner as in Example 1 except that this spacer was used. The value was in the range of 6.80±0.03 μm. Also, in the same manner as in Example 1, There was no color unevenness in the density when the polarizing sheet was attached to the crystal cell, and it was The display condition was also good.

Support design l After suspension polymerization of divinylbenzene, the average particle size was 705 μm, standard by classification. A spacer with a deviation of 0.29 μm was obtained.

The value of this spacer at compressive strain 1O% is 280 kgr/m　m2. Ta. Further, the recovery rate of the spacer after compression deformation was 35%.

A gear valve for a liquid crystal cell made in the same manner as in Example 1 except for using this spacer. The value was in the range of 678±0.06 μm. Also, in the same manner as in Example 1, the liquid crystal With the polarizing sheet pasted on the cell, no color unevenness was observed, and the display was displayed when the cell was lit. It was in good condition.

Yo tree! D Yu Average particle size of benzoguanamine polymer: 6.98 μm, standard deviation: 0.25 μm A liquid crystal display element was obtained in the same manner as in Example 1 using a spacer of m.

The value of the spacer used at 10% compressive strain is 600 kgf/mm2. , and the recovery rate of the spacer after compression deformation was 3%.

The gap of a liquid crystal cell made in the same manner as in Example 1 except that this spacer was used. The drop value was in the range of 692±0.07 μm. Also, in the same manner as in Example 1, the liquid crystal When I pasted polarized sorting on the cell, I noticed some color unevenness in the density, and the display with the lights on. The display conditions were insufficient.

Comparative example 2 Containing 30% by weight of triallylison annulate and 70% by weight of diallyl phthalate. After turbid polymerization, the average particle diameter was 703 μm, [width deviation 0.26 μm] by classification. I got a spacer.

The value of this spacer at compressive strain 1O% is 1t240k gf/mm”. It was. Further, the recovery rate of the spacer after compression deformation was 12%.

A gear valve for a liquid crystal cell made in the same manner as in Example 1 except for using this spacer. The value was in the range of 6.89±0.03 μm. Also, in the same manner as in Example 1, When a polarizing sheet was attached to the crystal cell, color unevenness was observed in the density, and it was difficult to see when the light was on. The display condition was also insufficient.

Tsutsumi comparison five Yu Spacer made of polystyrene with an average particle diameter of 6698 μm and a standard deviation of 025 μm. A spherical spacer was obtained in the same manner as in Example 1, except that a spherical spacer was used.

The value of this spacer at 10% compressive strain is 105 kgf/m m2. Ta. Furthermore, the recovery rate of the spacer after compression deformation could not be measured.

A gear valve for a liquid crystal cell made in the same manner as in Example 1 except for using this spacer. The values were in the range of 675±O, 07μI. Also, in the same manner as in Example 1, the liquid crystal When a polarizing sheet was attached to the cell, color unevenness was observed in the density, and the display in the lit state The display conditions were inadequate.

Anonymous Δ Average particle diameter of benzoguanamine polymer: 7.05 μm, standard deviation: 0.25 A liquid crystal display element was obtained in the same manner as in Example 1 except that a 11 m spacer was used.

The value of this spacer at 10% compressive strain is 620 kg 17 mm2, and the spacer The recovery rate of the pacer after compression deformation was 13%.

The pond using this spacer was created in the same way as in Example 1. The value was in the range of 688±0.05 μm. Also, in the same manner as in Example 1, the liquid crystal When a polarizing sheet was attached to the cell, color unevenness was observed in the density, and the display in the lit state The display conditions were insufficient.

Hakushu Xingdan Spacer made of silicon dioxide with an average particle diameter of 7.01 μm and a standard deviation of 019 μm. A liquid crystal display element was obtained in the same manner as in Example 1.

The value of this spacer at 10% compressive strain is 5000 kgf/mm2, The recovery rate of the spacer after compression deformation was 85%.

The pond using this spacer was created in the same way as in Example 1. The value was in the range of 699±010 μm. In addition, a liquid crystal cell was prepared in the same manner as in Example 1. When a polarizing sheet was pasted on the light, color unevenness was observed in the density, and the display when the light was on. The condition was unsatisfactory.

Branch Superintendent Gol After suspension polymerization of tetramethylolmethane triacrylate, the average Resin fine particles with a particle diameter of 7.03 μm and a standard deviation of 0.27 μm were obtained. This fine particle 1 0g: 100g of this concentrated sulfuric acid was added and reacted at 55°C for 6 hours.

On the other hand, 6 g of basic dye Chiron Buranok 5BH (manufactured by Hodogaya Chemical Co., Ltd.) was added to 30 I7 was dissolved in 0 ml of water and acetic acid was added to obtain a dye bath adjusted to pH 4. This above Acid-treated fine particles were added and dyed at 95° C. for 6 hours to obtain black spherical spacers. child The average particle diameter of the spherical spacer was 7.38 μm, and the standard deviation was 0°29 μm. Ta.

The value of this colored spacer at 10% compressive strain is 520 kgf/mm2. Ta. Also, the recovery after compressive deformation of this colored spacer when the reverse load value is 1grf. The rate was 55%.

A liquid crystal display element was obtained in the same manner as in Example 1 except that this spacer was used. liquid crystal The cell gap values were in the range of 6.98±0.03μ species.

In addition, when a polarizing sheet was attached to the liquid crystal cell in the same manner as in Example 1, the yellow-green color was No color unevenness was observed in the color density. LCD created in this way When the display element was connected to a power source and turned on, sufficient display performance was obtained.

Tomonao Otori Tetramethylolmethanetetraacrylate 75! Amount% and divinylbenzene2 After suspension polymerization of 5% by weight, the average particle size was 7.05 μm and the standard deviation was 0 by classification. ．． A 25 μm spacer was obtained.

This spacer was dyed in the same manner as in Example 6 to obtain a black spherical spacer. child The average particle diameter of the spherical spacer was 7.04 μm, and the standard deviation was 0.27 μm. Ta. The value of this colored spacer at 10% compressive strain is 420 k gf/mm It was 2.

Moreover, the recovery rate after compression deformation was 51%.

A gear valve for a liquid crystal cell made in the same manner as in Example 1 except for using this spacer. The value was in the range of 7.22±0.03 μm. Also, in the same manner as in Example 1, There is no unevenness in the background color when the polarizing sheet is attached to the crystal cell, and the lighting condition is The display condition was also good.

Bloodline Takumi Ei Tetramethylolmethanetetraacryle-hsofij 1% and divinylbenze After suspension polymerization of 50% by weight of Spacers with a difference of 0.26 μm were obtained. This spacer was dyed once as in Example 6. A black spherical spacer was obtained. The average particle diameter of this spherical spacer is 7.4 771 m, tm standard deviation was 0.28 μm.

The value of this spacer at 10% compressive strain was 370 kgf/mm2.

Furthermore, the recovery rate of the spacer after compression deformation was 47%.

A gear valve for a liquid crystal cell made in the same manner as in Example 1 except for using this spacer. The value was 1, which was in the range of 6.83±0.04 μm, and 1. There is no unevenness in the background color of the liquid crystal cell (with the polarizing sheet attached). The display condition in the lit state was also good.

A plateful of fish Tetramethylolmethane tetraacrylate 25fi amount% and divinylbenzene After suspension polymerization of 75% by weight, the average particle diameter was 7.03μm1 standard deviation by classification. A 0.28 μm spacer was obtained. This spacer was dyed in the same manner as in Example 6. , a black spherical spacer was obtained. The average particle diameter of this spherical spacer is 745 μm , the standard deviation was 0.30 μm.

The value of this spacer at 10% compressive strain was 360 kgf/mm2.

Further, the recovery rate of the spacer after compression deformation was 45%.

A gear valve for a liquid crystal cell made in the same manner as in Example 1 except for using this spacer. The values were in the range of 680±0.03μI. Also, in the same manner as in Example 1, the liquid crystal There is no unevenness in the background color when the polarizing sheet is attached to the cell, and it is lit. The display condition was also good.

11th master craftsmanship After suspension polymerization of divinylbenzene, the average particle size was 7.05 μm, t by classification. *A spacer with a jli deviation of 0.29 μm was obtained.

This spacer was dyed in the same manner as in Example 6 to obtain a black spherical spacer. child The average particle diameter of the spherical spacer was 7.40 μm, and the standard deviation was 0.30 μm. Ta.

The value of this spacer at 10% compressive strain was 270 kgf/mm2.

Further, the recovery rate of the spacer after compression deformation was 40%.

A gear valve for a liquid crystal cell made in the same manner as in Example 1 except for using this spacer. The value was in the range of 7.12±0.05 μm. Also, in the same manner as in Example 1, With the polarizing sheet attached to the crystal cell, there is no unevenness in the background color, and the light is on. The display condition was also good.

Saitaku Takumi Average particle size of benzoguanamine polymer: 6.98 μm, standard deviation: 025 μm The spacer was dyed red with an acid dye to obtain a colored spacer. This coloring strip The average particle size of the pacer was 7.01 μm with a standard deviation of 027 μm.

The value of this spacer at compressive strain lO% was 580 kgf/mm2.

Further, the recovery rate of the spacer after compression deformation was 11%.

A gear for a liquid crystal cell was prepared in the same manner as in Example 1 except for using this spacer. Knob values ranged from 6.96±0.08 μm. Also, in the same manner as in Example 1, When a polarizing sheet was pasted on the liquid crystal cell, color unevenness was observed in the background color, and the lighting state The display condition was insufficient.

Comparative example 7 Suspending 30% by weight of triallylisonoaslate and 1% by weight of 70% diallylphthalate. After turbid polymerization, the average particle size was 703 μva and the yAe deviation was 026 μm by classification. Got a spacer.

This spacer was dyed in the same manner as in Example 6 to obtain a red spherical spacer. child The average particle diameter of the spherical spacer was 7.38 Jim, and the standard deviation was 027 μm. Ta.

The value of this spacer at compressive strain 1O% is 220kg Special Table 10-50318 0 (12) It was f / m m2. In addition, the recovery rate after compressive deformation of the spacer is 12%. Met.

A gear valve for a liquid crystal cell made in the same manner as in Example 1 except for using this spacer. The value was in the range of 7.23±0.04μ. Also, in the same manner as in Example 1, When a polarizing sheet was pasted on the crystal cell, color unevenness was observed in the background color, and when the light was on, The display condition was also insufficient.

Anonymous Phoenix Spacer made of polystyrene with an average particle diameter of 6.98 μm and a standard deviation of 025 μm. A black spherical spacer was obtained by dyeing in the same manner as in Example 6, except that a black spherical spacer was used. this The average particle diameter of the colored spacer was 7.47 μm, and the standard deviation was 0.29 μm.

The value of this colored spacer at 10% compressive strain is 100 kgf/mm2. Ta. The recovery rate of the spacer after compressive deformation could not be measured.

A gear valve for a liquid crystal cell made in the same manner as in Example 1 except for using this spacer. The value was in the range of 6.75±0.07 μm. Also, in the same manner as in Example 1, When a polarizing sheet was pasted on the crystal cell, color unevenness was observed in the background color, and when the light was on, The display condition was insufficient.

Hidden temporary craftsman Made of benzoguanamine polymer, average particle diameter 7.05μ, Tfil deviation 0.2 A red spherical spacer was dyed in the same manner as in Comparative Example 6 except that a 5 μm spacer was used. I got a sir. The average particle diameter of this spherical spacer is 708 μm and the standard deviation is 0. It was 27 μm. The value of this colored spacer at 10% compressive strain is 605 k gf/mm2, and the recovery rate after compression deformation of the colored spacer is ti%. Ta.

The pond using this spacer was created in the same way as in Example 1. The value was in the range of 6.91±0.08 μm. Also, in the same manner as in Example 1, When a polarizing sheet was pasted on the crystal cell, color unevenness was observed in the background color, and when the light was on, The display condition was insufficient.

Let the toad be low A spacer made of silicon oxide with an average particle diameter of 701 μm and a standard deviation of 019 μm. A blue spherical spacer was obtained by staining with a basic dye. This colored spacer average The particle diameter was 7.04 μm, and the tf1m deviation was 021 μm. This colored spacer The value at 10% compressive strain is 5000 k gf/mm2, and the The recovery rate after compression deformation of the cer was 85%.

A gear valve for a liquid crystal cell made in the same manner as in Example 1 except for using this spacer. The value was in the range of 7.00±010 μm. Also, in the same manner as in Example 1, the liquid crystal When a polarizing sheet was pasted on the cell, uneven color was observed in the background color, and it was difficult to see when the cell was lit. The display condition was inadequate.

Branch Hill Works Tetramethylolmethanetetraacryle-1-75Ii amount% and divinylbenze After suspension polymerization of 25% by weight of Fine particles with a deviation of 0.40 μm were obtained.

For 10 g of this spacer, tetrapropoquine titanium (manufactured by Nippon Soda Co., Ltd.), Product name A-1) 0. ], add a solution of 5 g dissolved in beef sun to 15 ml of n- After mixing well with a spatula, n-hexane was evaporated. Then this mixture The mixture was thoroughly kneaded in a mortar to eliminate lumps.

On the other hand, polyethylene wax (Sanyo Chemical Industries, Ltd.) is used as a hot-melt adhesive resin. Co., Ltd., product name Sunwax 151-P) was added to toluene, and 80 Dissolved in a °C warm bath. The above tree treated with the above organic titanium compound is added to this solution. Add fine fat particles and disperse until completely milky, then heat at 90°C130C13O It was dried by heating under 0 reduced pressure.

In this way, resin particles coated with hot-melt adhesive resin form a mass. and 17. Next, add 20ml of glycerin to this mass and thoroughly mix it in a mortar. The mass was kneaded 1-1 and passed through three more rolls to completely break up the mass.

Next, this decomposed mass was filtered onto a glass filter using 1 liter of ethanol. After washing, it was suspended in an ethanol/Freon 113 mixed solution (2:1 by volume). I set it. Next, this mixture was allowed to stand for 15 hours, and the supernatant was decanted. Microscopic pieces of polyethylene wax were removed. Put the remaining lumps back into the glass. After filtering with a filter, it was washed with Freon 113. Heat this at 60℃. By drying in an oven, coated resin fine particles were obtained.

The average particle diameter of the coated resin fine particles was 10.32 μm, and the standard deviation was 0843 μm. there were. From this result, polyethylene wax has an average thickness of 0.16 μm and resin It was found that it was formed on the surface of fine particles. Also, it has been exposed to scanning electron microscopes. As a result of observing the surface of the resin-coated fine particles, it was found that the surface of the resin fine particles was coated with polyethylene without any gaps. It was found that the wax was evenly coated.

The value of the coated resin fine particles at 10% compressive strain is 450 kgf, ’mm2. Furthermore, the recovery rate after compressive deformation of this fine particle when the reversal load value is 1 grf is 63%. Met.

The liquid crystal display was prepared in the same manner as in Example 1 except that the coated resin fine particles were used as spacers. A display element was obtained. The gap value of the liquid crystal cell was in the range of 9.95±0.03 μm. Ta.

In addition, when a polarizing sheet was attached to the liquid crystal cell in the same manner as in Example 1, the yellow-green color was No color unevenness was observed in the background color. LCD display created in this way As a result of connecting a power source to the element and lighting it up, good display performance was obtained.'' D After suspension polymerization of divinylbenzene, it was classified to have an average particle size of 9.90 μm and a standard Fine particles with a standard deviation of 0.36 μm were obtained. For 10 g of these fine particles, tetrapropyl 0.15 g of oxytitanium (manufactured by Nippon Soda Co., Ltd., trade name A-1) was added to 15 ml of n- Add the solution dissolved in xane and mix well with a spatula, then add n-hexane. was evaporated. Next, this mixture was thoroughly kneaded in a mortar to eliminate lumps.

On the other hand, a solid epoxy resin with an epoxy equivalent of 480 and a softening point of 68°C Add 2g of Epoxy Co., Ltd. (trade name: Epicoat tool) to 40ml of acetone. After dissolving in water, 6 ml of water, 10 g of the above fine particles, and 2-ethyl as a hardening agent. After adding 0.4 g of Ru-4-methylimidazole 2E4M2 and mixing thoroughly, stir Acetone was evaporated while stirring. Then, mash the dried material in a mortar to break up the lumps. Completely disassembled.

The average particle diameter of the coated resin fine particles thus obtained was 10.32 μm, with a standard deviation of The difference was 0.46 μm. From this result, the thickness of the adhesive epoxy resin layer is 0. It was calculated to be 21μ■. The surface of the coated resin particles was also examined using a scanning electron microscope. As a result of observation, it was found that the surface of the resin particles was coated uniformly with an epoxy resin layer without any gaps. It was found that

The value of the coated resin fine particles at 10% compressive strain is 420 kgf/mm2. , and the recovery rate after compressive deformation of this fine particle when the reversal load value is 1 grf is 52%. Met.

The liquid crystal display was prepared in the same manner as in Example 1 except that the coated resin fine particles were used as spacers. A display element was obtained. The gear knob value of the liquid crystal cell was in the range of 9.83 ± 0.03 μm. Ta.

In addition, when a polarizing sheet was attached to the liquid crystal cell in the same manner as in Example 1, the background color changed. No color unevenness was observed. Connect the power supply to the liquid crystal display element created in this way. As a result, good display performance was obtained.

±J Inorganic fine particles made of silicate glass with an average particle diameter of 7.30μm and a standard deviation of 032I1m. Particles were obtained. For 10 g of these inorganic fine particles, tetrapropoquinotitanium (Japanese soda) 0.35g of B-1 (manufactured by Tatsu Co., Ltd., trade name) was dissolved in 15ml of n-hexane. After adding the solution and mixing well with a spatula, the n-beef san was evaporated. next Then, thoroughly knead this mixture in a mortar to remove any lumps.

On the other hand, ho! 1-As a melt-type adhesive resin, carboxylic acid-containing 1/-vinegar Acid vinyl copolymer (manufactured by Gakoku Yakuhin Kogyo Co., Ltd., trade name Duramin C-2280) 2 ．． 9g was used.

Coated inorganic fine particles were obtained in the same manner as in Example 11 except as described above. scanning electronic As a result of observing the surface of the coated resin fine particles using a microscope, it was found that the particles formed on the coated inorganic fine particles It was found that the thickness of the hot melt type aggregate layer was 0.43 μm.

The value of the compressive strain io% of this coated inorganic fine particle is 5500 k g f, y ”’m　m2, and the compressive deformation of this fine particle when the reversal load value is 1grr. The subsequent recovery rate was 85%.

The liquid was prepared in the same manner as in Example 1, except that coated resin fine particles of , - were used as spacers. A crystal display element was obtained.

The gear value of the liquid crystal cell was in the range of 7.25±003 μm.

In addition, when a polarizing sheet was attached to the liquid crystal cell in the same manner as in Example 1, the background color changed. Color unevenness was observed, and the display condition in the lit state was insufficient.

Salt Mosquito Master Solid particles are made of silicate glass with an average particle diameter of 730 μm and a standard deviation of 0.3. Inorganic fine particles of 2 μm were obtained. For this inorganic fine particle log, tetrapropoquine 0.35 g of titanium (manufactured by Nippon Soda Co., Ltd., trade name B-1) was added to 15 ml of il-hexane. Add the solution dissolved in San and mix well with a spatula, then add beef San to n-. Evaporated. Next, this material was kneaded in a mortar for 1 minute to eliminate lumps.

On the other hand, as a curing agent, dicyandiamide (Yuka Shell Epoxy Co., Ltd., trade name D ICY-7) 0. 2 g and 2-phenylimidazole-4,5-diyldi 0.2 g of Metatool (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name 2PHZ) was used.

Coated inorganic fine particles were obtained in the same manner as in Example 12 except for the above. scanning electron microscope As a result of observing the surface of the coated resin fine particles using a microscope, it was found that they were formed on the coated inorganic fine particles. The thickness of the adhesive epoxy resin layer was found to be 0.41 μm.

The value of the coated inorganic fine particles at 10% compressive strain is 5300 kgf/mm2. Moreover, the recovery rate after compressive deformation of this fine particle when the reversal load value is 1 grf is 87. %Met.

The liquid crystal display was prepared in the same manner as in Example 1 except that the coated resin fine particles were used as spacers. A display element was obtained. The gear value of the liquid crystal cell was in the range of 7.23 ± 003 μm. .

In addition, when a polarizing sheet was attached to the liquid crystal cell in the same manner as in Example 1, the background color changed. Color unevenness was observed, and the display condition in the lit state was insufficient.

Branch Chief Okaue After suspension polymerization of tetramethylolmethanetetraacrylate, it is flattened by classification. Fine particles with an average particle diameter of 6.98 μm and a standard deviation of 0.23 μm were obtained. The pressure of this particulate The value at shrinkage strain lO% is 633 kgf/mm2, and the reversal load value is 1 grf. The recovery rate after compression deformation in this case was 63%.

After performing electroless nickel plating on these resin particles, a total substitution reaction - Conductive fine particles on which a gold plating layer was formed were obtained. When we analyzed these conductive particles, The gold content was 28.0% by weight, and the nickel content was 23.8% by weight.

Moreover, the average particle diameter was 7.24 μm, and the standard deviation was 0.28 μm.

1 g of these conductive fine particles and glass fiber (diameter 5.5 μm, average length 27 mm). 5 μm), 75 g of epoxy resin (manufactured by Yoshikawa Kako, SE-4500) and Mix it with 25g of hardening agent to make a paste 1. Ta. Next, as shown in Figure 6 [The above paste 13 is applied in a prescribed manner on the glass electrode 12 on which the TO film is formed on the inner surface.] After applying it in thickness, another ITO1! The poles 14 were superimposed. Next, this laminate is Place it in a press and heat it for 30 minutes at a pressure of 35 kg/'Cm2 and a temperature of 160°C. It was heat-pressed.

The test piece C thus prepared was heated at 90°C for 11 hours on the high temperature side and for 14 hours on the low temperature side. Thermal shock tester (TSV-4 manufactured by Tabai Espec Co., Ltd.) operates at 0'C for 1 hour. 0 type) and tested up to 240 cycles.

In addition, another test piece prepared in the same manner as above was tested under the conditions of 80'C and 90% RH. Place it in a constant temperature and humidity chamber (Tabai Espec Co., Ltd., model PR-3F) operated at 50 Tested for 0 hours. The two sheets were tested before and after this thermal shock test and before and after the humidity test. When the contact resistance between the electrodes was measured using the four-terminal method, the results shown in Table 1 were obtained. Ta. These results show that the connection reliability of these conductive particles is extremely high. I found out.

Shigosho Jodo Tetramethylolmethane tetraacrylate 751111% and divinylbenze After suspension polymerization of 25% by weight, the particles were classified to have an average particle size of 7.05 μm, standard deviation. Fine particles with a difference of 0.25μ were obtained. The value of this fine particle at 10% compressive strain is 52 7kgf/mm", and the recovery rate after compressive deformation when the reverse load value is 1grf is 5. It was 5%.

After performing electroless nickel plating on these resin particles, nickel is removed by a total substitution reaction. - Conductive fine particles on which a gold plating layer was formed were obtained. When we analyzed these conductive particles, The gold content was 29.1% by weight, and the nickel content was 23.4% by weight.

Further, the average particle diameter was 7.29μ11 with a standard deviation of 0.29μ.

A test piece was obtained in the same manner as in Example 13 except that this conductive fine particle was used. When a reliability test was conducted on the test piece, the results shown in Table 1 were obtained. This conclusion The results showed that the connection reliability using these conductive particles was extremely high. Ta.

Soso” LLl Tetramethylolmethane tetraacrylate 50fi1% and divinylbenzene After suspension polymerization of 50% by weight, the average particle diameter was 7.01 μm, standard deviation by classification. Fine particles of 0.25 μm were obtained. The value of this fine particle at 10% compressive strain is 468 kgf, mm2, and the recovery rate after compressive deformation when the reverse load value is 1 grf is 5 It was 2%.

After performing electroless nickel plating on these resin particles, nickel is removed by total substitution reaction. - Conductive fine particles on which a gold plating layer was formed were obtained. When we analyzed these conductive particles, The gold content was 30.5% by weight, and the nickel content was 19.5% by weight.

Moreover, the average particle diameter was 7.25 μm, and the standard deviation was 0.29 μm.

A test piece was obtained in the same manner as in Example 13 except that this conductive fine particle was used. When a reliability test was conducted on the test piece, the results shown in Table 1 were obtained. This conclusion The results showed that the connection reliability using these conductive particles was extremely high. Ta.

friend] Tetramethylolmethanetetraacrylate 25% by weight and divinylbenzene 7% After suspension polymerization of 5% by weight, the average particle size was 7.03 μm and the standard deviation was 0 by classification. ．． Fine particles of 28 μι were obtained. The value of this fine particle at 10% compressive strain is 448k gf/mrn2, and the recovery rate after compressive deformation when the reverse load value is 1grf is 52 %Met.

After performing electroless nickel plating on these resin particles, nickel is removed by a total substitution reaction. - Conductive fine particles on which a gold plating layer was formed were obtained. When we analyzed these conductive particles, The gold content was 27.6% by weight, and the nickel content was 24.3% by weight.

Further, the average particle diameter was 7.27 μm with a standard deviation of 0.29 μm.

A test piece was obtained in the same manner as in Example 13 except that this conductive fine particle was used. When a reliability test was conducted on the test piece, the results shown in Table 1 were obtained. This conclusion The results showed that the connection reliability using these conductive particles was extremely high. Ta.

Dai 1ヱLLL After suspension polymerization of divinylbenzene, it was classified to have an average particle size of 7.05 μm and a standard particle size of 7.05 μm. Fine particles with a standard deviation of 0.29 μm were obtained. The value of this fine particle at compressive strain lO% is Recovery rate after compressive deformation at 330 kgf/mm2 and reverse load value 1 grf was 38%.

After performing electroless nickel plating on these resin particles, nickel is removed by a total substitution reaction. - Conductive fine particles on which a gold plating layer was formed were obtained. When we analyzed these conductive particles, The gold content was 25.6% by weight, and the nickel content was 18.3% by weight.

Moreover, the average particle diameter was 7.30 μm, and the standard deviation was 0.32 μm.

A test piece was prepared in the same manner as in Example 13 except that this conductive fine particle was used. When a reliability test was conducted on the test piece, the results shown in Table 1 were obtained. this The results show that the connection reliability of these conductive particles is extremely high. It was.

Yokie [Ll Average particle size of ben/guanamine polymer: 6.98 μm, standard deviation: 025 μm After electroless nickel plating on the spacer, nickel is removed by gold substitution reaction. Conductive fine particles on which a gold plating layer was formed were obtained. When we analyzed these conductive particles, The gold content was 30.4% by weight, and the nickel content was 19.6% by weight. Ma In addition, the average particle diameter was 7.23 μm, and the standard deviation was 027 μm. This conductive fine particle The value at 10% compression strain of the child is 690 k g f / mrn2, and the compression strain The recovery rate after molding was 12%.

The test was carried out in the same manner as in Example 13, except that the conductive fine particles were used as a spacer. A reliability test was conducted on this test piece, and the results shown in Table 1 were obtained. It was done. From this result, it can be concluded that the connection reliability due to these conductive particles is poor. Understood.

YouLL± 30% by weight of triallyl isocyanurate and 70% by weight of diallyl phthalate were added. After turbid polymerization, fine particles with an average particle size of 700 μl and a standard deviation of 0.28 μm were obtained by classification. Particles were obtained. The value of this fine particle at 10% compressive strain is 245 k g f/r nm", and the recovery rate of the spacer after compression deformation was 12%.

After electroless nickel plating is applied to these fine particles, nickel-gold is formed by a gold substitution reaction. Conductive fine particles on which a plating layer was formed were obtained. Analysis of these conductive particles The gold content was 29.3% by weight, and the nickel content was 20.9% by weight. Also The average particle diameter was 7.23 μm, and the standard deviation was 0.30 μm.

The test was carried out in the same manner as in Example 13, except that the conductive fine particles were used as a spacer. A reliability test was conducted on this test piece, and the results shown in Table 1 were obtained. It was done. This result indicates that the connection reliability due to these conductive particles is poor. There was no difference in fine particles made of listyrene with an average particle diameter of 6.98 μm and a standard deviation of 027 μm. After electrolytic nickel plating, a nickel-gold plating layer is formed by a gold substitution reaction. conductive fine particles were obtained. When this conductive fine particle was analyzed, the gold content was found to be 3. The nickel content was 2.2% by weight, and the nickel content was 18.3% by weight.

Moreover, the average particle diameter was 7.23 μm, and the standard deviation was 0.29 μm. This conductivity The value of fine particles at 10% compression strain is 116 kg f/mm2, and the compression The recovery rate after deformation was not measurable.

The test was conducted in the same manner as in Example 13, except that the conductive fine particles were used as an impasser. A reliability test was conducted on this test piece, and the results shown in Table 1 were obtained. It was done. From this result, it is concluded that the connection reliability due to conductive particles is poor. Understood.

Under construction [ Fine particles made of silicon dioxide with an average particle diameter of 7.01μm and a standard deviation of 019l1m I got it. The value of this fine particle at 10% compressive strain is 5100 k gf/mrn 2, and the recovery rate of the fine particles after compression deformation was 85%.

After performing electroless nickel plating on these fine particles, a total substitution reaction is performed. Conductive fine particles on which a plating layer was formed were obtained. Analysis of these conductive particles The gold content was 27°4% by weight, and the nickel content was 19.6% by weight. Also The average particle diameter was 7.25 μm with a standard deviation of 0.20 μm.

Experiments were carried out in the same manner as in Examples 1 and 3, except that these conductive fine particles were used as spacers. A test piece was obtained, and a reliability test was conducted on this test piece, and the results shown in Table 1 were obtained. Obtained. From this result, the connection reliability due to these conductive particles is poor. I understand.

cold m After suspending 8 portions of tetramethylolmethane tetraacrylate, it was clarified by classification. Fine particles with an average particle diameter of 6.98μ and a standard deviation of 0.23μ were obtained. The pressure of this particulate The value at 10% shrinkage strain is 570 kgf/rnm2, and the reversal load value of fine particles The recovery rate after compression deformation in the case of 1 grf was 63%.

After electroless copper plating is applied to these resin particles, the copper plating layer is injected by a substitution reaction. It was replaced with dium. Analysis of these conductive fine particles revealed that the indium content was was torn 23.4%.

1 g of these conductive fine particles and glass fiber (diameter 5.5μ, average length 27mm). 5 μm), 75 g of epoxy resin (manufactured by Yoshikawa Chemical Industry, SE-4500) and 25 g of a hardening agent to prepare a paste. Next, as shown in Figure 6. First, the paste 13 is placed on the glass electrode 12 with an ITO film formed on the inner surface. After coating with a constant thickness, another ITO electrode 14 was superimposed. Next, this laminate is Place in a press and heat at a pressure of 35 kg/'Cm2 and a temperature of 160°C for 30 minutes. It was crimped.

Test piece C prepared as described above was heated at 90°C for 1 hour on the high temperature side and 140°C on the low temperature side. Thermal shock tester (TSv-40 manufactured by Tabai Espeli Co., Ltd.) that operates for 11 hours at °C. The test was carried out for up to 240 cycles.

In addition, another test piece prepared in the same manner as above was prepared at 80°C and 90% RH. Place it in a constant temperature and humidity chamber (Tabai Espec Co., Ltd., PR-3F type) and leave it at 500 hours. Tested for a while. Between the two electrodes before and after this thermal shock test and before and after the humidity test When the contact resistance value was measured by the four-terminal method, the results shown in Table 2 were obtained.

These results show that the connection reliability of these conductive particles is extremely high. Understood.

Shigaran Hill Builder Tetramethylolmethanetetraacrylate) 75% by weight and 2% divinylbenzene After suspension polymerization of 5% by weight, the average particle diameter was 7.05μm1 standard deviation 0 by classification. ．． 25 μl of microparticles were obtained. The value of this fine particle at compressive strain lO% is 475k gf/mm2, and the rotation after compressive deformation when the reversal load value of this fine particle is 1grf. The recovery rate was 55%.

After electroless copper plating is applied to these resin particles, the copper plating layer is injected by a substitution reaction. Replaced with dium. Analysis of these resin particles revealed that they contained indium. The rate was 19.8%.

A test piece was obtained in the same manner as in Example 18 except that this conductive fine particle was used. When a reliability test was conducted on the test piece, the results shown in Table 2 were obtained. This conclusion The results showed that the connection reliability using these conductive particles was extremely high. Ta.

50% by weight of tetramethylolmethanetetraacrylate and 5% of divinylbenzene After suspension polymerization of 0% by weight, the average particle diameter was 7.0171 m, standard deviation was determined by classification. Fine particles of 0.25 μm were obtained. The value of this fine particle at 10% compressive strain is 422 kgf/mrr+2, and the pressure when the reversal load value of this fine particle is 1grf The recovery rate after shrinkage deformation was 52%.

After electroless copper plating is applied to these resin particles, the copper plating layer is injected by a substitution reaction. Replaced with dium. Analysis of these resin particles revealed that they contained indium. The rate was 20.3%.

A test piece was obtained in the same manner as in Example 18 except that this conductive fine particle was used. When a reliability test was conducted on the test piece, the results shown in Table 2 were obtained. This conclusion The results showed that the connection reliability using these conductive particles was extremely high. Ta.

1 discussion 1 After turbid polymerization of tetramethylolmethane triacrylate, the average Fine particles with a particle diameter of 7.53 μm and a standard deviation of 028 μm were obtained. Compressive strain of this fine particle The value at 10% is 282 kgf/mm2, and the reverse load of this fine particle is The recovery rate after compression deformation when the weight value was 1 grf was 58%.

After electroless copper plating is applied to these resin particles, the copper plating layer is injected by a substitution reaction. It was replaced with dium. When this material was analyzed, the indium content was 19. It was 6%.

A test piece was obtained in the same manner as in Example 18 except that this conductive fine particle was used. When a reliability test was conducted on the test piece, the results shown in Table 2 were obtained. This conclusion The results showed that the connection reliability using these conductive particles was extremely high. Ta.

salt 11 Average particle size of benzoguanamine polymer: 6.98 μl, standard deviation: 0.25 μl m fine particles were obtained. The value of this fine particle at 10% compressive strain is 620 kgf/m m2, and the recovery rate after compressive deformation when the reverse load value Igrf was 12%. . After electroless copper plating is applied to these fine particles, the copper plating layer is transformed into an ink layer by a substitution reaction. It was replaced with um. When this fine particle was analyzed, the indium content was 22. It was 6%.

A test piece using this conductive fine particle was obtained in the same manner as in Example 18, and this test When a reliability test was conducted on the piece, the results shown in Table 2 were obtained. As a result It was found that the connection reliability due to these conductive particles was poor.

Ratio "■1 above" - Fine particles made of silicon dioxide with an average particle diameter of 7.01 μm and a standard deviation of 0.19 μm. I got it. The value of this fine particle at 10% compressive strain is 4590 kgf/mm2 Met. Further, the recovery rate of the fine particles after compression deformation was 85%.

After electroless copper plating is applied to these fine particles, the copper plating layer is injected by a substitution reaction. It was replaced with um. When this fine particle was analyzed, the indium content was 9. It was 8% by weight.

A test piece was obtained in the same manner as in Example 18 except that this conductive fine particle was used, and this test When a reliability test was conducted on the piece, the results shown in Table 2 were obtained. As a result Therefore, it was found that the connection reliability due to these conductive particles was poor.

(Margin below) Figure 1 ↑ A mouth that teaches oneself Recitation 3 ↑ Figure 4 6th figure international search report +mwpm*++m11aevrtalImII&PCT/JP 91101 285 International Search Report Continuation of front page (31) Priority claim number: Patent application Hei 3-104299 (32) Priority date: Hei 3 (1) 991) May 9th (33) Priority claim country Japan (JP) (31) Priority claim Number: Patent Application Hei 3-104300 (32) Priority Date: May 9, 1991 (33) Priority claim country Japan (JP) (81) Designated country EP (AT, BE, C H, DE.

Claims (15)

[Claims] 1. K=(3/√2)・F・S−3/2・R−1/2 [Here, F and S are respectively The load value (kgf) and compressive displacement (mm) at 10% compressive deformation of the microspheres are and R is the radius (mm) of the microsphere] at 20°C. range of 250 kgf/mm2 to 700 kgf/mm2, and after compression deformation. A microsphere whose recovery rate is in the range of 30% to 80% at 20°C. 2. The microspheres according to claim 1, wherein the K value is 350 kgf/mm2 to 55. The range is 0 kgf/mm2. 3. The microspheres according to claim 1, wherein the recovery rate after compressive deformation is at 20°C. It is in the range of 40% to 70%. 4. The microspheres according to claim 1, wherein the microspheres are divinylbenzene polymers. , divinylbenzene-styrene copolymer, divinylbenzene-acrylic acid ester and diallyl phthalate polymers. It is also formed from a type of resin. 5. The microsphere according to claim 1, wherein the microsphere is perfectly spherical and has a diameter of 0. ．． It is in the range of 1 to 100 μm. 6. The microsphere according to claim 5, wherein the microsphere has a diameter in the range of 0.5 to 50 μm. It is surrounded. 7. The microsphere according to claim 6, wherein the microsphere has a diameter in the range of 1.0 to 20 μm. It is surrounded. 8. K=(3/√2)・F・S−3/2・R−1/2 [Here, F and S are respectively The load value (kgf) and compression displacement (m) at 10% compression deformation of the spherical spacer are m) and R is the radius (mm) of the spacer]. It is in the range of 250 kgf/mm2 to 700 kgf/mm2 at 20°C, and A liquid crystal display element whose recovery rate after compression deformation is in the range of 30% to 80% at 20°C Spherical spacer for children. 9. A colored spherical spacer for liquid crystal display elements containing colored base material microspheres. Then, K=(3/√2)・F・S−3/2・R−1/2 [Here, F and S are respectively Load value (kgf) and compression displacement at 10% compression deformation of the colored spherical spacer (mm) and R is the radius (mm) of the spacer] is in the range of 250 kgf/mm2 to 700 kgf/mm2 at 20°C. , and the recovery rate after compression deformation is in the range of 30% to 80% at 20°C. Colored spherical spacer for display devices. 10. A liquid crystal containing a base microsphere and an adhesive layer provided on the surface of the base microsphere. An adhesive spherical spacer for display elements, K=(3/√2)・F・S−3/2・R−1/2 [Here, F and S are respectively applicable. Load value (kgf) at 10% compression deformation of adhesive spherical spacer, compression displacement ( mm) and R is the radius (mm) of the spacer. , in the range of 250 kgf/mm2 to 700 kgf/mm2 at 20°C, A liquid crystal display whose recovery rate after compression deformation is in the range of 30% to 80% at 20°C. Adhesive spherical spacer for elements. 11. A liquid crystal display element using the spherical spacer according to claim 8. 12. A liquid crystal display element using the colored spherical spacer according to claim 9. 13. A liquid crystal display element using the adhesive spherical spacer according to claim 10. 14. A microsphere comprising the microspheres according to claim 1 and a conductive layer provided on the surface of the microspheres. conductive sphere. 15. The conductive microspheres according to claim 14, wherein the conductive layer is an indium plating layer. .