JP2000169591A - Particle coated with photo-setting resin, its production and production of liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To effectively fix a spacer only on the black matrix of a base plate to thereby obtain a liquid crystal element of high contrast by forming a photo- setting resin layer containing a high-purity photopolymerizable acrylate prepolymer having an impurity content below a specified value and a photopolymerization initiator and providing a protective layer on the surface of the layer. SOLUTION: The impurity content of a photopolymerizable prepolymer is 0-200 ppm by weight. A protective layer has a siloxane linkage derived from a silane coupling agent, A spacer comprising particles coated with a photo- setting resin is uniformly scattered on the surface of a base plate, only particles on the pixel part are photo-set to make them infusible, the base plate with the spacer is then heat treated at a temperature at which a prepolymer in the particles unexposed to light is dissolved out from the protective siloxane layer or above to melt the resin of the particles on the black matrix to thereby stick the particles to the base plate, and only the photo-set particles on the pixel part are then removed. The core particles preferably comprise silica particles or polyorganosilsesquioxane particles in particular.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photocurable resin-coated particle, a method for producing the same, a spacer comprising the particle, a method for producing a liquid crystal display device using the spacer, and a liquid crystal display device obtained by the method. . More specifically, the present invention relates to a photocurable resin-coated particle suitable as a fixed-type in-plane spacer for a liquid crystal display element, a method for efficiently producing the same, and a high-quality liquid crystal comprising the photocurable resin-coated particle. A fixed-type in-plane spacer for a liquid crystal display element providing a display element, a method of manufacturing a liquid crystal display element using the spacer and having excellent quality of high contrast without light leakage from a pixel, and a liquid crystal display element obtained by this method It is about.

[0002]

2. Description of the Related Art In recent years, the development of liquid crystal display devices has been remarkable. Not only those having a small display such as a clock, a calculator, a notebook computer, etc., but also having a large display such as a word processor, a desktop personal computer and a television. It is used as a display element of equipment.

This liquid crystal display element is generally composed of a large number of pixels, and each pixel is partitioned by a portion not related to display called a black matrix to prevent light leakage in a region other than the display pixel. Improving the contrast ratio has been performed.

In a liquid crystal display device, two transparent electrode substrates on which an alignment layer is formed are generally aligned and arranged at a predetermined gap via spacer particles, and the periphery is sealed to form a liquid crystal cell. And a structure in which a liquid crystal material is sandwiched between the electrode substrates. The spacer particles have a function of keeping the gap between the electrode substrates, that is, the thickness of the liquid crystal layer uniform, and are used in the peripheral sealing portion of the liquid crystal cell and inside the liquid crystal cell (in-plane, display portion).

Among the in-plane spacers for keeping the thickness of the liquid crystal layer of the liquid crystal display element constant, so-called fixed spacers having a function of preventing movement include thermoplastic resins, thermosetting resins, and optical spacers. True spherical particles coated with a curable resin are used, and are usually used by being uniformly dispersed on a substrate. However, in the case of uniform dispersion, since the spacers are also present on the pixels, light leaks from the spacers themselves or the surroundings thereof, resulting in an undesirable situation that the contrast is reduced.

Therefore, a technique for forming or disposing a spacer only on a black matrix has been studied. For example, (1) a method of forming a column or wall made of a polymer compound at an arbitrary position by an electrodeposition method, (2)
A method of forming a spacer using various photocurable resists by photolithography technology, and (3) a method of charging spherical particles, applying the same potential to a pixel electrode of a substrate, and spraying the same have been tried. I have.

However, the electrodeposition method (1) has drawbacks in that the production cost is inevitably high and it is difficult to adjust the height of the spacers with high accuracy and uniformity. Further, the method of using the photocurable resist of (2) has a limitation on a solvent for removing the resist, the strength is not sufficient with a polymer material or polysilane, and gap unevenness is likely to occur. In addition, a high heating temperature (150 ° C. or higher) is required for cross-linking, and the organic material portion of the device may be damaged. On the other hand, the method (3) has a problem in that it takes time and effort to print the voltage application pattern, and it is difficult to form a multiple pattern.

Further, a spacer having a thermoplastic resin layer in which a cross-linking agent and a photoinitiator are absorbed is used, and the spacer is uniformly dispersed on a color filter (pixel) and a black matrix. A method is disclosed in which only a spacer in a pixel portion is cured, and further, the thermoplastic resin of the spacer on the black matrix is melted by heating, the spacer is bonded, and only the light-cured spacer is removed (Japanese Patent Laid-Open No. Hei 6 (1994)). -289402
No.). However, in this method, (a) the cross-linking agent or photoinitiator is easily eluted into the liquid crystal, (b) during backside exposure, the amount of transmitted light varies depending on the color of the color filter, and curing hardly occurs uniformly in the pixel Therefore, the spacers may remain on the pixels, and (c) since the spacers themselves absorb liquid, the cross-linking agent or the like may elute during spraying and may adhere to the substrate. are doing.

[0009]

SUMMARY OF THE INVENTION The present invention overcomes the disadvantages of the prior art in which a spacer is provided only in a black matrix portion on a substrate in the manufacture of a liquid crystal display device, and a spherical particle is provided only on the black matrix of the substrate. It is intended to provide a method of manufacturing a high-contrast liquid crystal display element in which light is not leaked from the inside of a pixel by effectively fixing a spacer comprising, and a spacer comprising spherical particles used in this method. is there.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that a photocurable resin containing a specific photopolymerizable prepolymer is provided on the surface of core particles composed of spherical particles. Photocurable resin-coated particles having a curable resin layer, and having a protective layer having a siloxane bond on the surface of this layer,
Elution of the resin component does not occur under unheated conditions (room temperature), and the particles are used as fixed spacers for liquid crystal display elements, and by using a specific method, the particles are formed only on the black matrix of the substrate. It has been found that the spacer can be effectively fixed, and that the photocurable resin-coated particles can be efficiently produced by sequentially performing specific steps, and based on this finding, the present invention has been completed. Was.

That is, the present invention provides (1) a photo-curable resin layer containing a photo-polymerizable prepolymer and a photo-polymerization initiator on the surface of a core particle composed of spherical particles; Particles provided with a protective layer having a siloxane bond derived from a coupling agent, wherein the photopolymerizable prepolymer is a high-purity acrylate prepolymer having an impurity content of 0 to 200 ppm by weight. (2) (Step A) a step of subjecting a core particle composed of a spherical particle to a surface treatment with a silane coupling agent having a hydrophobic group to introduce a hydrophobic group into the surface of the core particle; Step B) The core particles surface-treated in step A are placed in an organic solvent solution containing a high-purity acrylate prepolymer having a photopolymerizable impurity content of 0 to 200 ppm by weight and a photopolymerization initiator. Is dispersed, after performing the process for depositing the photocurable resin on the core particle surface comprising a photopolymerizable prepolymer and a photopolymerization initiator, the solvent was removed,
A step of obtaining a dry powder in which the photocurable resin is precipitated on the surface of the core particles, (step C) subjecting the dry powder obtained in step B to an impact or shear force imparting treatment to obtain a photopolymerizable high purity A step of coating the surface of the core particles with a photocurable resin layer containing an acrylate prepolymer and a photopolymerization initiator, and (step D) the light of the particles coated with the photocurable resin layer obtained in step C. At least one selected from a silane coupling agent having a hydrophobic polymerizable group, a partial hydrolyzate of the silane coupling agent, and an oligomer obtained by hydrolytic condensation of the silane coupling agent with a curable resin. After absorbing the species of the silane coupling agent-based compound, the process of adding ammonia solution to promote the condensation of the silane coupling agent-based compound and forming a siloxane bond is sequentially performed. (1) the method for producing the photocurable resin-coated particles according to the above (1); (3) the fixed-type in-plane spacer for liquid crystal display elements comprising the photocurable resin-coated particles according to the above (1); After uniformly dispersing the spacer composed of the photocurable resin-coated particles on the substrate surface having the pixel portion and the black matrix, only the pixel portion is exposed from the spacer dispersing surface side via a photomask to the pixel portion. Only the upper particles are photo-cured to make them infusible, and then heat-treated to a temperature above the temperature at which the photopolymerizable prepolymer in the unexposed particles elutes from the protective layer having a siloxane bond, to remove the resin of the particles on the black matrix. A method of manufacturing a liquid crystal display element, characterized in that after melting and adhering the particles to the substrate, only the photocured particles on the pixel portion are removed; and (5) the method of (4) is obtained. The liquid crystal display element,
Is provided.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The photocurable resin-coated particles of the present invention have a photocurable resin layer on the surface of a core particle composed of spherical particles and a protective layer having a siloxane bond provided on the surface of this layer. It is.

The material of the spherical particles that can be used as the core particles in the present invention is substantially spherical particles, and can form a chemical bond by reacting with the hydrophilic functional group of the silane coupling agent. An inorganic material or an organic-inorganic composite material is exemplified. Specific examples of the material include silica; metal oxides such as WO ₃ , SnO ₂ , TiO ₂ , ZrO ₂ , and Al ₂ O ₃ ; silicate glass, borate glass, borosilicate glass, and aluminoborosilicate Glass such as glass, phosphate glass, germanate glass, tungstate glass, molybdate glass, tellurate glass; black particles and black particles with an insulating film disclosed in WO96 / 15986 An organic-inorganic composite such as polyorganosilsesquioxane, etc., which can be appropriately selected according to the intended use of the photocurable resin-coated particles.

The particle size of the core particles composed of the spherical particles can be appropriately selected according to the intended use of the photocurable resin-coated particles. For example, when the photocurable resin-coated particles of the present invention are used as a spacer for a liquid crystal display device (liquid crystal cell), the core particles have a particle size of 0.4 to 29 μm.
m silica particles or polyorganosilsesquioxane particles are particularly preferred. The coefficient of variation (hereinafter referred to as CV value) of the particle size distribution is 5% or less, particularly 2%.
%. The CV value is determined by the formula CV value (%) = (standard deviation of particle size / average particle size) × 100.

The photocurable resin layer covering the surface of the core particles is composed of a photopolymerizable prepolymer, a photopolymerization initiator, and a photopolymerizable monomer optionally used.

In the present invention, the photopolymerizable prepolymer is an alkali metal or alkaline earth which is solid at normal temperature, has a softening point of preferably about 40 to 150 ° C., and lowers the specific resistance of the liquid crystal. Metals and their metal salts,
Those having a total content of impurities such as halogen, amine and amine salt of 0 to 200 ppm by weight are used. Examples of such a material include epoxy acrylate, polyester acrylate, polyurethane acrylate, polyether acrylate, oligoacrylate, alkyd acrylate, and polyol acrylate. These may be used alone or in combination of two or more, and epoxy acrylate is particularly preferred.

The photopolymerizable acrylate prepolymer having such properties can be prepared, for example, by converting a high-purity raw material prepolymer into an acrylate by a known method, and then purifying the acrylate by washing or distillation. it can.

Examples of the photopolymerization initiator include known compounds which generate radicals by actinic rays such as ultraviolet rays, for example, biacetyl, acetophenone, 2,2-diethoxyacetophenone, α-hydroxyisobutyrophenone, and the like.
Benzophenone, Michler's ketone, benzyl, benzyl methyl ketal, benzoin, benzoin isobutyl ether, benzoin isopropyl ether, hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, tetramethyl thiuram sulfide, azobisisobutyronitrile, benzoyl peroxide, di-tert-
Butyl peroxide, 1-hydroxy-2-methyl-1
-Phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-
Examples thereof include 1-one, 2-chlorothioxanthone, and methylbenzoylformate. These may be used alone or in combination of two or more.

On the other hand, examples of the photopolymerizable monomer which is optionally used include known monomers having at least one double bond per molecule, such as acrylic acid, acrylamide, acrylonitrile, styrene and acrylate, such as lauryl. Acrylate, 2-hexyl acrylate, 2-hydroxy acrylate, 1,6-hexanediol monoacrylate, dicyclopentadiene acrylate, 1,3-butanediol diacrylate,
Examples thereof include 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol diacrylate, trimethylolpropane triacrylate, and pentaerythritol triacrylate. These may be used alone or in combination of two or more.

Regarding the content ratio of each of the above components in the photocurable resin layer, the photopolymerizable monomer is usually 0 to 500% by weight, preferably 0% by weight, based on the photopolymerizable prepolymer.
It is preferred that the content be contained at a ratio of about 200% by weight. It is advantageous that the photopolymerization initiator is contained in an amount of usually 0 to 20% by weight, preferably 0.001 to 10% by weight, based on the total amount of the photopolymerizable prepolymer and the photopolymerizable monomer. is there.

The photocurable resin layer in the coated particles of the present invention has the following structure. That is, the photopolymerizable prepolymer, the photopolymerization initiator and the photopolymerization monomer used as desired are substantially uniformly mixed, and cover the surface of the core particles, or the impact force or the shearing force described below. By the force imparting treatment, at least a part of each of the above components is melted, melted and mixed with each other, and present as a single layer, covering the surface of the core particles.

The coated particles of the present invention are preferably such that the core particles, the photopolymerizable prepolymer constituting the photocurable resin layer, and the photopolymerizable monomer optionally used are bonded via a silane coupling agent. preferable. That is, the silane coupling agent has a hydrophilic substituent and a hydrophobic group, and one of the hydrophilic substituents forms a chemical bond with a material constituting the core particle, and the other hydrophobic substituent. Preferably, the functional group forms a chemical or physical bond with the photopolymerizable prepolymer or photopolymerizable monomer. in this way,
Since the core particles and the photopolymerizable prepolymer and the photopolymerizable monomer are bonded via the silane coupling agent, the core particles and the photocurable resin layer are firmly joined together. There is no peeling of the photocurable resin layer due to, for example, and a high adhesive strength can be obtained. Thus, for example, when used as a fixed-type in-plane spacer for a liquid crystal display device, strong adhesion to a liquid crystal cell film can be achieved.

The silane coupling agent is not particularly limited as long as it has one or two hydrophobic groups as substituents and the hydrophilic substituent is an alkoxy group. Such materials include, for example, phenyltriethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β (aminoethyl) γ- Aminopropyltrimethoxysilane, N-β (aminoethyl) γ
-Aminopropylmethyldimethoxysilane, β- (3,
4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropylmethyldimethoxysilane, 3-
Examples thereof include aminopropyltriethoxysilane, and further include alkyltriethoxysilanes, alkyltrimethoxysilanes, dialkyldiethoxysilanes, and dialkyldimethoxysilanes. Among them, γ-methacryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane and the like are preferable. These silane coupling agents may be used alone or in combination of two or more.

When the material of the core particles is an inorganic material, tetraalkoxysilane (for example, tetraethoxysilane, tetramethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc.) may be used together with the above-mentioned silane coupling agent having a hydrophobic group. ) May be reacted. By reacting the silicon alkoxide with a high hydrolysis rate at the same time as the silane coupling agent, the surface of the core particles is made more hydrophobic, and the coating with the photocurable resin and the binding property between the core particles and the photocurable resin layer are better. Becomes

The thickness of the photocurable resin layer in the coated particles of the present invention can be appropriately selected depending on the intended use, but is usually 0.001 to 5.0 μm, preferably 0.005 to 3.0 μm. And particularly preferably 0.01 to
The range is 1.0 μm.

The coated particles of the present invention are provided on the surface of the photocurable resin layer with a siloxane bond derived from a hydrophilic functional group of a silane coupling agent bonded to a photopolymerizable prepolymer or a photopolymerizable monomer. -Si-O-) is provided.

The silane coupling agent is not particularly limited as long as it has a hydrophobic group, preferably a polymerizable group and a hydrophilic substituent, and is not particularly limited. It may be appropriately selected and used. Further, the same compound as that used for bonding the core particles to the photopolymerizable prepolymer or the photopolymerizable monomer or a different compound may be used.

One of the hydrophobic groups of the silane coupling agent used here forms a chemical or physical bond with a photopolymerizable prepolymer or a photopolymerizable monomer constituting the photocurable resin layer, and the other hydrophobic group. Hydrophilic substituents (alkoxy groups)
Is hydrolyzed, and the hydrophilic substituents of the silane coupling agent bind to each other to form a siloxane bond. Therefore,
The surface of the photocurable resin layer is a siloxane bond network (protective layer)
It is thought that it is in a state where it is covered by.

As described above, the presence of the protective layer having a siloxane bond on the particle surface prevents coalescence and aggregation between individual particles even after long-term storage. Also, even when sprayed as a fixed spacer by a wet method, coalescence and aggregation between particles do not occur. If a hydrophilic siloxane bond is present on the surface of the particles, the particles repel each other, so that the particles do not coalesce or aggregate, and the dispersibility of the particles increases. On the other hand, in the case of the coated particles having no siloxane bond on the surface of the particles, when the particles are sprayed by the wet method, coalescence and aggregation of the particles are likely to occur, and it is difficult to adopt the spray method by the wet method.

The total particle size of the coated particles of the present invention can be appropriately selected depending on the intended use. For example, when the purpose is to provide a fixed-type in-plane spacer for a liquid crystal display device, it is usually 0.5 μm. ３０30 μm, preferably 0.7 to 25
μm, particularly preferably in the range of 1.0 to 15 μm.
When a precision adhesive is intended, usually 0.5 to 100
μm, preferably 0.7 to 80 μm, particularly preferably 1.0 to 60 μm.

The coated particles of the present invention having such a constitution do not elute the resin component at room temperature, and therefore do not cause coalescence or aggregation between the particles and do not exhibit adhesiveness to the substrate. When the coated particles are heated above a certain temperature, the resin component elutes from the protective layer having siloxane bonds,
The above-mentioned elution does not occur if irradiation with actinic rays such as ultraviolet rays is carried out in advance and the composition is cured by light and made infusible. By utilizing such properties, the particles can be fixed only to the black matrix portion of the substrate, as described later. Therefore, the photocurable resin-coated particles of the present invention are extremely useful as fixed-type in-plane spacers for liquid crystal display elements. And when used as a fixed-type in-plane spacer for liquid crystal display elements, it has a high anti-movement ability, does not move during ultrasonic irradiation, liquid crystal material injection, extrusion, and the in-plane scatter density does not change, It is possible to keep the cell gap constant. Further, since the coated particles of the present invention maintain the monodispersibility of the core particles, the thickness of the liquid crystal cell can be regulated with extremely high accuracy.

When the coated particles of the present invention are used as a precision adhesive, shrinkage during curing is small, and bonding can be performed at a specific interval with extremely high precision. Therefore, it can be suitably used, for example, for fixing various micro optical members and connecting between the waveguide and the optical fiber. Further, by uniformly arranging and curing the coated particles of the present invention in one layer, a microfiltration filter having filtration holes of extremely fine and precise size can be obtained.

Next, the method for producing the coated particles of the present invention will be described. The method for producing the coated particles is as follows: Step A: Surface treatment of the core particles with a silane coupling agent; Step B: Precipitation treatment of the photopolymerizable prepolymer and photopolymerization initiator on the surface of the core particles; Step C: Impact force or And a step D: a siloxane bond forming treatment, which will be described in detail below for each step.

Step A: Core with silane coupling agent
In the particle surface treatment step A, a bond is formed between the hydrophilic substituent (alkoxy group) of the silane coupling agent and the substance constituting the core particle, and in the next step B, the core particle and the photopolymerizable prepolymer or This is a step of introducing a hydrophobic group for forming a chemical or physical bond with the photopolymerizable monomer onto the surface of the core particle. In step A, the core particles composed of spherical particles are surface-treated with a silane coupling agent having a hydrophobic group to introduce a hydrophobic group to the surface of the core particles.

In order to introduce the hydrophobic group of the silane coupling agent into the core particles, first, the core particles are dispersed in a solvent such as an alcohol solvent by using ultrasonic vibration or the like.
Preferably, aqueous ammonia is added to this dispersion, and then a silane coupling agent having a hydrophobic group is added and stirred, whereby the hydrophilic substituent (alkoxy group) of the silane coupling agent is hydrolyzed. A bond is formed between the core particle and a substance constituting the core particle, and a hydrophobic group is introduced to the surface of the core particle.

The alcohol solvent used in this step includes, for example, methanol, ethanol, n-propanol, isopropanol and the like. The solvent used at this time may be one kind of alcohol or a mixture of plural kinds of alcohols. The amount of the alcohol solvent used is preferably 5 to 30 times the weight of the core particles.

The amount of the silane coupling agent having a hydrophobic group to be used is usually 0.1 to 500% by weight, preferably 0.5 to 200% by weight, particularly preferably 1 to 100% by weight, based on the core particles. Range. If the amount of the silane coupling agent is less than 0.1% by weight, it is not possible to introduce a hydrophobic group that can provide a sufficient bond with a photopolymerizable prepolymer or a photopolymerizable monomer. Also, 500
If the amount exceeds the above range, the hydrolyzate of the silane coupling agent agglomerates and adheres to the surface of the particles to deteriorate the monodispersity of the particles, which is inconvenient. The amount of aqueous ammonia added to hydrolyze the hydrophilic substituent of the silane coupling agent is
The ratio is preferably 2 to 300 times the number of moles of the silane coupling agent.

The reaction temperature during the hydrolysis is usually from 20 to 80.
° C, and the reaction time is usually 1 to 24 hours.

As described above, when the material of the core particles is an inorganic material, a silicon alkoxide having a high hydrolysis rate may be used, if necessary, during the surface treatment of the core particles with a silane coupling agent having a hydrophobic group. By coexisting, it is possible to introduce a sufficient amount of a hydrophobic group to form a more uniform photocurable resin layer on the surface of the core particles.

Step B: Photopolymerizable prepolymer and photopolymerization
The precipitation treatment step B of the initiator on the surface of the core particles is performed on the surface-treated core particles obtained in the above step A,
This is a step of obtaining a dry powder in which a photocurable resin composed of a photopolymerizable prepolymer, a photopolymerization initiator and a photopolymerizable monomer optionally used is uniformly deposited, and the following step C
Is a pretreatment step for performing the impact force or shear force imparting treatment in the above.

Specifically, the surface treatment was carried out with a silane coupling agent in the above step A in a solution in which a photopolymerizable prepolymer, a photopolymerization initiator and, if desired, a photopolymerizable monomer were uniformly dissolved in an organic solvent. The core particles are added and uniformly dispersed using ultrasonic vibration or the like. To the resulting dispersion, a large amount of a photopolymerizable prepolymer, a photopolymerization initiator and a poor solvent for the photopolymerizable monomer optionally used are added, and the photopolymerizable prepolymer, the photopolymerization initiator and optionally used are used. A photo-curable resin composed of a photo-polymerizable monomer is precipitated on the surface of the core particles in a uniformly mixed state, and then the solvent is removed by a means such as distillation under reduced pressure to obtain a dry powder.

The organic solvent used for dissolving the components constituting the photocurable resin used herein includes, for example, acetone, methyl ethyl ketone, dimethyl formamide, dimethyl sulfoxide, diethyl ketone, dichloromethane,
Chloroform and the like can be mentioned. The amount of the organic solvent used may be any amount as long as the components can be completely dissolved.

Examples of the poor solvent for each component constituting the photocurable resin include water, methanol, ethanol and the like. If necessary, a plurality of these may be mixed and used. The amount of the poor solvent to be added depends on the amount of the organic solvent used.
More than twice is preferred.

The dry powder obtained in this step is composed of a photocurable resin comprising a photopolymerizable prepolymer, a photopolymerization initiator and a photopolymerizable monomer optionally used, which are much smaller in particle size than the core particles. , Are substantially uniformly mixed on the surface of the core particles and adhered with a uniform thickness. At this stage, the photocurable resin composed of the photopolymerizable prepolymer, the photopolymerization initiator and the photopolymerizable monomer optionally used is attached to the surface of the core particle or is adsorbed on the surface of the core particle with a weak force. It's just that.

As a method for precipitating a photopolymerizable prepolymer, a photopolymerization initiator and an optional photopolymerizable monomer uniformly on the surface of the core particles, in addition to the above-mentioned method of adding a poor solvent, It is also possible to use a method of removing the organic solvent under a stirring condition by using a heating and stirring device such as a Henschel mixer. The photopolymerizable prepolymer has an impurity content of 0 to 2 as described above.
A high-purity acrylate prepolymer of 00 ppm by weight is used.

Step C: Impact or Shearing Treatment Step C is a step of subjecting the dry powder obtained by depositing the photocurable resin obtained in the above step B on the core particle surface to an impact or shearing treatment, The photocurable resin adsorbed to the core particle surface with a weak force is thermally fused to the core particle surface, and at the same time, the hydrophobic group introduced on the core particle surface and the photopolymerizable prepolymer or photopolymerizable monomer This is a step of forming a chemical or physical bond therebetween to obtain coated particles in which the photocurable resin layer is fused to the surface of the core particles.

Here, as a preferred specific example of the impact or shear force imparting treatment that can be used in the present invention, a hybridization method can be mentioned. Hybridization is used to modify the surface of microparticles, and the core particles and the smaller microparticles for modification are generally mixed in a high-speed air stream to form a modified layer on the surface. Is the way. More specifically, a spherical particle serving as a core and a particle (having a smaller particle size than the core particle) serving as a material of a modified layer to be formed on the surface of the spherical particle are formed at a high speed of several tens of meters per second or more. The particles collide with each other while dispersing and moving in an airflow.The heat generated by the mechanical action such as collision force, compression force, frictional force, and shearing force, and the temperature rise due to the mechanical action such as shear force are applied to the surface of the core This is a method of forming a desired modified layer by deposition. Other specific examples of the impact or shearing force imparting treatment that can be used in the present invention include a mechanofusion method.

In the method of the present invention, in the above step B, a photopolymerizable prepolymer, a photopolymerization initiator, and a photopolymerization initiator, if necessary, which are particles for surface modification in advance of the impact or shear force imparting treatment. The photo-curable resin composed of a reactive monomer is deposited and adhered on the surface of the core particles in a uniformly mixed state, so that two or three kinds of particles for surface modification are more reliably mixed in a uniform state. Since it is possible to perform thermal fusion with a uniform thickness, the photocurable resin layer can be formed on the core particle surface with a uniform thickness. Also, at the time of this treatment, by impact force or shear force,
A chemical or physical bond is formed between the hydrophobic group of the silane coupling agent introduced on the core particle surface and the photopolymerizable prepolymer or photopolymerizable monomer.

The core particles in which the hydrophobic group of the silane coupling agent has not been introduced and the surface-modified particles obtained by simply subjecting the photocurable resin to an impact or shearing force treatment are modified to the core particles. Since there is no chemical or physical bond at the interface with the porous layer, and the modified layer is formed of an aggregate of fine particles, the ultrasonic durability and mechanical properties are not good.
Therefore, even if the photocurable resin is simply fused to the core particles that have not been surface-treated with a silane coupling agent having a hydrophobic group by, for example, a hybridization method, the photocurable resin layer fused to the core particles may be used. The binding force with
The photocurable resin layer is easily peeled off by ultrasonic treatment or other mechanical external force.

However, in the method of the present invention,
When a chemical or physical bond is formed between the core particles and the photopolymerizable prepolymer or photopolymerizable monomer by a silane coupling agent having a hydrophobic group, so that only impact force or shear force treatment is applied. Unlike this, an extremely high bonding force exists between the core particles and the photocurable resin layer.

The hybridization method used in this step can be performed using, for example, a hybridization system type O (NHS-O type) manufactured by Nara Machinery Co., Ltd. Preferred conditions for hybridization when using this hybridizer are as follows. Rotor rotation speed: 3000-16000 rpm Processing time: 3-30 minutes

Step D: Siloxane bond formation treatment Step D comprises a siloxane bond derived from a hydrophilic substituent of a silane coupling agent-based compound on the photocurable resin layer of the coated particles obtained in the above Step C, ie, the particle surface. This is a step of forming a protective layer having

In this step, first, the coated particles obtained in step C are subjected to silane coupling having a hydrophobic polymerizable group, partial hydrolysis of the silane coupling agent, and hydrolysis and condensation of the silane coupling agent. At least one silane coupling agent-based compound selected from the obtained oligomers is absorbed. At this time, the coated particles obtained in Step C are dispersed in an aqueous solvent solution containing a dispersion stabilizer, and It is advantageous that the silane coupling agent-based compound is added to be absorbed in the photocurable resin layer.
Examples of the aqueous solvent used in this step for dispersing the coated particles obtained in Step C include water and a water-alcohol solution. Examples of the alcohol in the case of the water-alcohol solution include methanol, ethanol, n-propanol, and isopropanol.

The dispersion stabilizer used in this step is not particularly limited as long as it can stably disperse the coated particles obtained in step C. For example, partially saponified polyvinyl alcohols, polyvinylpyrrolidone, hydroxypropyl Cellulose, or an ether type nonionic surfactant, specifically, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl ethers, polyoxyethylene alkylene alkyl ethers, polyoxyethylene polyoxypropylene block polymer, or the like, or Fatty acid esters of polyhydric alcohols, fatty acid esters of polyethylene glycol, sodium laurate, sodium laurylbenzenesulfonate,
Sodium polyoxyethylene lauryl ether sulfate,
And partially saponified polyvinyl alcohol. The concentration of these dispersion stabilizers is usually in the range of 0.01 to 30% by weight, preferably 0.05 to 25% by weight, particularly preferably 0.1 to 20% by weight.

In this step, first, a silane coupling agent having a hydrophobic polymerizable group in the photocurable resin layer, a partial hydrolyzate of the silane coupling agent, and a hydrolytic condensation of the silane coupling agent are obtained. Absorbs at least one silane coupling agent compound selected from oligomers to form a chemical or physical bond with a radically polymerizable acrylate prepolymer or a radically polymerizable monomer constituting the photocurable resin layer. Let it. The addition amount of the silane coupling agent-based compound is usually 5 to 3 with respect to the total amount of the photopolymerizable prepolymer and the photopolymerizable monomer.
000% by weight, preferably 10 to 2000% by weight, particularly preferably 20 to 1500% by weight.

Next, the silane coupling agent-based compound thus absorbed in the photocurable resin layer is subjected to a hydrolysis treatment. By this hydrolysis, a hydrophilic substituent (alkoxy group) of the silane coupling agent-based compound is hydrolyzed, and a protective layer having a siloxane bond on the particle surface is formed by a dehydration / condensation reaction. Here, it is not necessary that all of the hydrophilic substituents of the silane coupling agent-based compound absorbed by the photocurable resin layer are hydrolyzed to form a siloxane bond, and only a part thereof is hydrolyzed to form a siloxane bond. May be formed.

Although ammonia and amines can be used for the hydrolytic condensation, an aqueous ammonia solution is particularly preferred. The addition amount of the aqueous ammonia also varies when the ammonia concentration is different.
0% by weight, preferably in the range of 1 to 2000% by weight. By performing the above treatment, a network derived from a siloxane bond is formed on the particle surface, and it is possible to effectively suppress elution of elution components such as a crosslinking agent and a photopolymerization initiator into the liquid crystal.

The hydrolysis, dehydration / condensation reaction is usually performed at 0 to 70 ° C., preferably 5 to 60 ° C., particularly preferably 1 to 60 ° C.
The reaction is carried out in the range of 0 to 40 ° C, and the reaction time is usually 0.1 to
0 hours, preferably in the range of 1 to 30 hours. After completion of the reaction, the particles are collected according to a conventional method, sufficiently washed with water, and then dried by a freeze-drying method or the like to obtain the coated particles of the present invention.

In the method of the present invention, a photo-curable resin layer having a uniform thickness can be formed on the surface of the core particles by using an impact or shear force imparting treatment method. Coated particles have very high monodispersity (usually CV
(Value: 5% or less), and there is a bond between the core particles and the photocurable resin layer via a silane coupling agent, so that the photocurable resin layer does not peel off.

The fixed-type in-plane spacer for a liquid crystal display element of the present invention comprises the photocurable resin-coated particles of the present invention obtained as described above, and has a high migration-preventing ability and Since there is no movement at the time of sound wave irradiation, liquid crystal material injection, and extrusion, and the in-plane scattering density does not change, the cell gap can be kept constant. Further, since the monodispersibility of the core particles is maintained, the thickness of the liquid crystal cell can be regulated with extremely high accuracy. The spacer comprising the photocurable resin-coated particles of the present invention is suitable for wet or dry spraying.

Next, the method of the present invention for producing a liquid crystal display element using the spacer comprising the photocurable resin-coated particles of the present invention thus obtained will be described. First, spacers made of the coated particles are uniformly dispersed on a substrate surface having a pixel portion and a black matrix by a wet method or a dry method. Next, only the pixel portion is exposed to active light such as ultraviolet rays from the side where the spacers are scattered through a photomask through a photomask, and exposure is performed, and only the particles on the pixel portion are photo-cured and made infusible. At this time, the actinic ray to be used is not particularly limited as long as it can cure the photocurable resin layer of the spacer, but generally, ultraviolet rays from a mercury lamp or the like is preferably used. The light irradiation temperature may be any temperature at which the resin does not melt.

Next, a heat treatment is performed at a temperature not lower than the temperature at which the photopolymerizable prepolymer in the unexposed particles is eluted from the protective layer having a siloxane bond, usually at a temperature of 60 to 150 ° C. to melt the resin of the particles on the black matrix. To adhere the particles to the substrate. At this time, since the particles on the pixel portion are made infusible, it is difficult to adhere to the substrate. Next, if necessary, the entire surface is irradiated with an actinic ray so that the particles on the black matrix are photocured and firmly fixed to the substrate.

Finally, by removing only the photo-cured particles on the pixel portion, a substrate having the spacer fixed to only the black matrix portion can be obtained. The method of removing the photo-cured particles on the pixel portion is not particularly limited, and includes, for example, a method of sucking with a vacuum cleaner, a method of blowing off a gas, and a method of washing with a solvent. A method and a method of blowing gas are preferred.

The above substrates include glass substrates, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polysulfone, polycarbonate, polyetherimide, polyarylate, and the like.
A polymer film such as an acrylic resin can be used. When using a polymer film, for the purpose of improving solvent resistance and gas barrier properties, if desired,
The surface may be subjected to a coating treatment or a lamination treatment.

In such a method of the present invention, the curing wavelength can be arbitrarily selected by exposing from the side where the spacer is scattered, and the uniformity of the photocuring within the pixel is maintained. Further, since the particles on the black matrix are hardened after being melted, they have a high adhesive force and do not substantially move into the pixel when producing or using the liquid crystal display device. Further, since the particles on the pixel portion are light-cured under the protective layer having a siloxane bond, the adhesion to the substrate is extremely low and can be easily removed. Using a substrate having a spacer only in the black matrix portion obtained in this way, a liquid crystal display element is manufactured according to a conventional method.

The liquid crystal display device obtained by such a method has no light leakage from the inside of the pixel and has a high contrast. The present invention also provides a liquid crystal display device obtained by the above method.

[0067]

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

Production Example 1 Production of Epoxy Acrylate "Epicoat 1004A" manufactured by Yuka Shell Epoxy Co., Ltd. was placed in a 100 ml eggplant type flask equipped with a cooling tube.
After charging 23.13 g of F ", 0.005 g of hydroquinone, 0.012 g of lithium chloride and 8.72 g of acrylic acid, the system was heated in an oil bath at 140 ° C for 5 hours while replacing the system with nitrogen. The obtained mixture is purified water 100
The mixture was poured into 0 ml and stirred overnight. After the precipitated solid was settled, the supernatant was discarded and excess acrylic acid was removed. Next, the operation of adding the same amount of water, stirring for 5 hours, sedimentation and decantation was repeated 5 times. Finally, the powder was separated by filtration and vacuum dried.

The obtained prepolymer has a softening point of 60 ° C.
In the infrared absorption spectrum, absorption due to a strong ester bond was observed at 1,724 cm ⁻¹ and the fluorescence X
The total content of alkali metal, alkaline earth metal, and halogen was 120 ppm by weight as measured by X-ray and ICP emission spectrometry, and it was confirmed that the epoxy acrylate was high-purity.

Example 1 (1) Photocurable Resin Coated Particle Production Step A: Surface Treatment of Core Particles with Silane Coupling Agent
A silica fine particle having a monodisperse particle size distribution (average particle size: 6.43 μm, CV value: 0.9) was placed in a flask having a physical volume of 2 liters.
%, Individual particles are substantially true spheres) (100 g), 630 g of 2-propanol was added thereto, and the silica particles were uniformly dispersed by ultrasonic vibration. After adding 630 g of methanol to the dispersion and stirring at 40 ° C. for 15 minutes,
250 g of 25 wt% ammonia water was added and stirred at the same temperature for 15 minutes. A mixed solution of 43.0 g of γ-methacryloxypropyltrimethoxysilane and 5.6 g of tetraethoxysilane was added dropwise to the obtained solution over 10 minutes.
After completion of the dropwise addition, the temperature was raised to 60 ° C., and the mixture was stirred at the same temperature for 10 hours. After completion of the stirring, the reaction solution was allowed to stand still to settle the silica particles, and the supernatant was removed by decantation. Methanol was added to the residual silica particles, and the mixture was stirred and allowed to stand. The silica particles were allowed to settle, and the supernatant liquid was removed by decantation, whereby unreacted silane coupling agent was removed. Finally, after removing methanol, the obtained surface-treated silica particles were dried in an oven at 150 ° C. for 1 hour.

The average particle size of the obtained surface-treated silica fine particles was 6.45 μm, the CV value was 0.9%, and each particle was substantially a true sphere. A γ-methacryloxypropyl group was introduced on the surface of the silica particles, indicating water repellency. Further, in the infrared absorption spectrum, absorption of a vinyl group and an ester group was observed.

Step B: Photopolymerizable prepolymer and photopolymerizable
After the deposition process acetone 150ml the core particle surface of the initiator was dissolved high purity epoxy acrylate 1.97g obtained in Production Example 1, surface-treated silica fine particles 90g of this was obtained in the above step A
And dispersed uniformly by ultrasonic waves. As a curing agent (photopolymerization initiator), "Kayacure DET" manufactured by Nippon Kayaku
After adding 0.099 g of "X-S" and 0.099 g of "Kayacure EPA" manufactured by Nippon Kayaku Co., as a curing accelerator, 600 ml of water was added all at once to the uniform dispersion, and epoxy acrylate was added to the surface of the silica fine particles. And a photocurable resin composed of a photopolymerization initiator and a curing accelerator. Next, acetone was distilled off under reduced pressure, and freeze-drying treatment was performed to obtain silica particles having the photocurable resin adhered to the surface thereof.

Step C: Impact force or shear force imparting treatment (C
Ionization method) The particles obtained in the above step B were subjected to a rotation speed of 1 using a hybridizer [NHS-O type, manufactured by Nara Machinery Co., Ltd.].
By treating at 5,000 rpm for 10 minutes, a uniform photocurable resin layer comprising a photopolymerizable prepolymer and a photopolymerization initiator was formed on the silica surface, to obtain 70 g of the target coated particles.
As a result of measuring the particle size of the coated particles from a scanning electron microscope (SEM) photograph, the average particle size was 6.51 μm (C
(V value: 1.0%), no coalescence between the particles was observed, and the monodispersibility of the core particles was maintained.

Step D: Siloxane bond forming treatment 0.5% by weight of an aqueous solution of polyvinylpyrrolidone (“K-90” manufactured by Wako Pure Chemical Industries, Ltd.) was added to 300 ml of the above step C.
Was added and dispersed uniformly. Separately, a 200% aqueous solution of 0.5% by weight polyvinylpyrrolidone (“K-90” manufactured by Wako Pure Chemical Industries, Ltd.)
A solution was prepared by uniformly dissolving 3.0 g of a silane coupling agent, methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.),
It was added to the dispersion of the coated particles while stirring.

Next, 0.2 ml of 1N ammonia water was added to the stirred solution, and the mixture was stirred at room temperature for 2 hours to allow the hydrolysis condensate of the silane coupling agent to be absorbed in the resin layer. Thereafter, 2.0 milliliters of 25% by weight aqueous ammonia was added to promote the condensation of the silane coupling agent on the surface to form a siloxane bond. After stirring for an additional 2 hours, the mixture was allowed to stand, the particles were allowed to settle, and the supernatant was removed by decantation. 500 milliliters of water was added thereto, and the steps of stirring, standing, and decanting were repeated five times, followed by freeze-drying to obtain 50 g of the target photocurable resin-coated particles. The average particle size of the coated particles was 6.52 μm as a result of measuring the particle size from a SEM photograph.
(CV value: 1.1%), no coalescence between the particles was observed, and the monodispersibility of the core particles was maintained.

(2) Preparation of Liquid Crystal Display Element The photocurable resin-coated particles obtained in the above (1) were evenly sprayed on a liquid crystal display element substrate having a color filter and a black matrix by a wet sprayer. Then
Using a high-pressure mercury lamp exposure apparatus (output: 1 kW), only the pixel portion (color filter portion) was exposed through the mask from the side where the coated particles were scattered. Next, after heat-treating the substrate to 100 ° C., the entire surface was exposed by the above exposure apparatus without using a mask.

Next, a high-pressure nitrogen gas was blown from the nozzle onto the substrate to blow off only the particles in the pixel portion. The ratio of the number of particles remaining on the pixel portion to the number of particles remaining on the black matrix was determined by an optical microscope.
00. When this substrate was bonded to another substrate to produce a liquid crystal display device, a high-contrast liquid crystal display device with no light leakage from within the pixel was obtained.

Example 2 (1) Production of Photocurable Resin-Coated Particles 10 g of the particles obtained in Step C of Example 1 was added to 0.5% by weight of polyvinylpyrrolidone (“K-9” manufactured by Wako Pure Chemical Industries, Ltd.).
0 ") was added to 70 ml of the aqueous solution and uniformly dispersed. Separately, a solution was prepared by uniformly dissolving 0.4 g of vinyltrimethoxysilane and 0.2 g of dimethyldimethoxysilane in 30 ml of a 0.5% by weight aqueous solution of polyvinylpyrrolidone (“K-90” manufactured by Wako Pure Chemical Industries). The dispersion of the coated particles was added with stirring.

Next, 0.04 ml of 1N aqueous ammonia was added to the stirred solution, and the mixture was stirred at room temperature for 6 hours to allow the hydrolysis condensate of the silane coupling agent to be absorbed in the resin layer. Thereafter, 0.4 ml of 25% by weight aqueous ammonia was added to promote the condensation of the silane coupling agent on the surface to form siloxane bonds. Further, after stirring for 10 hours, the mixture was allowed to stand, the particles were settled, and the supernatant was removed by decantation. After 100 ml of water was added thereto, and the steps of stirring, standing, and decanting were repeated five times, freeze-drying treatment was performed to obtain target photocurable resin-coated particles. As a result of measuring the particle size of the coated particles from an SEM photograph, the average particle size was 6.53 μm (CV
(A value of 1.2%), no coalescence between the particles was observed, and the monodispersibility of the core particles was maintained.

(2) Production of Liquid Crystal Display Element A liquid crystal display element was produced in the same manner as in Example 1 using the coated particles obtained in the above (1). A liquid crystal display device was obtained.

Comparative Example 1 (1) Production of Photocurable Resin-Coated Particles 50 g of silica fine particles having an average particle diameter of 6.45 μm and a CV value of 0.9% and polymethyl methacrylate powder having an average particle diameter of 0.2 μm (Soken Chemical Co., Ltd.) (MP-1451) (2.0 g) was placed in 500 milliliters of water, uniformly dispersed by ultrasonic waves, and freeze-dried. The obtained dry powder was treated with a hybridizer [NHS-O type, manufactured by Nara Machinery Co., Ltd.] at a rotation speed of 15,000 rpm for 10 minutes, and the surface was uniformly coated with polymethyl methacrylate resin. 50 g of particles (average particle size 6.60 μm) were obtained.

In 1 g of methanol, 0.06 g of “Kayacure DETX-S” manufactured by Nippon Kayaku, 0.06 g of “Kayacure EPA” manufactured by Nippon Kayaku, and 0.3 g of divinylbenzene were added.
A solution in which 6 g is dissolved is added to the polymethyl methacrylate resin-coated particles, and after being uniformly mixed by a mill,
The mixture was left overnight to completely evaporate methanol to obtain photocurable resin-coated particles.

(2) Preparation of Liquid Crystal Display Element The photocurable resin-coated particles obtained in the above (1) were evenly sprayed on a liquid crystal display element substrate having a color filter and a black matrix by a dry sprayer. Then
Exposure was performed by a high-pressure mercury lamp exposure apparatus (output 1 kW) from the back side of the coated particle scattering surface. Then, this substrate was
After the heat treatment at 0 ° C., the entire surface was exposed with the above exposure apparatus without using a mask.

Next, a high-pressure nitrogen gas was blown from the nozzle to the substrate to blow off only the particles in the pixel portion. When the ratio of the number of particles remaining on the pixel portion and the number of particles remaining on the black matrix was determined by an optical microscope, the ratio was 30:
It was 100. When this substrate was bonded to another substrate to produce a liquid crystal display element, light leakage from inside the pixel was confirmed.

[0085]

As described above, the photocurable resin-coated particles of the present invention do not elute the resin component at room temperature, and therefore do not cause coalescence or aggregation between the particles and do not exhibit adhesiveness to the substrate. . When the coated particles are heated to a certain temperature or higher, the resin component is eluted from the protective layer having a siloxane bond. However, the elution does not occur if the active ingredient such as an ultraviolet ray is irradiated in advance and light-cured to make it infusible. . By utilizing such properties, the particles can be fixed only to the black matrix portion of the substrate. Therefore,
The photocurable resin-coated particles of the present invention are useful as fixed-type in-plane spacers for liquid crystal display elements.

According to the method of manufacturing a liquid crystal display element of the present invention using the photocurable resin-coated particles as spacers, the spacers can be effectively fixed only to the black matrix portion of the substrate. Thus, a high-contrast liquid crystal display device without light leakage can be obtained.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Eisuke Tachibana 2-1-1 Yabuta Nishi, Gifu City, Gifu Prefecture Ube Nitto Kasei Co., Ltd. F-term (reference) 2H089 LA03 LA07 MA04X MA05X NA10 NA13 NA17 PA05 PA09 QA14 QA16 4F070 AA32 AA46 AC52 AC92 AE27 DC02 DC04 4J002 BG031 CF00 CP002 DJ006 DJ016 4J038 DL032 FA231 FA251 HA251 KA04 KA15 MA02 PA07 PA17

Claims (9)

[Claims] 1. A siloxane derived from a silane coupling agent having a photocurable resin layer containing a photopolymerizable prepolymer and a photopolymerization initiator on the surface of a core particle composed of spherical particles. Particles provided with a protective layer having a bond, wherein the photopolymerizable prepolymer has an impurity content of 0
Photocurable resin-coated particles characterized by being a high-purity acrylate prepolymer of 200 ppm by weight. 2. The photocurable resin-coated particles according to claim 1, wherein the core particles are silica fine particles or polyorganosilsesquioxane particles. 3. The photocurable resin-coated particles according to claim 1, wherein the core particles have a CV value of 5% or less. 4. The photocurable resin-coated particles according to claim 1, wherein the high-purity acrylate prepolymer is an epoxy acrylate. 5. (Step A) a step of subjecting a core particle composed of spherical particles to a surface treatment with a silane coupling agent having a hydrophobic group to introduce a hydrophobic group to the surface of the core particle; (Step B) step A Dispersing the core particles surface-treated with a high-purity acrylate prepolymer having a photopolymerizable impurity content of 0 to 200 ppm by weight and an organic solvent solution containing a photopolymerization initiator, After performing a treatment for precipitating a photocurable resin containing a photopolymerization initiator on the surface of the core particles, the solvent is removed to obtain a dry powder having the photocurable resin precipitated on the surface of the core particles. And (Step C) a photocurable resin layer containing a photopolymerizable high-purity acrylate prepolymer and a photopolymerization initiator by subjecting the dry powder obtained in step B to an impact force or shear force imparting treatment. On the core particle surface (Step D) a silane coupling agent having a hydrophobic polymerizable group in the photocurable resin of the particles coated with the photocurable resin layer obtained in step C; After absorbing at least one silane coupling agent-based compound selected from oligomers obtained by hydrolyzing and condensing the partial hydrolyzate and the silane coupling agent,
The method for producing photocurable resin-coated particles according to claim 1, wherein a step of adding an ammonia solution to promote the condensation of the silane coupling agent-based compound to form a siloxane bond is sequentially performed. 6. A fixed in-plane spacer for a liquid crystal display device, comprising the photocurable resin-coated particles according to claim 1. Description: 7. A spacer comprising the photocurable resin-coated particles according to any one of claims 1 to 4, which is uniformly dispersed on a substrate surface having a pixel portion and a black matrix, and then only on the pixel portion. Exposure is performed from the side where the spacers are scattered through the photomask, and only the particles on the pixel part are cured by light to make it infusible. Heat treatment at a temperature higher than or equal to the temperature, melting the resin of the particles on the black matrix, bonding the particles to the substrate, and then removing only the photocured particles on the pixel portion. Production method. 8. After heating and melting the resin of the particles on the black matrix and adhering to the substrate, the entire surface is irradiated with light to harden the particles and fix the particles on the substrate. The method for manufacturing a liquid crystal display element according to claim 7, wherein only the photocurable particles are removed. 9. A liquid crystal display device obtained by the method according to claim 7. Description: