JP2000319309A - Polymer fine particle and its production, spacer for liquid crystal display element, electroconductive fine particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain polymer fine particles added with flexibility and good elasticity and useful for spacers for liquid crystal displays and electroconductive fine particles by limiting values of a compressive elasticity modulus, a compressive deformation recovery factor and fracture distortion to specific values. SOLUTION: Polymer fine particles are obtained by limiting a compressive elasticity modulus to 10-250 kgf/mm2 when 10% of the particle diameters are deformed, a compressive deformation recovery factor to >=30% and fracture distortion to >=30%. The aforementioned fine particles are obtained by adding an aqueous emulsion containing >=10 wt.% of a (poly)alkyl glycol group- containing di(meth)acrylate [e.g. polytetramethylene glycol di(meth)acrylate and the like] and an aqueous emulsion of an oil-soluble initiator (e.g. benzoyl peroxide and the like) into water in which polymer seed particles having 1,000-20,000 weight average molecular weight are dispersed, to be absorbed by the polymer seeds and subsequently polymerizing an ethylenic unsaturated monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer fine particle used for a spacer for a liquid crystal display element, a conductive fine particle and the like, and more particularly, to a spacer used for a liquid crystal display element, a conductive adhesive for mounting a micro element, The present invention relates to polymer fine particles used for conductive adhesives, conductive materials in conductive connection structures, and the like.

[0001]

2. Description of the Related Art Conventionally, in a liquid crystal display device, a spacer is arranged to keep a gap between substrates constant. The spacer is made of an inorganic material containing aluminum oxide, silicon dioxide, or the like, or an organic material (synthetic resin material) containing benzoguanamine, a polystyrene-based polymer, or the like. A spacer made of an inorganic material is disclosed in, for example, JP-A-63-73225 and JP-A-1-59974, and a spacer made of an organic material (synthetic resin material) is disclosed in
No. 0-220288 and Japanese Patent Application Laid-Open No. 1-293316.

When a liquid crystal display device is manufactured using the above-mentioned inorganic spacer, the spacer is too hard, so that the alignment control film is damaged when pressed against both substrates. There was a problem that can not be maintained.

[0003] In the field of electronics packaging, in order to connect a pair of fine electrodes, a conductive paste is prepared by mixing metal particles such as gold, silver, and nickel and a binder resin, and this paste is mixed with a pair of fine electrodes. The connection between the fine electrodes is performed by filling between the electrodes. However, it is difficult to uniformly disperse such metal particles in the binder resin because of their non-uniform shape and higher specific gravity than the binder resin.

On the other hand, Japanese Unexamined Patent Publication (Kokai) No. 59-2815 discloses a method in which a metal plating layer is provided on the surface of particles such as glass beads, silica beads, and glass fibers having a relatively uniform particle size to form conductive fine particles. Is disclosed. Here, the conductive fine particles need to have a large contact area with the electrode surface from the viewpoint of providing good conduction between the electrodes. For this reason, the required performance requirements include that the polymer fine particles are flexible and do not break when the particles are deformed, and that the particles can withstand elastic recovery for continuous use.

However, in the conductive fine particles disclosed in the above publication, the particles at the center are too hard to be compressed and deformed. Therefore, it is difficult to connect the electrodes using the conductive fine particles. However, the contact area between the conductive fine particles and the electrode surface did not increase, and it was difficult to reduce the contact resistance. In addition, when the amount of compressive deformation of the conductive fine particles is increased in order to increase the contact area, there is a problem that the connection reliability is reduced because the particles are destroyed when the distortion of the particles increases.

Japanese Unexamined Patent Publications Nos. 62-185749 and 1-2225776 disclose conductive fine particles using polyphenylene sulfide particles or phenol resin particles as base particles. However, conductive fine particles using such synthetic resin particles as base particles have poor deformation recovery after compression deformation. Therefore, when the connection between the electrodes is performed using the conductive fine particles, if a compressive load acting on both electrodes is removed, a slight gap is formed at the interface between the conductive fine particles and the electrode surface, and as a result, However, there is a problem that poor contact is caused.

Further, Japanese Patent Publication No. Hei 5-19241 discloses that
Conductive fine particles in which a soft low-density crosslinked polymer containing styrene as a main component is used as base particles and the surface thereof is coated with a conductive material are disclosed. The conductive fine particles using such soft base particles have a small compression deformation recovery rate of 10% or less after removal by applying a load, and the restoring force decreases with time. When used as a conductive adhesive, there is a problem that the connection resistance increases with the passage of time and the reliability of the conductive adhesive is lacking.

Further, polymer fine particles used for such a spacer for liquid crystal display and conductive fine particles are required to be monodisperse fine particles having a uniform particle size distribution. As a method of obtaining such fine particles, for example, a method of classifying fine particles obtained by suspension polymerization to obtain a uniform particle size distribution has been known for a long time, and many methods are still used today. However, the fine particles obtained by suspension polymerization have a wide particle size distribution, and it is difficult to take out only fine particles of the same size even if classification is performed, and further, classification is performed to obtain fine particles having a uniform particle size distribution. For this purpose, it takes several months, and since only the required particle size is classified and taken, the remaining portion is lost and the efficiency is poor.

[0009]

SUMMARY OF THE INVENTION In order to solve the above problems, the present invention, when used as a spacer for a liquid crystal display device, damages the alignment control film of the liquid crystal display device and modulates the alignment characteristics of the liquid crystal. When used as conductive fine particles without inducing or deteriorating the quality of the displayed image, it has the flexibility not to damage the substrate and its wiring, and has an appropriate compressive deformation property and deformation recovery property. It is an object of the present invention to provide polymer fine particles having good conductivity without breaking even when the particles are largely deformed in order to improve a contact area when the particles are arranged between substrates such as a touch panel.

Further, the present invention provides a spacer for a liquid crystal display element using the above polymer fine particles, and a conductive adhesive for mounting a micro element, an anisotropic conductive adhesive, a conductive adhesive using the above polymer fine particles. An object of the present invention is to provide flexible conductive fine particles having excellent connection resistance and connection reliability used as a conductive material in a connection structure or the like.

[0011]

Means for Solving the Problems The polymer fine particles of the present invention have a compression elastic modulus (1) at a displacement of 10% of the particle diameter.
(0% K value) 10 to 250 kgf / mm ² , polymer fine particles having a compression deformation recovery rate of 30% or more and a breaking strain of 30% or more.

The compression modulus (hereinafter referred to as 10% K value) when 10% of the particle diameter is displaced is 10 kgf / m.
If it is less than m ² , the strength of the polymer fine particles decreases,
If it exceeds 0 kgf / mm ² , the flexibility of the polymer fine particles is reduced, so that it is limited to 10 to 250 kgf / mm ² .

The above 10% K value is determined by using a micro-compression tester (PCT-200 manufactured by Shimadzu Corporation) and measuring the smooth hardness of a diamond cylinder having a diameter of 50 μm with a compression hardness of 0.27 g /
It is a value obtained by measuring the load value, compression displacement, and the like when compressing the fine particles obtained at a maximum test load of 10 g in seconds, and obtaining the following formula.

K = (3 / √2) ・^FS -3 / 2 ・ R- ^{1 / 2} F: Load value at 10% compressive deformation of fine particles (kg) S: Compressive displacement at 10% compressive deformation of fine particles (Mm) R: radius of fine particles (mm)

The above 10% K value universally and quantitatively represents the hardness of the fine particles. By using the 10% K value, the suitable hardness of the polymer fine particles of the present invention can be quantitatively determined. And it can be expressed uniquely.

If the compressive deformation recovery rate is less than 30%, the elasticity of the polymer fine particles is reduced, so that it is limited to 30% or more. The compressive deformation recovery rate is obtained by measuring the relationship between the load value and the compressive displacement when the load is reduced after compressing the fine particles to a reversal load value of 1.0 gf with the tester. The end point at which the load is removed is the origin load value 0.1 gf, and the compression speed 0.0 at the load and unload.
Measured as 29 gf / sec and the displacement (L
1) and the displacement (L
This is a value in which the ratio (L2 / L1) to 2) is expressed in%.

When the breaking strain is less than 30%, the polymer fine particles are broken, so that the breaking strain is limited to 30% or more. The fracture strain is defined as the amount of deformation at the time when the fine particles are broken by performing a test using the above-mentioned micro-compression tester, and is the ratio between the particle diameter (D) and the displacement (L) up to the time of breaking. (L / D) is a value expressed in%.

The material of the polymer fine particles of the present invention is not particularly limited, and examples thereof include urethane resin, unsaturated polyester resin, (meth) acrylate resin, polyethylene,
Polypropylene, polyvinyl chloride, polystyrene, polytetrafluoroethylene, butadiene resin, epoxy resin, phenol resin, melamine resin, polymethylpentene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, polysulfone, polyphenylene oxide, polyacetal, etc. Is mentioned.

Among them, it is preferable to use a (meth) acrylate resin. The crosslinkable monomer used in the (meth) acrylate resin is not particularly limited,
For example, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, dimethylol tricyclodecane diacrylate,
Di (meth) acrylate derivatives such as -hydroxy-1-acryloxy-3-methacryloxypropanedi (meth) acrylate.

It is also preferable to use an alkyl glycol group-containing di (meth) acrylate as the crosslinkable monomer. That is, the alkyl glycol group-containing di (meth) acrylate is not particularly limited. For example, polyethylene glycol di (meth) acrylate such as ethylene glycol di (meth) acrylate; polypropylene glycol di (meth) acrylate such as propylene glycol di (meth) acrylate (Meth) acrylate; polytetramethylene glycol di (meth) acrylate; neopentyl glycol di (meth) acrylate; 1,3-butylene glycol di (meth) acrylate; 2,2-bis [4- (methacryloxyethoxy) phenyl] 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propanedi (meth) acrylate such as propanedi (meth) acrylate; 2,2-hydrogenated bis [4- (acryloxypolyethoxy) phenyl] propanedi (meth) acrylate ) Acrylate, 2, 2-bis [4- (acryloxyethoxy poly propoxy) phenyl] propanedioic (meth) acrylate.

The above alkyl glycol group-containing di (meth)
The amount of the acrylate is preferably from 5 to 100% by weight, more preferably from 40 to 100% by weight of the crosslinking monomer used.
100% by weight. If the amount is less than 5% by weight, the flexibility of the polymer fine particles may decrease.

The monomer used in combination with the crosslinkable monomer is not particularly restricted but includes, for example, polymerizable unsaturated monomers copolymerizable with the crosslinkable monomer. Specific examples thereof include styrene derivatives such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, and chloromethylstyrene; vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; and styrene derivatives such as acrylonitrile. Saturated nitriles; conjugated dienes such as butadiene and isoprene; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate; (Meth) acrylate derivatives such as ethylene glycol (meth) acrylate, trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, and cyclohexyl (meth) acrylate; trimethylolpropane tri (meth) acrylate, tetra Methylolmethane tri (meth) acrylate, tetramethylolpropanetetra (meth) acrylate, diallyl phthalate and its isomers; triallyl isocyanurate and its derivatives; pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol hexa (meth) acrylate, and the like.

Particle size (diameter) of the polymer fine particles of the present invention
When the particle size is less than 0.1 μm, the polymer particles tend to agglomerate, and the use of polymer particles exceeding 5000 μm is rarely used. Therefore, the particle size is preferably from 0.1 to 5000 μm, more preferably from 1 to 100 μm.

If the Cv value of the particle diameter (diameter) exceeds 25%, the connection reliability of the obtained conductive fine particles may decrease, and therefore, the Cv value is preferably 25% or less. In addition, the said Cv value means the value calculated | required by the following formula. Cv value (%) = (standard deviation of particle diameter / average particle diameter) × 1
00

The method for producing the polymer fine particles used in the present invention is not particularly limited, and for example, a suspension polymerization method, a seed polymerization method and the like are preferably used. Among them, a seed polymerization method that does not require a step of uniformizing the particle size distribution by classification is preferable because of high productivity. For details of the seed polymerization method,
For example, it is described in Japanese Patent Publication No. 1-39455.

Specific examples of the seed polymerization method include:
For example, an aqueous emulsion of an ethylenically unsaturated monomer containing 10% by weight or more of polytetramethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, or the like in water in which polymer seed particles are dispersed; A method of adding an aqueous emulsion of an oil-soluble initiator, absorbing the ethylenically unsaturated monomer and the oil-soluble initiator into the polymer seed particles, and then polymerizing the ethylenically unsaturated monomer.

The weight average molecular weight of the polymer seed particles is preferably from 1,000 to 20,000, and the amount of the ethylenically unsaturated monomer is 1 to 1 part by weight of the polymer seed particles.
It is preferable to absorb 0 to 500 parts by weight.

The radical polymerization initiator used in the production of the polymer fine particles is not particularly limited, and for example, organic peroxides, azo compounds and the like are preferably used. Examples of the organic peroxide include benzoyl peroxide and its derivatives, lauroyl peroxide, acetyl peroxide, dicumyl peroxide, di-t-butyl peroxide, t-butyl peroxide, and t-butyl peroxyviva. Rate, t-butyl peroxybenzoate, t-butyl peroxy octoate, t-butyl peroxy acetate, t-butyl peroxyisobutyrate, t-butyl-2-ethylhexanoate and the like.

Examples of the azo compound include azo compounds such as azobisisobutyronitrile, azobiscyclohexacarbonitrile, and azobis (2,4-dimethylvaleronitrile).

The amount of the radical polymerization initiator is usually 0.1 to 15 parts by weight per 100 parts by weight of the polymerizable monomer.
Parts by weight are preferred.

In the polymerization of the polymer fine particles, a surfactant, a dispersion stabilizer and the like can be used, if necessary. As the surfactant, for example, anionic,
A surfactant such as a cationic or nonionic surfactant is used.

As the dispersion stabilizer, a polymer which is soluble in a medium is usually used. Examples of the dispersion stabilizer include polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, ethylcellulose, polyacrylic acid, polyacrylamide, polyethylene oxide, starch, carboxymethylcellulose, and the like. Examples include water-soluble polymers such as hydroxyethyl cellulose and polysodium methacrylate, barium sulfate, calcium sulfate, aluminum sulfate, calcium carbonate, calcium phosphate, talc, clay, diatomaceous earth, and metal oxide powder.

The amount of the dispersion stabilizer is preferably 0.01 to 20 parts by weight based on 100 parts by weight of the polymerizable monomer. These may be used alone or in combination of two or more.

The spacer for a liquid crystal display element of the present invention uses the above polymer fine particles as they are, or covers the surface of the polymer fine particles with an organic substance, binds an organic substance or the like to the surface, It is obtained by reforming or the like.

The conductive fine particles of the present invention are obtained by using the above-mentioned polymer fine particles as base particles and coating the surface with a conductive material to form a conductive layer. The metal used for the conductive layer is not particularly limited. For example, nickel, gold, silver, copper, cobalt, tin, indium, ITO,
And alloys containing these as main components.

The method for forming the metal layer on the surface of the base particles is not particularly limited, and examples thereof include a method by electroless plating, a method of coating a paste obtained by mixing metal fine powder alone or with a binder, and a method of vacuum coating. Evaporation,
Examples include physical vapor deposition methods such as ion plating and ion sputtering.

The electroless plating method includes, for example, a gold displacement plating method. The working steps of the gold displacement plating method are divided into an etching step, an activation step, a chemical nickel plating step, and a gold displacement plating step. The etching step is a step of forming irregularities for adhering the catalyst to the surface of the base particles, as an etchant, for example, aqueous caustic soda, concentrated hydrochloric acid,
Examples include concentrated sulfuric acid and chromic anhydride.

The activation step is a step for forming a catalyst layer on the surface of the etched fine particles and activating the catalyst layer. That is, the catalyst layer containing Pd ²⁺ and Sn ²⁺ on the surface of the fine particles is treated with concentrated sulfuric acid or concentrated hydrochloric acid to metallize Pd ²⁺ , and the metalized palladium is a palladium activator such as a concentrated solution of sodium hydroxide. Is activated and sensitized. The activation of the catalyst layer promotes the deposition of metallic nickel in a chemical nickel plating step described below.

The chemical nickel plating step is a step of further forming a metal nickel layer on the surface of the base particles on which the catalyst layer has been formed. For example, nickel chloride is reduced with sodium hypophosphite, and nickel is reduced. Precipitates on the surface of the substrate particles.

The gold displacement plating step is a step of placing the fine particles coated with nickel in a potassium gold cyanide solution, eluting nickel while increasing the temperature, and depositing gold on the surface of the base particles.

The thickness of the conductive layer in the conductive fine particles of the present invention is preferably 0.02 to 5 μm. The thickness of the conductive layer is 0.
If it is less than 02 μm, it is difficult to obtain desired conductivity,
When the thickness exceeds 5 μm, the flexibility of the conductive fine particles is not effectively exerted when both the electrodes are pressurized with the conductive fine particles sandwiched between a pair of electrodes, and the conductive fine particles easily aggregate.

[0042]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 (Synthesis of seed particles) 1.2 parts by weight of polyvinylpyrrolidone (weight average molecular weight (Mw) 30,000), aerosol OT
While stirring 0.57 parts by weight (manufactured by Wako Pure Chemical Industries, Ltd.) and 1.43 parts by weight of azobismethylvaleronitrile in 74 parts by weight of methanol and 10 parts by weight of water, styrene 18 was stirred under a nitrogen stream. After adding 0.1 parts by weight and 1.9 parts by weight of α-methylstyrene, the mixture was heated to 60 ° C. and polymerized for 24 hours to obtain seed particles. The obtained seed particles had a weight average molecular weight (Mw) of 15000 and an average particle size of 2.
It was 0 μm.

(Synthesis of Polymer Fine Particles) Seed Particle 5
After adding 200 parts by weight of ion-exchanged water and 0.13 parts by weight of sodium lauryl sulfate to the parts by weight and dispersing them uniformly, polytetramethylene glycol diacrylate (PTMG)
A) 80 parts by weight, 20 parts by weight of isoamyl acrylate and 3 parts by weight of benzoyl peroxide were mixed, dispersed by a homogenizer, and finely dispersed and emulsified to 0.2 μm. The obtained emulsion is added to the dispersion of the seed particles, and 25 ° C., 100 rpm
The mixture was stirred at a rotation speed of m for 12 hours to be absorbed by the seed particles. After 100 parts by weight of a 3% by weight aqueous solution of polyvinyl alcohol was added to this dispersion, the dispersion was heated at 80 ° C. under a nitrogen stream at 12 ° C.
Polymerization was carried out for hours. The dispersion was removed from the resulting dispersion by centrifugation, and the dispersant was completely washed with hot water and acetone, and then dried to obtain polymer fine particles.

(Production of Conductive Fine Particles) The conductive fine particles having a nickel-gold plated layer formed thereon by etching the surface of the obtained polymer fine particles with sodium hydroxide, performing electroless nickel plating, and then performing a gold substitution reaction. I got

(Evaluation of Polymer Fine Particles and Conductive Fine Particles)
The 10% K value and the compression deformation recovery rate of the obtained polymer fine particles were measured. Further, the obtained conductive fine particles were put into a ball mill, and the peeling state of the metal layer after crushing for 6 hours was observed by a scanning electron microscope (SEM). Table 1 shows the obtained results.

Example 2 Polytetramethylene glycol diacrylate (PTMGA) 50 was used instead of 80 parts by weight of polytetramethylene glycol diacrylate (PTMGA) and 20 parts by weight of isoamyl acrylate in the synthesis of polymer fine particles.
Polymer fine particles and conductive fine particles were obtained in the same manner as in Example 1, except that 50 parts by weight of isooctyl acrylate and 50 parts by weight of isooctyl acrylate were used. The obtained polymer fine particles and conductive fine particles were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 3 Instead of 80 parts by weight of polytetramethylene glycol diacrylate (PTMGA) and 20 parts by weight of isoamyl acrylate in the synthesis of polymer fine particles, 60 parts by weight of NK ester APG700 (manufactured by Shin-Nakamura Chemical Co.) and pentaerythritol Except that 40 parts by weight of triacrylate was used, polymer fine particles and conductive fine particles were obtained in the same manner as in Example 1, and the obtained polymer fine particles and conductive fine particles were evaluated in the same manner as in Example 1, and the results were obtained. Are shown in Table 1.

Example 4 Instead of 80 parts by weight of polytetramethylene glycol diacrylate (PTMGA) and 20 parts by weight of isoamyl acrylate in the synthesis of polymer fine particles, 80 parts by weight of NK ester APG700 (manufactured by Shin-Nakamura Chemical Co.) and trimethylol Except for using 20 parts by weight of propane triacrylate, polymer fine particles and conductive fine particles were obtained in the same manner as in Example 1, and the obtained polymer fine particles and conductive fine particles were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 5 Instead of 80 parts by weight of polytetramethylene glycol diacrylate (PTMGA) and 20 parts by weight of isoamyl acrylate in the synthesis of polymer fine particles, 100 parts by weight of NK ester APG700 (manufactured by Shin-Nakamura Chemical Co., Ltd.) was used. Except for the above, polymer fine particles and conductive fine particles were obtained in the same manner as in Example 1, and the obtained polymer fine particles and conductive fine particles were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 6 In the synthesis of polymer fine particles, 100 parts by weight of NK ester APG400 (manufactured by Shin-Nakamura Chemical Co.) was used instead of 80 parts by weight of polytetramethylene glycol diacrylate (PTMGA) and 20 parts by weight of isoamyl acrylate. Except for the above, polymer fine particles and conductive fine particles were obtained in the same manner as in Example 1, and the obtained polymer fine particles and conductive fine particles were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 7 In a separable flask, 1.3 parts by weight of benzoyl oxide as a polymerization initiator were uniformly mixed with 15 parts by weight of polytetramethylene glycol diacrylate and 5 parts by weight of isooctyl acrylate. After adding 20 parts by weight of a 3% aqueous solution (manufactured by Kuraray Co., Ltd.) and 0.5 part by weight of sodium dodecyl sulfate and stirring well, 140 parts by weight of ion-exchanged water was added. The solution was reacted at 80 ° C. for 15 hours under a nitrogen stream while stirring. The obtained fine particles were washed with hot water and acetone, and then classified to obtain polymer fine particles having an average particle size of 5 μm. Conductive fine particles were prepared using the obtained polymer fine particles, and the polymer fine particles and the conductive fine particles were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 8 Instead of 15 parts by weight of polytetramethylene glycol diacrylate and 5 parts by weight of isooctyl acrylate,
Polymer fine particles having an average particle size of 5 μm were obtained in the same manner as in Example 7, except that 18 parts by weight of NK ester APG400 and 2 parts by weight of isoamyl acrylate were used. Conductive fine particles were prepared using the obtained polymer fine particles, and the polymer fine particles and the conductive fine particles were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 9 Instead of 15 parts by weight of polytetramethylene glycol diacrylate and 5 parts by weight of isooctyl acrylate,
Polymer fine particles having an average particle size of 5 μm were obtained in the same manner as in Example 7, except that 20 parts by weight of NK ester APG700 was used. Conductive fine particles were prepared using the obtained polymer fine particles, and the polymer fine particles and the conductive fine particles were prepared in Example 1.
The evaluation was performed in the same manner as described above, and the results are shown in Table 1.

Comparative Example 1 The procedure of Example 1 was repeated, except that 100 parts by weight of divinylbenzene was used in place of 80 parts by weight of polytetramethylene glycol diacrylate (PTMGA) and 20 parts by weight of isoamyl acrylate in the synthesis of polymer fine particles. Thus, polymer fine particles and conductive fine particles were obtained, and the obtained polymer fine particles and conductive fine particles were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 2 Same as Example 1 except that 100 parts by weight of isooctyl acrylate was used instead of 80 parts by weight of polytetramethylene glycol diacrylate (PTMGA) and 20 parts by weight of isoamyl acrylate in the synthesis of polymer fine particles. To obtain polymer fine particles, but could not be evaluated because they were dissolved in acetone at the washing stage.

Comparative Example 3 In the synthesis of polymer fine particles, instead of 80 parts by weight of polytetramethylene glycol diacrylate (PTMGA) and 20 parts by weight of isoamyl acrylate, 80 parts by weight of divinylbenzene and 20 parts by weight of trimethylolpropane triacrylate were used. Polymer fine particles and conductive fine particles were obtained in the same manner as in Example 1 except for the difference, and the obtained polymer fine particles and conductive fine particles were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 4 Except that 100 parts by weight of 1,9-nonanediol diacrylate was used in place of 80 parts by weight of polytetramethylene glycol diacrylate (PTMGA) and 20 parts by weight of isoamyl acrylate in the synthesis of polymer fine particles. Polymer fine particles were obtained in the same manner as in Example 1, but many small particles adhered to the surface. Conductive fine particles were prepared using the obtained polymer fine particles, and the obtained polymer fine particles and conductive fine particles were evaluated in the same manner as in Example 1,
The results are shown in Table 1.

Comparative Example 5 In place of 80 parts by weight of polytetramethylene glycol diacrylate (PTMGA) and 20 parts by weight of isoamyl acrylate in the synthesis of polymer fine particles, 100 parts by weight of light acrylate 14EG-A (manufactured by Kyoeisha Chemical Co., Ltd.) was used. Polymer particles were obtained in the same manner as in Example 1, except that the monomer used was water-soluble, and could not be emulsified.

Comparative Example 6 Instead of 15 parts by weight of polytetramethylene glycol diacrylate and 5 parts by weight of isooctyl acrylate,
Except for using 20 parts by weight of divinylbenzene, polymer fine particles and conductive fine particles were obtained in the same manner as in Example 7, and the obtained polymer fine particles and conductive fine particles were evaluated in the same manner as in Example 1. Are shown in Table 1.

Comparative Example 7 Instead of 15 parts by weight of polytetramethylene glycol diacrylate and 5 parts by weight of isooctyl acrylate,
Except that 20 parts by weight of 1,9-nonanediol diacrylate was used, polymer fine particles and conductive fine particles were obtained in the same manner as in Example 7, and the obtained polymer fine particles and conductive fine particles were obtained in the same manner as in Example 1. Table 1 shows the results.
It was shown to.

[0062]

[Table 1]

[0063]

The polymer fine particles of the present invention have a particle diameter of 1%.
Compressive modulus at 0% displacement (10% K value) 10
Since it is 250 kgf / mm ² , the compressive deformation recovery rate is 30% or more, and the breaking strain is 30% or more, when used as a spacer for a liquid crystal display element, the alignment control film of the liquid crystal display element is damaged and the alignment characteristics of the liquid crystal are deteriorated. When used as conductive fine particles without inducing modulation or deteriorating the quality of the displayed image, it has the flexibility not to damage the substrate and its wiring, and has an appropriate compressive deformability and deformation recovery. Has the nature
When placed between substrates such as a touch panel, the particles do not break even when the particles are greatly deformed to improve the contact area, and have excellent connection resistance and connection reliability.

The polymer fine particles of the present invention are given flexibility by containing a soft (poly) alkyl glycol group having a main chain in the polymer fine particles. When adjusted in such a manner, good elasticity is imparted, so that it is suitably used as a spacer for liquid crystal display, conductive fine particles, or the like.

The present invention also includes a spacer for a liquid crystal display element and conductive fine particles using the above polymer fine particles. Further, the spacer for a liquid crystal display element is suitably used for a liquid crystal display element, and the conductive fine particles are preferably used for a conductive adhesive for mounting a micro element, an anisotropic conductive adhesive, and a conductive material in a conductive connection structure.

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Claims (6)

[Claims] The present invention is characterized in that the compression elastic modulus (10% K value) when 10% of the particle diameter is displaced is 10 to 250 kgf / mm ² , the compression deformation recovery rate is 30% or more, and the breaking strain is 30% or more. Polymer particles. 2. Polymer fine particles containing a di (meth) acrylate having a (poly) alkyl glycol group. 3. The polymer fine particles according to claim 1, wherein the average particle diameter is 0.1 to 5000 μm and the Cv value is 25% or less. 4. Polytetramethylene glycol di (meth) acrylate or polypropylene glycol di (meth) acrylate is dispersed in water in which polymer seed particles are dispersed.
An aqueous emulsion composed of an ethylenically unsaturated monomer containing 0% by weight or more and an aqueous emulsion of an oil-soluble initiator were added, and the ethylenically unsaturated monomer and the oil-soluble initiator were absorbed by the polymer seed particles. Thereafter, a method for producing polymer fine particles by polymerizing an ethylenically unsaturated monomer, wherein the weight average molecular weight of the polymer seed particles is 1,000 to 2
4. The polymer fine particles according to claim 1, wherein the polymer fine particles have a molecular weight of 0.000 and absorb 10 to 500 parts by weight of the ethylenically unsaturated monomer per 1 part by weight of the polymer seed particles. Manufacturing method. 5. A spacer for a liquid crystal display device, wherein the polymer fine particles according to claim 1 are used. 6. A conductive fine particle comprising the polymer fine particle according to claim 1 and a conductive layer formed on the surface thereof.