TWI838336B - Resin particles, connecting material and connecting structure - Google Patents

Abstract

The present invention provides a resin particle that can effectively relieve internal stress and effectively suppress the generation of rebound. The resin particle of the present invention is that the total number of the T unit and the Q unit is 4% or less out of the total number of 100% of the M unit represented by the general formula: [(R) ₃ SiO _1/2 ], the D unit represented by the general formula: [(R) ₂ SiO _2/2 ], the T unit represented by the general formula: [(R)SiO _3/2 ] and the Q unit represented by the general formula: [SiO _4/2 ].

Description

Resin particles, connecting material and connecting structure

The present invention relates to a resin particle containing a polysilicone resin, and also to a connecting material and a connecting structure using the resin particle.

The miniaturization, lightness, and thinness of electrical and electronic components are progressing rapidly. Along with this, the dimensional stability, warpage reduction, and crack prevention of printed wiring boards or multi-layer boards have become issues. As a method to solve the above issues, there are methods such as relieving internal stress. As a method to relieve internal stress, for example, a method of adding stress relieving materials such as polysilicone particles to the resin composition has been proposed.

As an example of the polysilicone particles, the following patent document 1 discloses spherical polysilicone elastomer particles. The main component of the spherical polysilicone elastomer particles is polysilicone elastomer. The average particle size of the spherical polysilicone elastomer particles is 0.1 to 500 μm. The spherical polysilicone elastomer particles do not substantially contain metal elements derived from the hardening catalyst.

In addition, the following patent document 2 discloses polysilicone particles having 100 parts by mass of polysilicone elastic body spherical particles and 0.5 to 25 parts by mass of polyorganosilsesquioxane covering the surface thereof. The volume average particle size of the polysilicone elastic body spherical particles is 0.1 to 100 μm. The polyorganosilsesquioxane is in granular form. The size of the polyorganosilsesquioxane is less than 60 nm.

Furthermore, the following patent document 3 discloses sponge-like polysiloxane particles obtained by copolymerizing a silane compound having three functional groups represented by formula (1) and a silane compound having two functional groups represented by formula (2). The sponge-like polysiloxane particles are formed by clustering spherical polysiloxane particles having an average primary particle size of 0.1 to 50 μm. The average particle size of the sponge-like polysiloxane particles is 1 to 100 μm. The sponge-like polysiloxane particles are capable of re-discharging more than 70% of the temporarily absorbed oil. [Prior art document] [Patent document]

[Patent Document 1] Japanese Patent Publication No. 2006-104456 [Patent Document 2] Japanese Patent Publication No. 2013-40241 [Patent Document 3] Japanese Patent Publication No. 2015-140356

[The problem the invention is trying to solve]

When forming a connection portion that electrically connects electrodes or a bonding layer that connects two connection target components, the connection portion or bonding layer may be heated to harden an adhesive such as a resin. If the connection portion or bonding layer is heated, internal stress may be generated due to the hardening and shrinkage of the adhesive such as the resin. The generated internal stress becomes a factor of cracking in the connection portion or bonding layer, so it is necessary to relieve the internal stress. As described in Patent Documents 1 to 3, it is difficult for the previous polysilicone particles to fully relieve the internal stress generated in the connection portion or bonding layer.

Furthermore, when using the conventional polysilicone particles described in Patent Documents 1 to 3 as spacers, the compressed polysilicone particles try to restore their original shape, which may cause a phenomenon called rebound. If the polysilicone particles mixed in the bonding layer as spacers rebound, peeling may occur at the interface between the bonding layer and the substrate after a long period of time.

The object of the present invention is to provide a resin particle that can effectively relieve internal stress and effectively suppress the generation of rebound. In addition, the object of the present invention is to provide a connection material and a connection structure using the above resin particles. [Technical means to solve the problem]

According to a broader aspect of the present invention, a resin particle is provided, wherein the _{total number of the T units and the Q units is 4% or less out of the total number of 100% of the M units represented by the general formula: [(R) 3 SiO 1/2} ], the D units represented by the general formula: [(R) 2 SiO _2/2 ], the T units represented by the general formula: [(R)SiO _{3/2 ] and the Q units represented by the general formula: [SiO 4/2} ].

In a specific embodiment of the resin particles of the present invention, the compression recovery rate at a compression deformation of 40% is less than 10%.

In a specific embodiment of the resin particles of the present invention, the 10% K value is less than 500 N/mm ² .

In a specific embodiment of the resin particles of the present invention, the particle size is greater than or equal to 0.5 μm and less than or equal to 500 μm.

In a specific aspect of the resin particles of the present invention, the resin particles are particles containing polysilicone resin.

In a specific aspect of the resin particles of the present invention, the resin particles are used as spacers.

According to a broader aspect of the present invention, a connecting material is provided, which includes the above-mentioned resin particles and an adhesive or particles containing metal atoms.

In a specific aspect of the connecting material of the present invention, the connecting material includes an adhesive.

In a specific aspect of the connection material of the present invention, the connection material contains particles containing metal atoms.

In a specific aspect of the connection material of the present invention, the thermal decomposition temperature of the resin particles is higher than the melting point of the particles containing metal atoms.

In a specific aspect of the connection material of the present invention, the connection material is used to form a connection portion connecting two connection target members, and the connection material is used to form the connection portion by a sintered body of the particles containing metal atoms.

According to a broad aspect of the present invention, a connection structure is provided, which includes: a first connection target member, a second connection target member, and a connection portion connecting the first connection target member and the second connection target member, and the material of the connection portion includes the resin particles. [Effects of the Invention]

The resin particles of the present invention are such that the total number of the T unit and the Q unit is 4% or less out of the total number of 100 _% of the M unit represented by the general formula: [(R) ₃ SiO _1/2 ], the D unit represented by the general formula: [(R) ₂ SiO _2/2 ], the T unit represented by the general formula: [(R)SiO _3/2 ], and the Q unit represented by the general formula: [SiO 4/2 ]. The resin particles of the present invention have the above-mentioned structure, so they can effectively alleviate the internal stress and effectively suppress the occurrence of rebound.

Hereinafter, the present invention will be described in detail.

(Resin particles) The resin particles of the present invention are such that the total number of the T unit and _the Q unit is 4 _% or less out of the total number of 100% of the M unit represented by the general formula: [(R) ₃ SiO _1/2 ], the D unit represented by the general formula: [(R) 2 SiO _2/2 ], the T unit represented by the general formula: [(R)SiO _3/2 ], and the Q unit represented by the general formula: [SiO 4/2 ]. Furthermore, the M unit, the D unit, the T unit, and the Q unit are well known as represented by the general formula. R in the general formula represents an arbitrary group. As an arbitrary group of R, an O _1/2 group bonded to Si other than the unit of the general formula is excluded.

Since the resin particles of the present invention have the above-mentioned structure, they can effectively alleviate the internal stress and effectively suppress the occurrence of rebound.

The resin particles of the present invention have the above-mentioned structure, so the compression recovery rate is relatively low, and the compressed resin particles are relatively difficult to recover to their original shape, and are not easy to rebound. For example, when the resin particles of the present invention are used as spacers, the spacers can be fully in contact with components for liquid crystal display elements, etc., and the gap can be controlled with higher precision.

When forming a connection portion that electrically connects electrodes, or a bonding layer that connects two connection target components, the connection portion or bonding layer may be heated in order to harden an adhesive such as a resin. If the connection portion or bonding layer is heated, internal stress may be generated due to the hardening and shrinkage of the adhesive such as the resin. The generated internal stress becomes a cause of cracking, etc., so it is better to eliminate the internal stress. As a method of eliminating internal stress, a method of performing heat treatment can be listed. However, if a resin is used for the connection portion or bonding layer, it is difficult to fully eliminate the internal stress even by heat treatment. Since the resin particles of the present invention have the above-mentioned structure, the compression recovery rate is relatively low, and the function of the compressed resin particles to restore the original shape is relatively difficult to play. By using the resin particles of the present invention in the connection part or the bonding layer, even if the internal stress of the connection part or the bonding layer is generated due to heating, the internal stress of the connection part or the bonding layer can be effectively alleviated by the deformation of the resin particles. As a result, the occurrence of cracks in the connection part or the bonding layer can be effectively suppressed.

From the viewpoint of more effectively alleviating the internal stress and more effectively suppressing the occurrence of springback, the resin particles are preferably particles containing a polysiloxane resin. The polysiloxane resin preferably contains a specific organic siloxy unit (silicon bond-containing unit).

The above-mentioned organosiloxy units include monofunctional organosiloxy units called M units, difunctional organosiloxy units called D units, trifunctional organosiloxy units called T units, and tetrafunctional organosiloxy units called Q units. The Q unit is a unit that does not contain an organic group having a carbon atom directly bonded to a silicon atom, but in the present invention, it is regarded as an organosiloxy unit.

In the above-mentioned organosilaneoxy unit, the siloxane bond is a bond between two silicon atoms via one oxygen atom, so the oxygen atom in the siloxane bond is considered to be 1/2 for each silicon atom, and is represented by O _1/2 in the general formula. Specifically, for example, in one D unit, one silicon atom contained in the D unit is bonded to two oxygen atoms, and each oxygen atom is bonded to a silicon atom of another unit. That is, the structure of the D unit is [-O _1/2 -(R) ₂ Si-O _1/2 -], and there are two O _1/2 , so the D unit is represented by the general formula: [(R) ₂ SiO _2/2 ].

The M unit is an organic silaneoxy unit represented by the general formula: [(R) ₃ SiO _1/2 ]. Specifically, the M unit has a structure represented by the following formula (1).

[Chemistry 1]

In the above formula (1), R1, R2 and R3 represent arbitrary groups. R1, R2 and R3 preferably represent alkyl, aryl, allyl, hydrogen atom, or divalent organic group with 1 to 5 carbon atoms. The above organic group may also contain carbon atoms, hydrogen atoms, and oxygen atoms. The above organic group may also be a divalent hydrocarbon group with 1 to 5 carbon atoms. The main chain of the above organic group is preferably a divalent hydrocarbon group. In the above organic group, a carboxyl group or a hydroxyl group may also be bonded to the divalent hydrocarbon group. The structure represented by the above formula (1) may also be bonded to other structures via R1, R2 or R3. The oxygen atom in the above formula (1) may form a siloxane bond with a silicon atom of other structures, and may also form a bond with an atom other than a silicon atom of other structures.

From the viewpoint of more effectively alleviating the internal stress and more effectively suppressing the occurrence of springback, the structure represented by the above formula (1) is preferably bonded to another structure via a divalent hydrocarbon group. From the viewpoint of more effectively alleviating the internal stress and more effectively suppressing the occurrence of springback, the oxygen atom in the above formula (1) preferably forms a siloxane bond with a silicon atom of another structure, and preferably bonds to a divalent hydrocarbon group of another structure.

The D unit is an organic silaneoxy unit represented by the general formula: [(R) ₂ SiO _2/2 ]. Specifically, the D unit has a structure represented by the following formula (2).

[Chemistry 2]

In the above formula (2), R4 and R5 represent arbitrary groups respectively. R4 and R5 are preferably alkyl, aryl, allyl, hydrogen atom, or divalent organic group with 1 to 5 carbon atoms respectively. The above organic group may also contain carbon atoms, hydrogen atoms, and oxygen atoms. The above organic group may also be a divalent hydrocarbon group with 1 to 5 carbon atoms. The main chain of the above organic group is preferably a divalent hydrocarbon group. In the above organic group, a carboxyl group or a hydroxyl group may also be bonded to the divalent hydrocarbon group. The structure represented by the above formula (2) may also be bonded to other structures via R4 or R5. The oxygen atom in the above formula (2) may form a siloxane bond with a silicon atom of other structures, and may also form a bond with an atom other than a silicon atom of other structures.

From the viewpoint of more effectively alleviating the internal stress and more effectively suppressing the occurrence of springback, the structure represented by the above formula (2) is preferably bonded to another structure via a divalent hydrocarbon group. From the viewpoint of more effectively alleviating the internal stress and more effectively suppressing the occurrence of springback, the oxygen atom in the above formula (2) preferably forms a siloxane bond with a silicon atom of another structure, and preferably bonds to a divalent hydrocarbon group of another structure.

The T unit is an organic silaneoxy unit represented by the general formula: [(R)SiO _3/2 ]. Specifically, the T unit has a structure represented by the following formula (3).

[Chemistry 3]

In the above formula (3), R6 represents an arbitrary group. R6 preferably represents an alkyl group, an aryl group, an allyl group, a hydrogen atom, or a divalent organic group having 1 to 5 carbon atoms. The above organic group may also contain carbon atoms, hydrogen atoms, and oxygen atoms. The above organic group may also be a divalent hydrocarbon group having 1 to 5 carbon atoms. The main chain of the above organic group is preferably a divalent hydrocarbon group. In the above organic group, a carboxyl group or a hydroxyl group may also be bonded to the divalent hydrocarbon group. The structure represented by the above formula (3) may also be bonded to other structures via R6. The oxygen atom in the above formula (3) may form a siloxane bond with a silicon atom of other structures, and may also form a bond with an atom other than a silicon atom of other structures.

From the viewpoint of more effectively alleviating the internal stress and more effectively suppressing the occurrence of springback, the structure represented by the above formula (3) is preferably bonded to another structure via a divalent hydrocarbon group. From the viewpoint of more effectively alleviating the internal stress and more effectively suppressing the occurrence of springback, the oxygen atom in the above formula (3) preferably forms a siloxane bond with a silicon atom of another structure, and preferably bonds to a divalent hydrocarbon group of another structure.

The Q unit is an organic siloxy unit (siloxy unit) represented by the general formula: [SiO _4/2 ]. Specifically, the Q unit has a structure represented by the following formula (4).

[Chemistry 4]

The oxygen atom in the above formula (4) may form a siloxane bond with a silicon atom in another structure, or may form a bond with an atom other than a silicon atom in another structure. From the viewpoint of more effectively alleviating the internal stress and more effectively suppressing the occurrence of springback, the oxygen atom in the above formula (4) preferably forms a siloxane bond with a silicon atom in another structure, and preferably forms a bond with a divalent alkyl group in another structure.

In the resin particles of the present invention, out of the total number of M units represented by the general formula: [(R) ₃ SiO _1/2 ], D units represented by the general formula: [(R) ₂ SiO _2/2 ], T units represented by the general formula: [(R)SiO _3/2 ] and Q units represented by the general formula: [SiO _4/2 ] (100%), the total number of the T units and the Q units (TnQn) is 4% or less.

From the viewpoint of further effectively alleviating the internal stress and further effectively suppressing the occurrence of springback, the above-mentioned TnQn is preferably 3% or less, and more preferably 2% or less, out of the total number 100% of the above-mentioned M unit, the above-mentioned D unit, the above-mentioned T unit, and the above-mentioned Q unit. The lower limit of the above-mentioned TnQn is not particularly limited. The above-mentioned TnQn may be 0% (the number is 0) or may exceed 0%.

The above TnQn can be calculated by performing ²⁹ Si-solid NMR (nuclear magnetic resonance) analysis on the resin particles. Specifically, it can be calculated in the following manner.

Calculation method of TnQn: Using fully dried resin particles, the integral value of the signal quantity of each unit above can be obtained by ²⁹ Si-solid NMR measurement (DD (Dipolar decoupling, high power proton decoupling)/MAS (Magic Angle Spinning) method) under the following measurement conditions. TnQn can be calculated based on the integral value of the signal quantity of each unit above.

²⁹ Si-solid NMR measurement (DD/MAS method) measurement conditions: Equipment: "JNM-ECX400" manufactured by Jeol Resonance Co., Ltd. Observation nucleus: ²⁹ Si Probe: 8 mm probe for solid NMR MAS speed: 7 kHz Measurement method: Single pulse (DD/MAS) Pulse width: 3.45 μs ( ²⁹ Si/90 degrees) Delay time: 315 seconds Acquisition time: 21 milliseconds Scanning times: 500 times

In general, the chemical shift of ²⁹ Si-solid NMR derived from the above-mentioned units is as follows. The chemical shift of ²⁹ Si-solid NMR derived from the above-mentioned units can be appropriately determined by taking into account any group bonded to the Si group.

M unit: 5 ppm to 15 ppm D unit: -30 ppm to -5 ppm T unit: -75 ppm to -50 ppm Q unit: -120 ppm to -100 ppm

From the viewpoint of more effectively alleviating the internal stress and more effectively suppressing the occurrence of springback, the compression recovery rate of the resin particles when they are compressed and deformed by 40% is preferably 10% or less, more preferably 9% or less, and preferably 0.1% or more, more preferably 1% or more.

The compression recovery rate of the above resin particles when they are compressed and deformed by 40% can be measured in the following manner.

Spread resin particles on the test stand. For each of the dispersed resin particles, use a micro compression tester to apply a load (reverse load value) to the smooth indentation end face of a cylinder (diameter 100 μm, made of diamond) in the center direction of the resin particle at 25°C until the resin particle is compressively deformed by 40%. Thereafter, unload the load until the load value at the origin (0.40 mN) is reached. The load-compression displacement during this period is measured, and the compression recovery rate at 40% compression deformation at 25°C can be calculated according to the following formula. In addition, the load speed is set to 0.33 mN/sec. As the micro compression tester, for example, "Micro Compression Tester MCT-W200" manufactured by Shimadzu Corporation, "Fischerscope H-100" manufactured by Fischer Corporation, etc. can be used.

Compression recovery rate (%) = [L2/L1] × 100 L1: Compression displacement from the load value at the origin when the load is applied to the reversal load value L2: Unloading displacement from the reversal load value when the load is released to the load value at the origin

The 10%K value of the resin particles is preferably 5 N/mm ² or more, more preferably 10 N/mm ² or more, and preferably 500 N/mm ² or less, more preferably 200 N/mm ² or less, further preferably 150 N/mm ² or less, and particularly preferably 100 N/mm ² or less. If the 10%K value of the resin particles is above the lower limit and below the upper limit, the internal stress can be further effectively relieved, and the occurrence of rebound can be further effectively suppressed.

The 10% K value of the above resin particles can be measured in the following manner.

Using a micro compression tester, compress one resin particle at 25°C, at a compression rate of 0.3 mN/sec, and a maximum test load of 20 mN on the smooth compression head end of a cylinder (diameter 100 μm, made of diamond). Measure the load value (N) and compression displacement (mm) at this time. The 10% K value at 25°C can be calculated based on the obtained measured values and the following formula. As the above-mentioned micro compression tester, for example, the "Micro Compression Tester MCT-W200" manufactured by Shimadzu Corporation, the "Fischerscope H-100" manufactured by Fischer, etc. can be used. The 10% K value of the resin particles is preferably calculated by arithmetically averaging the 10% K values of 50 randomly selected resin particles.

10%K value (N/ ^mm2 ) = (3/2 ^1/2 )・F・S- ^3/2・R ^-1/2 F: Load value when the resin particle is compressed and deformed by 10% (N) S: Compression displacement when the resin particle is compressed and deformed by 10% (mm) R: Radius of the resin particle (mm)

The K value generally and quantitatively indicates the hardness of the resin particles. By using the K value, the hardness of the resin particles can be quantitatively and uniquely indicated.

The particle size of the resin particles can be appropriately set depending on the purpose. The particle size of the resin particles is preferably 0.5 μm or more, more preferably 1 μm or more, and preferably 500 μm or less, more preferably 450 μm or less, further preferably 100 μm or less, further preferably 50 μm or less, and particularly preferably 20 μm or less. If the particle size of the resin particles is above the lower limit and below the upper limit, the internal stress can be further effectively relieved, and the occurrence of rebound can be further effectively suppressed. If the particle size of the resin particles is 0.5 μm or more and 20 μm or less, the resin particles can be preferably used as stress relievers. If the particle size of the resin particles is greater than or equal to 1 μm and less than or equal to 100 μm, the resin particles can be preferably used as a gap control material.

The particle size of the resin particles described above refers to the diameter when the resin particles are truly spherical, and refers to the maximum diameter when the resin particles are not truly spherical.

The particle size of the resin particles is preferably an average particle size, and more preferably a number average particle size. The particle size of the resin particles is obtained using a particle size distribution measuring device or the like. For example, a particle size distribution measuring device that applies principles such as laser scattered light, resistance value change, and image analysis after shooting can be used. Specifically, as a method for measuring the particle size of the resin particles, for example, there can be listed: using a particle size distribution measuring device ("Multisizer 4" manufactured by Beckman Coulter), the particle size of approximately 100,000 resin particles is measured and the average value is calculated. The particle size of the resin particles is preferably obtained by observing any 50 resin particles using an electron microscope or an optical microscope and calculating the average value.

From the viewpoint of further effectively relieving internal stress, the coefficient of variation (CV value) of the particle size of the resin particles is preferably 10% or less, more preferably 7% or less, and further preferably 5% or less. If the coefficient of variation (CV value) of the particle size of the resin particles is below the upper limit, the resin particles can be suitably used as a stress relieving material or a gap controlling material.

The above-mentioned coefficient of variation (CV value) can be measured in the following manner.

CV value (%) = (ρ/Dn) × 100 ρ: Standard deviation of the particle size of the resin particles Dn: Average value of the particle size of the resin particles

The shape of the resin particles is not particularly limited. The resin particles may be spherical or may be other than spherical, such as flat.

The use of the above-mentioned resin particles is not particularly limited. The above-mentioned resin particles can be preferably used for various purposes. The above-mentioned resin particles are preferably used as spacers. As the use method of the above-mentioned spacers, there can be listed: spacers for liquid crystal display elements, spacers for gap control, and spacers for stress relief, etc. The above-mentioned spacers for gap control can be used for gap control of laminated chips to ensure the height and flatness of the bracket, and gap control of optical parts to ensure the smoothness of the glass surface and the thickness of the adhesive layer. The above-mentioned spacers for stress relief can be used for stress relief of sensor chips, etc., and stress relief of the connection part connecting two connection object components. The above-mentioned spacers for stress relief can be used as connection materials for power devices, adhesives for sensors, etc. The above-mentioned spacer is preferably a connection material for power devices, and is preferably an adhesive for sensors.

The resin particles are preferably used as spacers for liquid crystal display elements, and are preferably used as peripheral sealants for liquid crystal display elements. In the peripheral sealants for liquid crystal display elements, the resin particles are preferably used as spacers. Since the resin particles have good compression deformation properties, when the resin particles are used as spacers and arranged between substrates, the spacers are efficiently arranged between the substrates. Furthermore, the resin particles can suppress damage to components for liquid crystal display elements, and thus the liquid crystal display element using the liquid crystal display element spacers is less likely to have display defects.

Furthermore, the resin particles can also be suitably used as inorganic fillers, additives for toner, shock absorbers or vibration absorbers. For example, the resin particles can be used as substitutes for rubber or springs.

(Other details of resin particles) From the viewpoint of more effectively alleviating internal stress and more effectively suppressing the occurrence of springback, the resin particles are preferably particles containing polysilicone resin.

The material of the polysilicone resin is preferably a silane compound having a free radical polymerizable group and a silane compound having a hydrophobic group with a carbon number of 5 or more, and preferably a silane compound having a free radical polymerizable group and a hydrophobic group with a carbon number of 5 or more, and preferably a silane compound having a free radical polymerizable group at both ends. When these materials are reacted, siloxane bonds are formed. In the obtained polysilicone resin, free radical polymerizable groups and hydrophobic groups with a carbon number of 5 or more generally remain. By using such a material, particles containing the polysilicone resin having a particle size of 1 μm or more and 200 μm or less can be easily obtained, and the chemical resistance of the particles containing the polysilicone resin can be improved, and the moisture permeability can be reduced.

The silane compound having a free radical polymerizable group is preferably one in which the free radical polymerizable group is directly bonded to the silicon atom. The silane compound having a free radical polymerizable group may be used alone or in combination of two or more.

The silane compound having a free radical polymerizable group is preferably an alkoxysilane compound. Examples of the silane compound having a free radical polymerizable group include vinyltrimethoxysilane, vinyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, divinylmethoxyvinylsilane, divinylethoxyvinylsilane, divinyldimethoxysilane, divinyldiethoxysilane, and 1,3-divinyltetramethyldisiloxane.

The silane compound having a hydrophobic group with a carbon number of 5 or more is preferably a compound having a hydrophobic group with a carbon number of 5 or more directly bonded to a silicon atom. The silane compound having a hydrophobic group with a carbon number of 5 or more may be used alone or in combination of two or more.

The silane compound having a hydrophobic group with a carbon number of 5 or more is preferably an alkoxysilane compound. Examples of the silane compound having a hydrophobic group with a carbon number of 5 or more include phenyltrimethoxysilane, dimethoxymethylphenylsilane, diethoxymethylphenylsilane, dimethylmethoxyphenylsilane, dimethylethoxyphenylsilane, hexaphenyldisiloxane, 1,3,3,5-tetramethyl-1,1,5,5-tetraphenyltrisiloxane, 1,1,3,5,5-pentaphenyl-1,3,5-trimethyltrisiloxane, hexaphenylcyclotrisiloxane, phenyltris(trimethylsiloxy)silane, and octaphenylcyclotetrasiloxane.

The silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms is preferably a free radical polymerizable group directly bonded to a silicon atom, and preferably a hydrophobic group having 5 or more carbon atoms is directly bonded to a silicon atom. The silane compound having a radical polymerizable group and a hydrophobic group having 5 or more carbon atoms may be used alone or in combination of two or more.

Examples of the silane compound having a free radical polymerizable group and a hydrophobic group having 5 or more carbon atoms include phenylvinyldimethoxysilane, phenylvinyldiethoxysilane, phenylmethylvinylmethoxysilane, phenylmethylvinylethoxysilane, diphenylvinylmethoxysilane, diphenylvinylethoxysilane, phenyldivinylmethoxysilane, phenyldivinylethoxysilane, and 1,1,3,3-tetraphenyl-1,3-divinyldisiloxane.

In order to obtain the above-mentioned particles containing polysilicone resin, it is preferred that the above-mentioned silane compound having a free radical polymerizable group and the above-mentioned silane compound having a hydrophobic group having 5 or more carbon atoms are used in the following weight ratio. The above-mentioned silane compound having a free radical polymerizable group and the above-mentioned silane compound having a hydrophobic group having 5 or more carbon atoms are preferably used in a weight ratio of 1:1 to 1:20, and more preferably 1:5 to 1:15.

In the whole silane compound used to obtain the above-mentioned particles containing polysiloxane resin, the ratio of the number of free radical polymerizable groups to the number of hydrophobic groups with a carbon number of 5 or more is preferably 1:0.5 to 1:20, more preferably 1:1 to 1:15.

The particles containing the polysiloxane resin preferably have a dimethylsiloxane skeleton with two methyl groups bonded to one silicon atom, and the material of the polysiloxane resin preferably includes a silane compound with two methyl groups bonded to one silicon atom. In this case, the internal stress can be further effectively alleviated, and the occurrence of rebound can be further effectively suppressed.

From the viewpoint of further effectively relieving the internal stress and further effectively suppressing the occurrence of the rebound, the above-mentioned particles containing polysilicone resin are preferably formed by reacting the above-mentioned silane compound with a free radical polymerization initiator to form a siloxane bond. Generally speaking, when the above-mentioned particles containing polysilicone resin are synthesized by condensation using an acid or alkaline catalyst, it is difficult to obtain particles containing polysilicone resin having a particle size of 10 μm or more and 500 μm or less, and it is particularly difficult to obtain particles containing polysilicone resin having a particle size of 100 μm or less. In view of this, by using a free radical polymerization initiator and the silane compound of the above composition, particles containing polysilicone resin having a particle size of 1 μm or more and 500 μm or less can be obtained, particles containing polysilicone resin having a particle size of 10 μm or more can be obtained, and particles containing polysilicone resin having a particle size of 100 μm or less can be obtained.

In order to obtain the above-mentioned particles containing polysilicone resin, it is also possible not to use silane compounds having hydrogen atoms bonded to silicon atoms. In this case, instead of using a metal catalyst, a free radical polymerization initiator can be used to polymerize the silane compound. As a result, the above-mentioned particles containing polysilicone resin can be free of metal catalysts, and the content of metal catalysts in the above-mentioned particles containing polysilicone resin can be reduced, which can further effectively alleviate internal stress and further effectively suppress the occurrence of rebound.

From the viewpoint of reducing moisture permeability, the resin particles are preferably resin particles containing silicone resin and a resin different from silicone resin, and the outer surface of the silicone resin is covered with a resin different from the silicone resin. From the viewpoint of reducing moisture permeability, the particles containing silicone resin are preferably particles containing silicone resin and a resin different from silicone resin, and the outer surface of the silicone resin is covered with a resin different from the silicone resin.

When the resin particles include silicone resin and a resin different from silicone resin, the entire outer surface of the silicone resin may be covered with the resin different from silicone resin, and there may be a portion not covered with the resin different from silicone resin.

Examples of the resin different from the silicone resin include resins having a vinyl group (vinyl resin), etc. The resin different from the silicone resin may be used alone or in combination of two or more.

From the viewpoint of further reducing moisture permeability, the resin different from the silicone resin is preferably a resin having a vinyl group, more preferably divinylbenzene or styrene.

As a specific method for producing the above-mentioned particles containing polysilicone resin, there can be listed: a method of producing particles containing polysilicone resin by polymerizing a silane compound by suspension polymerization, dispersion polymerization, mini-emulsion polymerization, or emulsion polymerization. It is also possible to produce particles containing polysilicone resin by polymerizing a silane compound to obtain an oligomer, and then polymerizing the silane compound as a polymer (oligomer, etc.) by suspension polymerization, dispersion polymerization, mini-emulsion polymerization, or emulsion polymerization. For example, a silane compound having a vinyl group can be polymerized to obtain a silane compound having a vinyl group bonded to a silicon atom at the end. A silane compound having a phenyl group can be polymerized to obtain a silane compound having a phenyl group bonded to a silicon atom as a side chain as a polymer (oligomer, etc.). A silane compound having a vinyl group and a silane compound having a phenyl group can be polymerized to obtain a silane compound having a vinyl group bonded to a silicon atom at the terminal and a phenyl group bonded to a silicon atom as a side chain as a polymer (oligomer, etc.).

In order to obtain resin particles whose outer surfaces of the polysilicone resin are covered with a resin different from the polysilicone resin, the polysilicone resin and the resin different from the polysilicone resin may be polymerized after the polysilicone resin is prepared.

(Connecting material) The connecting material is used to form a connecting portion connecting two connecting target components. The connecting material comprises the resin particles, and an adhesive or particles containing metal atoms. The connecting material is preferably used to form the connecting portion by a sintered body of particles containing metal atoms. The adhesive does not contain the resin particles of the present invention. The particles containing metal atoms do not contain the resin particles of the present invention.

The thermal decomposition temperature of the resin particles is preferably higher than the melting point of the particles containing metal atoms. The thermal decomposition temperature of the resin particles is preferably higher than the melting point of the particles containing metal atoms by 10°C or more, more preferably higher than 30°C or more, and most preferably higher than 50°C or more.

As the above-mentioned particles containing metal atoms, there can be listed: metal particles and metal compound particles, etc. The above-mentioned metal compound particles contain metal atoms and atoms other than the metal atoms. As specific examples of the above-mentioned metal compound particles, there can be listed: metal oxide particles, metal carbonate particles, metal carboxylate particles and metal complex particles, etc. The above-mentioned metal compound particles are preferably metal oxide particles. For example, the above-mentioned metal oxide particles are sintered after becoming metal particles by heating during connection in the presence of a reducing agent. The above-mentioned metal oxide particles are precursors of metal particles. As the above-mentioned metal carboxylate particles, there can be listed metal acetate particles, etc.

Examples of the metal constituting the metal particles and the metal oxide particles include silver, copper, and gold. The metal constituting the metal particles and the metal oxide particles is preferably silver or copper, and more preferably silver. Therefore, the metal particles are preferably silver particles or copper particles, and more preferably silver particles. The metal oxide particles are preferably silver oxide particles or copper oxide particles, and more preferably silver oxide particles. When silver particles and silver oxide particles are used, slag can be reduced after connection, and the volume reduction rate can be made very small. Examples of the silver oxide in the silver oxide particles include Ag ₂ O and AgO.

The particles containing metal atoms are preferably sintered by heating at a temperature lower than 400° C. The temperature at which the particles containing metal atoms are sintered (sintering temperature) is more preferably 350° C. or lower, and more preferably 300° C. or higher. If the temperature at which the particles containing metal atoms are sintered is higher than the lower limit or lower than the upper limit, sintering can be performed efficiently, thereby reducing the energy required for sintering and reducing the environmental load.

When the metal atom-containing particles are metal oxide particles, it is preferred to use a reducing agent. Examples of the reducing agent include alcohol compounds (compounds having an alcoholic hydroxyl group), carboxylic acid compounds (compounds having a carboxyl group), and amine compounds (compounds having an amino group). The reducing agent may be used alone or in combination of two or more.

As the above-mentioned alcohol compound, alkanols and the like can be listed. As specific examples of the above-mentioned alcohol compound, for example, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol and eicosanol can be listed. In addition, as the above-mentioned alcohol compound, it is not limited to a primary alcohol type compound, and a secondary alcohol type compound, a tertiary alcohol type compound, an alkanediol and an alcohol compound having a ring structure can also be used. Furthermore, as the above-mentioned alcohol compound, a compound having multiple alcohol groups such as ethylene glycol and triethylene glycol can also be used. In addition, as the above-mentioned alcohol compound, compounds such as citric acid, ascorbic acid and glucose can also be used.

As the carboxylic acid compound, alkyl carboxylic acids can be listed. As specific examples of the carboxylic acid compound, butyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid and eicosanoic acid can be listed. In addition, the carboxylic acid compound is not limited to a primary carboxylic acid type compound, and a secondary carboxylic acid type compound, a tertiary carboxylic acid type compound, a dicarboxylic acid and a carboxyl compound having a ring structure can also be used.

As the above-mentioned amine compound, alkylamines and the like can be listed. As specific examples of the above-mentioned amine compound, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine and eicosylamine and the like can be listed. In addition, the above-mentioned amine compound can also have a branched structure. As the amine compound having a branched structure, 2-ethylhexylamine and 1,5-dimethylhexylamine and the like can be listed. The above-mentioned amine compound is not limited to a primary amine compound, and a secondary amine compound, a tertiary amine compound and an amine compound having a ring structure can also be used.

The reducing agent may be an organic substance having an aldehyde group, an ester group, a sulfonyl group or a ketone group, or may be an organic substance such as a carboxylic acid metal salt. The carboxylic acid metal salt may be used as a precursor of metal particles, and on the other hand, since it contains an organic substance, it may also be used as a reducing agent for metal oxide particles.

The content of the reducing agent is preferably 1 part by weight or more, more preferably 10 parts by weight or more, and preferably 1000 parts by weight or less, more preferably 500 parts by weight or less, and further preferably 100 parts by weight or less, relative to 100 parts by weight of the metal oxide particles. If the content of the reducing agent is above the lower limit, the particles containing metal atoms can be sintered more densely. As a result, the heat dissipation and heat resistance of the connection formed by the sintered body of the particles containing metal atoms are also improved.

If a reducing agent having a melting point lower than the sintering temperature (joining temperature) of the above-mentioned metal atom-containing particles is used, agglomeration occurs during joining and pores tend to be generated at the joint. By using a carboxylic acid metal salt, the carboxylic acid metal salt will not melt due to heating during joining, so the generation of pores can be suppressed. Furthermore, in addition to the carboxylic acid metal salt, a metal compound containing an organic substance can also be used as a reducing agent.

From the viewpoint of further effectively improving the connection strength, the above-mentioned connecting material preferably includes an adhesive. The above-mentioned adhesive is not particularly limited. As the above-mentioned adhesive, a well-known insulating resin can be used. The above-mentioned adhesive preferably includes a thermoplastic component (thermoplastic compound) or a curable component, and more preferably includes a curable component. As the above-mentioned curable component, there can be listed: a photocurable component and a thermocurable component. The above-mentioned photocurable component preferably includes a photocurable compound and a photopolymerization initiator. The above-mentioned thermocurable component preferably includes a thermocurable compound and a thermocuring agent. As the above-mentioned adhesive, for example, there can be listed: vinyl resins, thermoplastic resins, curable resins, thermoplastic block copolymers and elastomers. The above-mentioned adhesives may be used alone or in combination of two or more.

Examples of the above-mentioned ethylene resin include vinyl acetate resin, acrylic resin, and styrene resin. Examples of the above-mentioned thermoplastic resin include polyolefin resin, ethylene-vinyl acetate copolymer, and polyamide resin. Examples of the above-mentioned curable resin include epoxy resin, polyurethane resin, polyimide resin, and unsaturated polyester resin. Furthermore, the above-mentioned curable resin may be a room temperature curing resin, a heat curing resin, a light curing resin, or a moisture curing resin. The above-mentioned curable resin may also be used in combination with a curing agent. Examples of the thermoplastic block copolymer include styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, hydrogenated styrene-butadiene-styrene block copolymer, and hydrogenated styrene-isoprene-styrene block copolymer. Examples of the elastomer include styrene-butadiene copolymer rubber and acrylonitrile-styrene block copolymer rubber.

Furthermore, the binder may be a solvent. Examples of the solvent include water and organic solvents. From the perspective of further improving the removability of the solvent, the solvent is preferably an organic solvent. Examples of the organic solvent include alcohol compounds such as ethanol; ketone compounds such as acetone, methyl ethyl ketone, and cyclohexanone; aromatic hydrocarbon compounds such as toluene, xylene, and tetramethylbenzene; glycol ether compounds such as solvent, methyl solvent, butyl solvent, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, and tripropylene glycol monomethyl ether; ester compounds such as ethyl acetate, butyl acetate, butyl lactate, acetic acid solvent, butyl acetic acid solvent, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbon compounds such as octane and decane; and petroleum-based solvents such as petroleum ether and naphtha.

From the perspective of more effectively improving the connection strength, the above-mentioned connection material preferably includes epoxy resin.

In order to effectively exert the effect of the resin particles of the present invention, when the connecting material includes the metal atom-containing particles, the content of the metal atom-containing particles in the connecting material is preferably greater than the content of the resin particles, more preferably greater than 10 wt %, and further preferably greater than 20 wt %.

In 100 wt % of the connecting material, the content of the resin particles is preferably 0.1 wt % or more, more preferably 1 wt % or more, and preferably 50 wt % or less, more preferably 30 wt % or less. If the content of the resin particles is above the lower limit and below the upper limit, the internal stress in the connecting portion can be further effectively alleviated.

When the connection material includes the metal atom-containing particles, the content of the metal atom-containing particles is preferably 0.3% by weight or more, more preferably 3% by weight or more, and preferably 50% by weight or less, more preferably 40% by weight or less in 100% by weight of the connection material. If the content of the metal atom-containing particles is above the lower limit and below the upper limit, the connection resistance is further reduced.

When the connecting material includes an adhesive, the content of the adhesive is preferably 5 volume % or more, more preferably 10 volume % or more, and preferably 40 volume % or less, more preferably 20 volume % or less in 100 volume % of the connecting material. If the content of the adhesive is above the lower limit and below the upper limit, the connection strength can be further effectively improved.

(Connected Structure) By connecting components to be connected using the above-mentioned connecting material containing resin particles and adhesive or particles containing metal atoms, a connected structure can be obtained.

The connection structure comprises: a first connection target member, a second connection target member, and a connection portion connecting the first connection target member and the second connection target member. The material of the connection portion includes the resin particles. The material of the connection portion is preferably the connection material. The connection portion is preferably a connection structure formed by the connection material.

FIG. 1 is a cross-sectional view showing an example of a connected structure using the resin particles of the present invention.

The connection structure 51 shown in FIG. 1 includes a first connection target member 52 , a second connection target member 53 , and a connection portion 54 that connects the first connection target member 52 and the second connection target member 53 .

The connecting portion 54 includes the above-mentioned resin particles 1. The resin particles 1 are not in contact with both the first and second connecting target members 52 and 53. The resin particles 1 are used as spacers for stress relief. In FIG. 1 , the resin particles 1 are shown in a schematic diagram for the convenience of illustration.

The connecting portion 54 includes a gap control particle 61 and a metal connecting portion 62. In the connecting portion 54, one gap control particle 61 is in contact with both the first and second connecting target components 52 and 53. The gap control particle 61 may be a conductive particle or a non-conductive particle. The metal connecting portion 62 is a sintered body of particles containing metal atoms. The metal connecting portion 62 is formed by sintering particles containing metal atoms. The metal connecting portion 62 is formed by melting particles containing metal atoms and then solidifying them. The metal connecting portion 62 is a molten solidified body of particles containing metal atoms.

The first connection target member may also have a first electrode on its surface. The second connection target member may also have a second electrode on its surface. Preferably, the first electrode and the second electrode are electrically connected via the connection portion.

The manufacturing method of the above-mentioned connection structure is not particularly limited. As an example of the manufacturing method of the connection structure, there can be cited a method of arranging the above-mentioned connection material between the first connection target component and the second connection target component, obtaining a laminate, and then heating and pressurizing the laminate. The pressure of the above-mentioned pressurization is about 9.8×10 ⁴ to 4.9×10 ⁶ Pa. The temperature of the above-mentioned heating is about 120 to 220°C. The pressure of the above-mentioned pressurization for connecting the electrodes of the flexible printed circuit board, the electrodes arranged on the resin film, and the electrodes of the touch panel is about 9.8×10 ⁴ to 1.0×10 ⁶ Pa.

Specifically, the above-mentioned connection target components include: electronic components such as semiconductor chips, capacitors and diodes, and electronic components such as printed circuit boards, flexible printed circuit boards, glass epoxy substrates and glass substrates. The above-mentioned connection target components are preferably electronic components. At least one of the above-mentioned first connection target component and the above-mentioned second connection target component is preferably a semiconductor wafer or a semiconductor chip. The above-mentioned connection structure is preferably a semiconductor device.

The above-mentioned connection material can also be suitably used in touch panels. Therefore, the above-mentioned connection target component is also preferably a flexible substrate, or a connection target component with electrodes arranged on the surface of a resin film. The above-mentioned connection target component is preferably a flexible substrate, and is preferably a connection target component with electrodes arranged on the surface of a resin film. When the above-mentioned flexible substrate is a flexible printed substrate, etc., the flexible substrate generally has electrodes on the surface.

The electrode disposed on the above-mentioned connecting object component may be a gold electrode, a nickel electrode, a tin electrode, an aluminum electrode, a copper electrode, a silver electrode, a molybdenum electrode, a tungsten electrode, or other metal electrodes. When the above-mentioned connecting object component is a flexible substrate, the above-mentioned electrode is preferably a gold electrode, a nickel electrode, a tin electrode, or a copper electrode. When the above-mentioned connecting object component is a glass substrate, the above-mentioned electrode is preferably an aluminum electrode, a copper electrode, a molybdenum electrode, or a tungsten electrode. Furthermore, when the electrode is an aluminum electrode, it may be an electrode formed of aluminum alone or an electrode formed by stacking an aluminum layer on the surface of a metal oxide layer. Examples of the material of the metal oxide layer include indium oxide doped with a trivalent metal element and zinc oxide doped with a trivalent metal element. Examples of the trivalent metal element include Sn, Al, and Ga.

Furthermore, the resin particles can be suitably used as a spacer for a liquid crystal display element. The first connection target component can also be a first liquid crystal display element component. The second connection target component can also be a second liquid crystal display element component. The connecting portion can also be a sealing portion that seals the outer periphery of the first liquid crystal display element component and the second liquid crystal display element component when the first liquid crystal display element component and the second liquid crystal display element component are facing each other.

The resin particles can also be used as a sealant for a liquid crystal display element. The liquid crystal display element comprises: a first liquid crystal display element component, a second liquid crystal display element component, a sealing portion, and a liquid crystal. The sealing portion seals the outer periphery of the first liquid crystal display element component and the second liquid crystal display element component in a state where the first liquid crystal display element component and the second liquid crystal display element component are opposite to each other. The liquid crystal is arranged between the first liquid crystal display element component and the second liquid crystal display element component on the inner side of the sealing portion. In the liquid crystal display element, the sealing portion is formed by applying a liquid crystal dropping method and thermally curing the sealant for the liquid crystal dropping method.

FIG. 2 is a cross-sectional view showing an example of a liquid crystal display element using the resin particles of the present invention as spacers for a liquid crystal display element.

The liquid crystal display element 81 shown in FIG. 2 has a pair of transparent glass substrates 82. The transparent glass substrates 82 have insulating films (not shown) on the opposite surfaces. As the material of the insulating film, _SiO2 and the like can be listed. A transparent electrode 83 is formed on the insulating film in the transparent glass substrate 82. As the material of the transparent electrode 83, ITO and the like can be listed. The transparent electrode 83 can be formed by patterning by photolithography, for example. An alignment film 84 is formed on the transparent electrode 83 on the surface of the transparent glass substrate 82. As the material of the alignment film 84, polyimide and the like can be listed.

Liquid crystal 85 is sealed between a pair of transparent glass substrates 82. A plurality of resin particles 1 are arranged between a pair of transparent glass substrates 82. Resin particles 1 are used as spacers for liquid crystal display elements. The spacing between a pair of transparent glass substrates 82 is limited by a plurality of resin particles 1. A sealant 86 is arranged between the edge portions of a pair of transparent glass substrates 82. The sealant 86 prevents liquid crystal 85 from flowing to the outside. The sealant 86 contains resin particles 1A that are different from the resin particles 1 only in particle size. In FIG. 2 , for the convenience of illustration, the resin particles 1 and 1A are shown in outline.

The arrangement density of the liquid crystal display element spacers per 1 mm ² in the liquid crystal display element is preferably 10 or more/mm ² , and preferably 1000 or less/mm ^2. If the arrangement density is 10 or more/mm ² , the cell gap becomes more uniform. If the arrangement density is 1000 or less/mm ² , the contrast of the liquid crystal display element becomes better.

The present invention is specifically described below with reference to the following embodiments and comparative examples. The present invention is not limited to the following embodiments.

(Example 1) (1) Preparation of resin particles A (polysilicone particles A) A solution A was prepared by dissolving 0.5 parts by weight of tert-butyl peroxy-2-ethylhexanoate (polymerization initiator, "PERBUTYL O" manufactured by NOF Corporation) in 30 parts by weight of polysilicone oil with acrylic acid at both ends ("X-22-2445" manufactured by Shin-Etsu Chemical Co., Ltd.). A solution B was prepared by mixing 0.8 parts by weight of a 40% by weight aqueous solution of triethanolamine lauryl sulfate salt (emulsifier) and 80 parts by weight of a 5% by weight aqueous solution of polyvinyl alcohol (polymerization degree: about 2000, saponification degree: 86.5 to 89 mol %, "Gohsenol GH-20" manufactured by Nippon Synthetic Chemical Co., Ltd.) in 150 parts by weight of ion-exchanged water. After adding the above-mentioned solution A to a separable flask placed in a hot bath, the above-mentioned aqueous solution B is added. Thereafter, emulsification is performed by using a Shirasu Porous Glass (SPG) membrane (average pore diameter of about 5 μm). Thereafter, the temperature is raised to 85°C and polymerization is performed for 9 hours. After all the particles after polymerization are washed with water by centrifugal separation, a classification operation is performed, and then freeze-dried to obtain resin particles A (polysilicone particles A).

(2) Preparation of connecting material 40 parts by weight of silver particles (average particle size 15 nm), 1 part by weight of divinylbenzene resin particles (average particle size 30 μm, CV value 5%), 10 parts by weight of the above-mentioned resin particles A, and 40 parts by weight of toluene as a solvent were mixed to prepare a connecting material.

(3) Fabrication of connection structure A power semiconductor element is prepared as the first connection target component. An aluminum nitride substrate is prepared as the second connection target component.

The above-mentioned connection material is applied to the second connection target member in a manner of about 30 μm in thickness to form a connection material layer. Thereafter, the above-mentioned first connection target member is laminated on the connection material layer to obtain a laminate. The obtained laminate is heated at 300° C. for 10 minutes to sinter the silver particles contained in the connection material layer to produce a connection structure.

(4) Preparation of liquid crystal display elements Preparation of sealant for liquid crystal dropping method: Prepare the following materials. Resin particles A (polysilicone particles A) 30 parts by weight Bisphenol A epoxy methacrylate (thermosetting compound, "KRM7985" manufactured by Daicel-Allnex) 50 parts by weight Caprolactone-modified bisphenol A epoxy acrylate (thermosetting compound, "EBECRYL3708" manufactured by Daicel-Allnex) 20 parts by weight Partially acrylic-modified bisphenol E epoxy resin (thermosetting compound, "KRM8276" manufactured by Daicel-Allnex) 30 parts by weight 2,2-dimethoxy-2-phenylacetophenone (photoradical polymerization initiator, "IRGACURE651" manufactured by BASF Japan) 2 parts by weight Malonyl hydrazide (thermosetting agent, "MDH" manufactured by Otsuka Chemical Co., Ltd.) 10 parts by weight Silica (filler, "Admafine SO-C2" manufactured by Admatechs) 20 parts by weight 3-Glyceryloxypropyltrimethoxysilane (silane coupling agent, "KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by weight

The above materials were prepared, stirred using a planetary stirring device ("Defoaming Stirring Taro" manufactured by Thinky Co.), and then uniformly mixed using a ceramic three-roll grinder to obtain a sealant for liquid crystal display elements (sealant).

Preparation of liquid crystal display elements: For 100 parts by weight of the obtained sealant, 1 part by weight of spacer particles (average particle size 5 μm, "Micropearl SP-205" manufactured by Sekisui Chemical Industry Co., Ltd.) is prepared, and a planetary stirring device is used to uniformly disperse the spacer particles in the sealant. The obtained sealant containing the spacer particles is filled in a drop-coating syringe ("PSY-10E" manufactured by Musashi High-Tech Corporation) and defoamed. Thereafter, a dispenser ("SHOTMASTER300" manufactured by Musashi High-Tech Corporation) is used to apply the sealant containing the spacer particles in the form of a rectangular frame on a transparent electrode substrate formed with an ITO film. Next, using a liquid crystal dropping device, tiny drops of TN liquid crystal ("JC-5001LA" manufactured by Chisso Corporation) were applied to the inner side of the rectangular area of the transparent electrode substrate coated with a sealant containing spacer particles. Using a vacuum bonding device, the transparent electrode substrate coated with a sealant and TN liquid crystal was bonded to a transparent electrode substrate not coated with a sealant and TN liquid crystal under a vacuum of 5 Pa. Next, using a metal halogen lamp, the portion coated with the sealant was irradiated with ultraviolet light of 100 mW/ ^cm2 for 30 seconds, and then heated at 120°C for 1 hour to thermally cure the sealant, thereby obtaining a liquid crystal display element (cell gap 5 μm).

(Example 2) Resin particles B (polysilicone particles B) were obtained in the same manner as in Example 1 except that "X-22-1602" manufactured by Shin-Etsu Chemical Co., Ltd. was used instead of "X-22-2445" manufactured by Shin-Etsu Chemical Co., Ltd. when preparing resin particles. A connecting material, a connecting structure, and a liquid crystal display element were obtained in the same manner as in Example 1 except that resin particles A were replaced by resin particles B.

(Example 3) (1) Preparation of Resin Particles C (Resin-coated Polysilicone Particles C) In a 500 ml separable flask placed in a warm bath, 6.5 parts by weight of the resin particles A (polysilicone particles A) obtained in Example 1, 0.6 parts by weight of hexadecyltrimethylammonium bromide, 240 parts by weight of distilled water, and 120 parts by weight of methanol were added and stirred at 40°C for 1 hour. Subsequently, 3.0 parts by weight of divinylbenzene and 0.5 parts by weight of styrene were added to the separable flask, the temperature was raised to 75°C, and the mixture was stirred for 0.5 hours. Next, 0.4 parts by weight of dimethyl 2,2'-azobis(isobutyrate) was added to the separable flask and stirred for 8 hours to perform a polymerization reaction. After the polymerization reaction, centrifugal separation was performed to obtain particles, which were then washed with water to obtain resin particles C (resin-coated silicone particles C).

A connection material, a connection structure and a liquid crystal display element were obtained in the same manner as in Example 1 except that the resin particles A were replaced with resin particles C.

(Comparative Example 1) A connection material, a connection structure, and a liquid crystal display element were obtained in the same manner as in Example 1 except that polysilicone powder "KMP-605" (manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of resin particles A.

(Comparative Example 2) When preparing the connection material and the liquid crystal display element, a connection material, a connection structure and a liquid crystal display element were obtained in the same manner as in Example 1 except that polysilicone powder "KMP-590" (manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the resin particles A.

(Evaluation) (1) Total number of T units and Q units (TnQn) The total number of the T unit and the Q unit (TnQn) in ^the total number of the M unit, the D unit, the T unit and the Q unit (100%) was calculated by the above method by performing 29 Si-solid NMR analysis.

(2) Particle size The particle size of approximately 100,000 resin particles was measured using a particle size distribution measuring device ("Multisizer 4" manufactured by Beckman Coulter), and the average value was calculated to determine the particle size of the obtained resin particles.

(3) Coefficient of variation (CV value) The coefficient of variation of the obtained resin particles was measured using the above method.

(4) 10% K value The 10% K value of the obtained resin particles was measured using the above method.

(5) Compression recovery rate at compression deformation of 40% The compression recovery rate of the obtained resin particles at compression deformation of 40% was measured using the above method.

(6) Joint Strength The joint strength of the obtained joint structure was measured at 260°C using a mount strength measuring device. The joint strength was determined according to the following criteria.

[Joint strength criteria] ○○: Shear strength is 150 N/ ^cm2 or more ○: Shear strength is 100 N/ ^cm2 or more but less than 150 N/ ^cm2 ×: Shear strength is less than 100 N/ ^cm2

(7) Rebound Using a scanning electron microscope, observe whether the connection part of the obtained connection structure has rebound. The rebound is determined according to the following criteria.

[Bounce criteria] ○: No bounce occurred ×: Bounce occurred

(8) Internal stress relaxation characteristics The connection parts of the obtained connection structures were observed using a scanning electron microscope to see if cracks occurred. The internal stress relaxation characteristics were determined based on the following criteria.

[Criteria for judging internal stress relaxation characteristics] ○: No cracking ×: Cracking

(9) Hot and cold cycle characteristics (connection reliability) A hot and cold cycle test was performed for 1000 cycles. The hot and cold cycle test was performed by heating the obtained connection structure from -65°C to 150°C and then cooling it to -65°C as one cycle. The ultrasonic flaw detector (SAT) was used to observe whether cracks and peeling occurred in the connection part. The hot and cold cycle characteristics (connection reliability) were determined based on the following criteria.

[Cold and hot cycle characteristics (connection reliability) judgment criteria] ○: No cracks or peeling in the connection part ×: There are cracks or peeling in the connection part

(10) Moisture permeability The obtained liquid crystal display element was stored in an environment of temperature 80°C and humidity 90%RH for 72 hours, then driven with a voltage of AC3.5 V, and the periphery of the intermediate color seal was visually observed. The moisture permeability was determined according to the following criteria.

[Criteria for judging moisture permeability] ○: No color unevenness around the seal △: Very little color unevenness around the seal ×: Obvious color unevenness around the seal

The results are shown in Table 1 below.

[Table 1]

1‧‧‧Resin particles 1A‧‧‧Resin particles 51‧‧‧Connection structure 52‧‧‧First member to be connected 53‧‧‧Second member to be connected 54‧‧‧Connection portion 61‧‧‧Gap control particles 62‧‧‧Metal connection portion 81‧‧‧Liquid crystal display element 82‧‧‧Transparent glass substrate 83‧‧‧Transparent electrode 84‧‧‧Alignment film 85‧‧‧Liquid crystal 86‧‧‧Sealant

Fig. 1 is a cross-sectional view showing an example of a connection structure using the resin particles of the present invention. Fig. 2 is a cross-sectional view showing an example of a liquid crystal display element using the resin particles of the present invention as a spacer for a liquid crystal display element.

Claims (10)

A resin particle comprises a polysilicone resin and a resin particle different from the polysilicone resin, wherein the outer surface of the polysilicone resin is covered by a resin different from the polysilicone resin, the material of the resin different from the polysilicone resin is divinylbenzene or styrene, and in the polysilicone resin, an M unit represented by the general formula: [(R) ₃ SiO _1/2 ], a D unit represented by the general formula: [(R) ₂ SiO _2/2 ], a T unit represented by the general formula: [(R)SiO _3/2 ] and a unit represented by the general formula: [SiO _4/2 ] Of the total number of Q units represented by 100%, the total number of the above-mentioned T units and the above-mentioned Q units is less than 4%, and the particle size of the above-mentioned resin particles is greater than 0.5μm and less than 500μm. For example, the resin particles in claim 1 have a compression recovery rate of less than 10% when the compression deformation is 40%. For resin particles in claim 1 or 2, the 10% K value is less than 500N/ ^mm2 . The resin particles as in claim 1 or 2 are used as spacers. A connecting material comprising: resin particles as described in any one of claims 1 to 4, and adhesive or particles containing metal atoms. The connecting material as in claim 5 includes an adhesive. The connecting material of claim 5 or 6 contains particles containing metal atoms. As in claim 7, the thermal decomposition temperature of the resin particles is higher than the melting point of the particles containing metal atoms. The connecting material of claim 7 is used to form a connecting portion connecting two connecting target components, and is used to form the above-mentioned connecting portion by a sintered body of the above-mentioned particles containing metal atoms. A connection structure, comprising: a first connection target component, a second connection target component, and a connection portion connecting the first connection target component and the second connection target component, wherein the material of the connection portion includes the resin particles as described in any one of claims 1 to 4.