CN107365491A - Resin combination comprising electroconductive particle and the electronic equipment comprising the resin combination - Google Patents
Resin combination comprising electroconductive particle and the electronic equipment comprising the resin combination Download PDFInfo
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- CN107365491A CN107365491A CN201710164744.0A CN201710164744A CN107365491A CN 107365491 A CN107365491 A CN 107365491A CN 201710164744 A CN201710164744 A CN 201710164744A CN 107365491 A CN107365491 A CN 107365491A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/44—Amides
- C08G59/46—Amides together with other curing agents
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4028—Isocyanates; Thioisocyanates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/42—Phenols and polyhydroxy ethers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Polymers & Plastics (AREA)
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Abstract
The present invention provides comprising electroconductive particles such as semiconductor particles and can also solidify in a low temperature of 100 DEG C~150 DEG C and can assign the resin combination of sufficient adhesive strength, electric conductivity.The resin combination of the present invention is the resin combination comprising electroconductive particle, the resin combination includes semiconductor particles (composition A) and is used as above-mentioned electroconductive particle, and also include epoxy resin (composition B), phenoxy resin (composition C) and curing agent (components D), above-mentioned curing agent includes as the cyanate ester resin of the first curing agent and is selected from acid anhydrides as the second curing agent, phenolic resin, curing agent in imidazolium compounds and dicyandiamide, the content of above-mentioned semiconductor particles on the basis of the gross mass of above-mentioned resin combination for the mass % of 1 mass %~40 in the range of.
Description
Technical field
The present invention relates to the resin combination comprising electroconductive particle, more particularly to it can be used as and be used for circuit board each other
Connection, the resin for including electroconductive particle that uses of the anisotropically conducting adhesive that is connected with circuit board of electronic unit
Composition.
Background technology
In recent years, in the electrical connection of the engagement of flexible base board and rigid substrates, electronic unit and circuit board using making
With the connected mode of anisotropically conducting adhesive (such as slurry form, diaphragm state).
For anisotropically conducting adhesive, propose for example in the thermosetting for ensuring electrical insulating property and adhesive strength
Be combined with resin anisotropically conducting adhesives of electroconductive particle such as metal epithelium, the solder of gold, silver, nickel etc. etc. (such as
Patent document 1).Such as electronic unit is set to be crimped with circuit board using this anisotropically conducting adhesive, so that the electricity
Pole contacts and engaged each other by electroconductive particle etc., it may thereby be ensured that electric conductivity.On the other hand, in electronic unit, wiring
In the interelectrode gap of substrate, the anisotropically conducting adhesive in above-mentioned resin to be embedded to conductive particle etc.
State is present, therefore insulating properties, interelectrode cementability etc. are may insure between adjacent electrode.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2006-108523 publications
The content of the invention
The invention problem to be solved
However, for the composition of conventional anisotropically conducting adhesive, such as semiconductor particles are being used as conductive
Property particle in the case of, may insure the connection under low load using the melting of the particle, but the solidification of resin needs
Higher reaction temperature (such as 200 DEG C) and longer reaction time (such as 30 seconds).
Therefore, deformation, the quantitative change of warpage of substrate (glass substrate, glass epoxy substrate, flexible printed board etc.) are big,
Promote maximization, narrow frame, the LCD module of slimming installation in the presence of because of the deformation, warpage reducing display quality
The problem of.
Therefore, the problem in the present invention be to provide comprising electroconductive particles such as semiconductor particles and even in 100 DEG C~
It can also solidify in a low temperature of 150 DEG C, and the resin combination of sufficient adhesive strength, electric conductivity can be assigned.
Means for solving the problems
In order to reach above-mentioned problem, the resin combination comprising electroconductive particle of the invention is (below sometimes also referred to as
For " resin combination ") it is characterised by, it includes semiconductor particles (be denoted as below " composition A ") and is used as above-mentioned electroconductive particle,
And also comprising epoxy resin (be denoted as below " composition B "), phenoxy resin (be denoted as below " composition C ") and curing agent is (below
It is denoted as " components D ") resin component is used as, above-mentioned curing agent includes as the cyanate ester resin of the first curing agent and solid as second
The curing agent in acid anhydrides, phenolic resin, imidazolium compounds and dicyandiamide of agent, the content of above-mentioned semiconductor particles is with above-mentioned
On the basis of the gross mass of resin combination for the mass % of 1 mass %~40 in the range of.
In the resin combination of the present invention, above-mentioned semiconductor particles can include the alloy of Bi-In systems.In addition, above-mentioned solder
The content of Bi in particle relative to Bi and In total 100 mass % is preferably more than 33 mass % and below 85 mass %
In the range of.
Relative to above-mentioned epoxy resin, above-mentioned phenoxy resin and above-mentioned curing agent in the resin combination of the present invention
Total 100 mass parts, the above-mentioned phenoxy resin in the range of the mass parts of about 15 mass parts~about 30 is preferably comprised, is preferably comprised
Above-mentioned first curing agent in the range of the mass parts of about 25 mass parts~about 45, preferably comprise the mass of about 1.0 mass parts~about 7.0
Above-mentioned second curing agent in the range of part, preferably comprise the above-mentioned asphalt mixtures modified by epoxy resin in the range of the mass parts of about 30 mass parts~about 50
Fat.
And then the present invention can also provide the electronic equipment for including above-mentioned resin combination.
Invention effect
The present invention's is low even in 100 DEG C~150 DEG C as the resin combination of electroconductive particle comprising semiconductor particles
It can also solidify under temperature, and sufficient adhesive strength, electric conductivity can be provided.Further, since in 100 DEG C~150 DEG C of low temperature
Under can solidify, therefore in the manufacture of LCD module etc. the deformation of substrate, amount of warpage reduce, can realize should diminish it is good
Electrical connection, therefore the product of high-quality can be provided.
Brief description of the drawings
Fig. 1 is the sectional view for the resin combination comprising electroconductive particle for schematically showing embodiments of the present invention.
Fig. 2 is to schematically show the resin combination for including electroconductive particle using preparing in an embodiment of the present invention
And the glass substrate and the sectional view of the example of the conjugant of flexible base board made.
Fig. 3 is the sectional view for schematically showing the overview for peeling off adhesive strength experiment.
Embodiment
The present invention relates to the resin combination comprising electroconductive particle, it is characterised in that the resin combination includes solder
Particle (composition A) is used as electroconductive particle, and also includes epoxy resin (composition B), phenoxy resin (composition C) and curing agent
(components D), mentioned component D curing agent are included as the cyanate ester resin of the first curing agent and being selected from as the second curing agent
Curing agent in acid anhydrides, phenolic resin, imidazolium compounds and dicyandiamide, the content of mentioned component A semiconductor particles is with the resin
On the basis of the gross mass of composition for the mass % of 1 mass %~40 in the range of.It should be noted that in this manual, have
When above-mentioned composition B, C and D are also referred to as " resin component ", pass through this resin component, it can be ensured that insulating properties, cementability
Deng.
As an embodiment of the invention, such as figure 1 illustrates the resin combination 1 comprising electroconductive particle 2.
As illustrated, the resin combination preferably has membranaceous or sheet shape.Resin combination 1 includes electroconductive particle 2 and tree
Fat composition 3, electroconductive particle 2 are scattered in resin component 3.It should be noted that electroconductive particle 2 preferably uniformly disperses.
Each composition A~D is described in detail below.
[composition A]
For composition A " semiconductor particles ", as long as there is electric conductivity, just its material is not particularly limited, can be arranged
Illustrate metal such as comprising Sn, In, Bi element, alloy etc..As semiconductor particles, preferably use comprising at least containing Sn and In
Sn-In systems alloy or Bi-In systems alloy at least containing Bi and In semiconductor particles.Wherein, from more than 85 DEG C and 100
From the viewpoint of fusing point, manufacturing cost below DEG C etc., the semiconductor particles of the alloy comprising Bi-In systems are preferably used.
In the semiconductor particles of the alloy comprising Bi-In systems, Bi content is relative to Bi and In total 100 mass %
Such as 33 more than mass % and in below 85 mass % scope, preferably more than 40 mass % and below 85 mass % scope
It is interior.If Bi content is in above-mentioned scope, semiconductor particles can be in the temperature melting below the solidification temperature of resin component.
In addition, the load applied to resin combination can be reduced when manufacturing LCD module etc., and then can be greatly reduced to substrate
Stress.
In the range of a diameter of such as 1 μm~20 μm, preferably 3 μm~10 μm of semiconductor particles.If semiconductor particles is straight
Less than 1 μm, then electrical connection sometimes becomes difficult in footpath, if the diameter of semiconductor particles more than 20 μm, has such as semiconductor particles and pressed from both sides
It is miscellaneous to cause the possibility of short circuit etc. between adjacent electrode.
The content of semiconductor particles is such as 1 mass %~40 on the basis of the gross mass (100 mass %) of resin combination
Quality %, in the range of being preferably the mass % of 3 mass %~30.If for the content of semiconductor particles less than 1 mass %, existing can not
The risk of the reliability of electrical connection is ensured, if the content of semiconductor particles exists for example because of adjacent solder more than 40 mass %
The mutual contact of particle or semiconductor particles are mixed between adjacent electrode and cause the possibility of short circuit etc..
[composition B]
Handling easiness (processing when composition B " epoxy resin " is to improve the cementability of the resin combination, be formed
Property) for the purpose of and the resin component that can coordinate.
As epoxy resin, such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, naphthalene type ring oxygen tree can be used
Fat, novolac type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene-type epoxy resin, type ring containing glycidyl ether
Oxygen tree fat, rubber modified epoxy resin etc..In addition, in above-mentioned epoxy resin, in addition to its precursor (such as phenyl glycidyl is sweet
The glycidol such as oily ether ethers) etc..These epoxy resin can be used alone or be used in any combination as needed a variety of epoxies
Resin.It is preferred that normal temperature be liquid or show mobility epoxy resin, wherein, particularly preferred bisphenol A type epoxy resin, bis-phenol
F types epoxy resin, the epoxy resin of type containing glycidyl ether.
The equivalent of epoxy resin is such as more than 150, is preferably 160~250, in the range of more preferably 170~200.
If the equivalent of epoxy resin is in above-mentioned scope, formative of the cementability of the resin combination, film or piece etc. improves.
The content of epoxy resin is mass parts of such as 30 mass parts~50, more preferably relative to the mass parts of resin component 100
In the range of the mass parts of 35 mass parts~45.By the way that the content of epoxy resin is set in such scope, can be set
The formability of the cementability of oil/fat composition, film or piece improves and other effects.
[composition C]
Composition C " phenoxy resin " be by assign it is flexible for the purpose of and the resin component that coordinates, such as may insure with
The cementability of base material.
Phenoxy resin can enumerate for example with bisphenol A-type skeleton, bisphenol-f type skeleton, bisphenol S type skeleton, biphenyl backbone,
Phenoxy resins of skeleton such as novolac skeleton, naphthalene skeleton, acid imide skeleton etc., are preferably selected from these phenoxy resins
One kind or two or more use.
The weight average molecular weight of phenoxy resin is such as more than 30000, preferably 35000~100000, more preferably
In the range of 38000~70000.In addition, softening point is about 80 DEG C~about 160 DEG C, solid-state is shown at normal temperatures, as thermoplasticity
Resin plays a role, therefore the formative of film or piece is excellent.
The content of phenoxy resin is mass parts of such as 15 mass parts~30, preferably relative to the mass parts of resin component 100
In the range of the mass parts of 20 mass parts~25.If the content of phenoxy resin is in above-mentioned scope, make each of solid-like
The making of anisotropy conductive material becomes easy, such as the shaping of piece, film etc. becomes easy.Furthermore it is also possible to suppress by resin
The reduction of adhesive strength caused by the solidification deficiency of composition.
[components D]
" curing agent " of components D includes " the first curing agent " and " the second curing agent " described further below.
First curing agent
First curing agent is cyanate ester resin, and can enumerating such as novolac type, (phenol novolac type, alkyl phenol are linear
Phenol aldehyde type etc.) cyanate ester resin, dicyclopentadiene-type cyanate ester resin, bisphenol type (bisphenol A-type, bisphenol-f type, bisphenol S type etc.)
Cyanate ester resin and one part carry out prepolymer of triazine etc., and a kind or 2 is selected preferably from these cyanate ester resins
Kind is used above.By using the first curing agent, it can be ensured that the curability of the temperature below 150 DEG C.
The molecular weight of cyanate ester resin is such as more than 230g/mol, preferably 240g/mol~280g/mol, more preferably
In the range of 250g/mol~270g/mol.If the molecular weight of cyanate ester resin is in above-mentioned scope, may insure
The curability of less than 150 DEG C of temperature.
The content of first curing agent is the mass parts of such as 25 mass parts~45 relative to the mass parts of resin component 100, preferably
In the range of the mass parts of 30 mass parts~40.If the content of the first curing agent be above-mentioned scope in, solid-like it is each to
The making of different in nature conductive material becomes easy, such as the shaping of piece or film etc. becomes easy.Furthermore it is also possible to suppress by resin into
The reduction of adhesive strength caused by the solidification deficiency divided.
Second curing agent
Second curing agent is the curing agent in acid anhydrides, phenolic resin, imidazolium compounds and dicyandiamide.By using
Two curing agent, above-mentioned resin solidification can be made before and after the fusing point of semiconductor particles.As the second curing agent, preferably using acid
Acid anhydride, wherein, particularly preferably using cyclic acid anhydride.
As cyclic acid anhydride, such as phthalic anhydride, methyl nadic anhydride, tetrahydrophthalic acid can be enumerated
The polynary carboxylics such as the double dehydration trimellitates of acid anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, benzoyl oxide, ethylene glycol
Acid anhydrides etc..
As phenolic resin, such as novolac type, bisphenol type, naphthalene type, dicyclopentadiene-type, phenol aralkyl can be enumerated
The phenolic resin etc. of (Phenol aralkyl) type, trihydroxy benzene methylmethane type.
As imidazolium compounds, such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenyl -4- methyl miaows can be enumerated
Azoles, 1 one benzyls -2-methylimidazole etc..
The content of second curing agent is the mass parts of such as 1.0 mass parts~7.0 relative to the mass parts of resin component 100, excellent
In the range of electing the mass parts of 1.2 mass parts~5.0 as.If the content of the second curing agent is in above-mentioned scope, solid-like
The making of anisotropic conductive material becomes easy, such as the shaping of piece, film etc. becomes easy.Furthermore it is also possible to suppress by setting
The reduction of adhesive strength caused by the solidification deficiency of fat composition.
[manufacture method and application method of the resin combination comprising electroconductive particle]
The resin combination of the above-mentioned embodiment of the present invention for example can be by by above-mentioned composition A~D mixers
Manufactured etc. being mixed.Now, composition B phenoxy resin mixes with other compositions again after being dissolved in advance in solvent
Close.As long as phenoxy resin can be dissolved, then to used solvent, there is no particular restriction, for example, from the viewpoint of formability,
It is preferred that the solvent that steam forces down and boiling point is less than 100 DEG C is used alone or combined such as toluene, MEK, ethyl acetate
Using a variety of.
And then it can also use bar coater etc. that resin combination is configured into the shapes such as membranaceous, sheet.Now, resin group
There is no particular restriction for the thickness after forming of compound, usually 5 μm~30 μm.It should be noted that the present invention's includes conduction
The shape of the resin combination of property particle is not limited to the shapes such as membranaceous, sheet.
The resin combination of the present invention can be made its solidification, at the same time can be led by pressurizeing to provide by heating
Electrically.
Heating-up temperature is such as 70 DEG C~150 DEG C, is preferably 80 DEG C~140 DEG C, more preferably 80 DEG C~130 DEG C.In addition,
The pressure of application is such as 0.5MPa~5MPa, is preferably 0.5MPa~3MPa.The time of heating and/or pressurization is such as 5 seconds
~20 seconds, preferably 8 seconds~15 seconds.
The resin combination of the above-mentioned embodiment of the present invention can provide excellent bonding after above-mentioned heating, pressurization
Intensity, electric conductivity.Such as according to the evaluation method described in detail in following embodiment, there is such as more than 0.35N/mm, excellent
More than 1.5N/mm stripping adhesive strength is selected, is had for example less than 60k Ω, preferably less than 10k Ω connection resistance value.
[electronic equipment]
The present invention the resin combination comprising electroconductive particle can be used for for example LCD module, camera module, firmly
The electronic equipments such as disk, Electronic Paper, touch panel, printhead, IC-card, label, mobile phone inside.
Embodiment
Hereinafter, enumerate embodiment to illustrate the present invention in more detail, still, the present invention is not by following examples
Limit.
[embodiment 1~11 and comparative example 1~6]
The tree of embodiments of the invention 1~11 and comparative example 1~6 is prepared according to the use level shown in following table 1, table 2
Oil/fat composition.Specific preparation method is as shown below.
Each composition is mixed according to the use level shown in following table 1,2.It is kneaded, is made using rotation-revolution mixer
Standby slurry.
Phenoxy resin is dissolved in advance using toluene and ethyl acetate, and it is added to according to the solid constituent amount of regulation
It is kneaded in above-mentioned slurry.
Above-mentioned made slurry is coated with according to thickness 15 for μ μm~20 μm, it is dried at normal temperatures using bar coater, by
This obtains the resin combination of sheet.
Each composition used in embodiment and comparative example is as shown below.
Bisphenol A type epoxy resin：JER828 Mitsubishi Chemicals (strain) make
Phenylglycidyl ether：NacalaiTesque (strain) makes
Phenoxy resin：PKHC bars of industry (strain) system
Cyanate ester resin：Primaset LECY Lonza (strain) make
Acid anhydrides：The new Japan Chemicals of RikacidMH (strain) are made
Semiconductor particles：Bi-In systems (55Bi45In)
3 μm~5 μm of particle diameter
[peel off adhesive strength and connect the evaluation of resistance value]
Adhesive strength and connection electricity are peeled off as caused by the resin combination prepared in embodiment and comparative example to evaluate
For the purpose of resistance, having prepared evaporation has ITO glass substrate and implements plating Au polyimides flexible base board.Glass substrate
Size be 30mm × 30mm × 0.3mm, ITO thickness is(angstrom).Polyimides flexible base board
Size is 35mm × 16mm × 0.08mm, and the thickness for plating Au is 0.03~0.5 μm.
The resin combination (1.5mm × 15mm) of the sheet prepared in embodiment and comparative example is arranged respectively at glass base
Between plate and flexible base board, being pressurizeed 10 seconds with 1MPa pressure when being heated to 130 DEG C makes its bonding, thus obtains conjugant
(Fig. 2).
According to following evaluation method, evaluate peeling off adhesive strength and connection resistance value, its result is in table 3, table 4
In show.
<Peel off adhesive strength evaluation method>
Using cupping machine (Shimadzu AGS-X), determined under conditions of 90 ° of peel angle and peeling rate 1mm/min
The stripping adhesive strength (Fig. 3) of each conjugant.
By peel off adhesive strength be more than 1.5N/mm be evaluated as "○", will peel off adhesive strength be more than 0.35N/mm and
" Δ " is evaluated as less than 1.5N/mm, adhesive strength will be peeled off and be evaluated as "×" less than 0.35N/mm.
Here, if it is more than 1.5N/mm to peel off adhesive strength, state can be also remained engaged with even if applying power, if peeling off
Adhesive strength can not then remain engaged with state, it, which is handled, becomes difficult less than 0.35N/mm.
<Connect resistance value evaluation method>
Determined using tester (MULTI MEASURING INSTRUMENTS Co., Ltd (strain), MCD008) and respectively connect
Fit connection resistance value.
Connection resistance value is evaluated as "○" less than 10k Ω, connection resistance value is commented for more than 10k Ω and less than 60k Ω
Valency is " Δ ", is that more than 60k Ω are evaluated as "×" by connection resistance value.
If connecting resistance value less than 10k Ω, engagement state is very good, can provide stable conduction, if connection
Resistance value is more than 60k Ω, then is unstable conducting state, poor reliability.
<Synthetic determination>
Comprehensively resin combination is judged by the evaluation result of stripping adhesive strength and connection resistance value.
Peel off adhesive strength and connect resistance value evaluation be zero ＞ Δs ＞ × order, and by either one for ×
Situation is determined as "×", and both are determined as into " Δ " for the situation of Δ, and both are determined as into " ◎ " for zero situation, will remove these
Situation beyond situation is determined as "○".
It should be noted that in the present invention, it is determined as that the situation of " ◎ " or "○" can be with above-mentioned synthetic determination
Substantially ensure that and peel off adhesive strength and initial connection resistance, and play excellent effect.
【Table 1】
【Table 2】
【Table 3】
【Table 4】
[investigation on use level]
In embodiment 1, relative to resin component gross mass, the use level of epoxy resin is set to 41.4 mass parts, benzene
The use level of epoxide resin is set to 22.6 mass parts, the use level of cyanate ester resin is set to 34.5 mass parts, the use level of acid anhydrides
1.5 mass parts are set to, and the use level of semiconductor particles is set to 7.4 mass % (table 1) relative to resin combination gross mass.
Its result is as follows：It is low due to flexible caused by the phenoxy resin, cyanate ester resin as curing agent and acid anhydrides
Warm curability, the result for peeling off adhesive strength evaluation are zero, and the result of connection resistance value evaluation is also zero, good (table 3).
In example 2, the use level of the semiconductor particles in the resin combination of embodiment 1 is changed to 1.0 mass %
(table 1).
Its result is as follows：Because the use level of semiconductor particles tails off, therefore the result for connecting resistance value evaluation is Δ, and with
Embodiment 1 is same, and the result for peeling off adhesive strength evaluation is zero (table 3).
In embodiment 3, the use level of the semiconductor particles in the resin combination of embodiment 1 is changed to 40 mass %
(table 1).
Its result is as follows：Because the use level of semiconductor particles is more, the electrical connection of conjugant is stable, therefore connects resistance value and comment
The result of valency is zero, but because the use level of the resin component in resin combination is few, therefore peel off the knot of adhesive strength evaluation
Fruit is Δ (table 3).
In example 4, the use level of the cyanate ester resin in resin component is set to 25 mass parts, and by resin combination
The use level of semiconductor particles in thing is set to 7.4 mass % (table 1).
Its result is as follows：Because the use level of cyanate ester resin tails off, therefore curability at low temperatures reduces, so as to peel off bonding
The result of intensity evaluation is Δ, and because the solidification of resin aggravates, therefore the result for connecting resistance value evaluation is zero (table 3).
In embodiment 5, the use level of the cyanate ester resin in resin component is set to 45 mass parts, and by resin combination
The use level of semiconductor particles in thing is set to 7.4 mass % (table 1).
Its result is as follows：Due to the use level increase of cyanate ester resin, thus there is curability at low temperatures, but due to causing
Solidification hinders, therefore the result for peeling off adhesive strength evaluation is Δ, and because the solidification of resin aggravates, therefore connect resistance value and comment
The result of valency is zero (table 3).
In embodiment 6, the use level of the acid anhydrides in resin component is set to 1.0 mass parts, and by resin combination
The use levels of semiconductor particles be set to 7.4 mass % (table 1).
Its result is as follows：Because the use level of acid anhydrides reduces, therefore curability at low temperatures reduces, and peels off adhesive strength evaluation
As a result it is Δ, and because the solidification of resin aggravates, therefore the result for connecting resistance value evaluation is zero (table 3).
In embodiment 7, the use level of the acid anhydrides in resin component is set to 7.0 mass parts, and by resin combination
The use levels of semiconductor particles be set to 7.4 mass % (table 1).
Its result is as follows：The result for peeling off adhesive strength evaluation is Δ, and the result of connection resistance value evaluation is zero (table 3).
It is thought that due to：Cause solidification bad because of the increase of the use level of the acid anhydrides as curing agent in resin combination, and draw
The reduction for peeling off adhesive strength is acted, but is fully electrically connected.
In embodiment 8, the use level of the phenoxy resin in resin component is set to 15 mass parts, and by resin combination
The use level of semiconductor particles in thing is set to 7.4 mass % (table 1).
Its result is as follows：Because the use level that can assign the flexible phenoxy resin for ensuring closing force is few, therefore shell
Result from adhesive strength evaluation is Δ, and the result for connecting resistance value evaluation is zero (table 3).
In embodiment 9, the use level of the phenoxy resin in resin component is set to 30 mass parts, and by resin combination
The use level of semiconductor particles in thing is set to 7.4 mass % (table 1).
Its result is as follows：Because the cooperation quantitative change of phenoxy resin is more, therefore adaptation improves, but solidifies deficiency, therefore
The result for connecting resistance value evaluation is Δ, and the result for peeling off adhesive strength evaluation is zero (table 3).
In embodiment 10, the use level of the epoxy resin in resin component is set to 30 mass parts, and by resin combination
The use level of semiconductor particles in thing is set to 7.4 mass % (table 1).
Its result is as follows：Because the use level of epoxy resin is few, it is difficult to obtain the conjugant of sheet, therefore it is strong to peel off bonding
The result of degree evaluation is Δ, and because the solidification of resin aggravates, therefore the result for connecting resistance value evaluation is zero (table 3).
In embodiment 11, the use level of the epoxy resin in resin component is set to 50 mass parts, and by resin combination
The use level of semiconductor particles in thing is set to 7.4 mass % (table 1).
Its result is as follows：Because epoxy resin coordinates quantitative change more, therefore, it is difficult to obtain the conjugant of sheet, it is strong to peel off bonding
The result of degree evaluation is Δ, and because the solidification of resin aggravates, therefore the result for connecting resistance value evaluation is zero (table 3).
In the above embodiments 1~11, the synthetic determination shown in table 3 is ◎ or zero, resin combination of the invention
Can below 150 DEG C in a low temperature of solidify, and can provide sufficiently peel off adhesive strength and connection resistance value.
On the other hand, in comparative example 1, only conjugant has been made with the resin component of embodiment 1.Therefore, do not match somebody with somebody completely
Close semiconductor particles (table 2).
Its result is as follows：Due to being only made up of resin component, therefore it is zero to peel off adhesive strength, but due to completely unmated
For ensuring the semiconductor particles of electrical connection, therefore connection resistance value can not determine (-) (table 4).
In comparative example 2, the semiconductor particles use level in the resin combination of comparative example 1 is set to 50 mass % (table 2).
Its result is as follows：It because the use level of semiconductor particles is more, therefore can not be kneaded, and sheet can not be configured to, shell
It can not be determined (-) (table 4) from adhesive strength, connection resistance value.
In comparative example 3, unmated cyanate ester resin, i.e., curing agent is set to only acid anhydrides, and by resin combination
The use levels of semiconductor particles be set to 7.4 mass % (table 2).
Its result is as follows：The result for connecting resistance value evaluation is Δ, and the result for peeling off adhesive strength evaluation is × (table 4).
Think that these results are due to：Curing agent is set to only acid anhydrides, although thus being consolidated with defined temperature and heat time
Change, but solidify deficiency, peeling off adhesive strength will not uprise.
In comparative example 4, unmated acid anhydrides, i.e., curing agent is set to only cyanate ester resin, and by resin combination
Semiconductor particles use level be set to 7.4 mass % (table 2).
Its result is as follows：The result for connecting resistance value evaluation is Δ, and the result for peeling off adhesive strength evaluation is × (table 4).
It is thought that due to：Curing agent is set to only cyanate ester resin, although thus being consolidated with defined temperature and heat time
Change, but solidify deficiency, peeling off adhesive strength will not uprise.
In comparative example 5, unmated phenoxy resin, the use level of the semiconductor particles in resin combination is set to 7.4
Quality % (table 2).
Its result is as follows：Sheet can not be configured to and each evaluation has been carried out with pulp-like.
Due to the solidification of epoxy resin, the result of connection resistance value evaluation is Δ, is used to assign flexibility due to unmated
Phenoxy resin, therefore the result for peeling off adhesive strength evaluation is × (table 4).
In comparative example 6, unmated epoxy resin, the use level of the semiconductor particles in resin combination is set to 7.4 matter
Measure % (table 2).
Its result is as follows：Cohesive during piece formation is high, is the piece of operating difficulties, but due to phenoxy resin there occurs
Solidification, therefore the evaluation result for peeling off adhesive strength and connection resistance value is Δ (table 4).
In above-mentioned comparative example 1~6, the synthetic determination shown in table 4 is × or Δ, it is seen that the resin combination of comparative example
Thing, which can not provide, sufficiently peels off adhesive strength, connection resistance value.
As can be known from the above results：In order to meet required stripping adhesive strength and connection resistance value, by least using
It is the mass % of 1 mass %~40 semiconductor particles on the basis of the gross mass of resin combination, and uses epoxy resin, conduct
Flexibility assigns the phenoxy resin and the curing agent such as cyanate ester resin and acid anhydrides of material, so as to low temperature (such as 150 DEG C with
Under, preferably less than 130 DEG C), obtain good solidfied material under conditions of the short time (such as less than 20 seconds, preferably 10 seconds or so).
It is thought that because the curing agent of acid anhydrides etc. second suppresses the reactive spy of (postponement) as the cyanate ester resin of the first curing agent
Special effect fruit.In addition, it is assumed that the phenoxy resin used in the present invention because the polarity of its functional group is high, therefore can compared with
Reacted under low temperature with the first curing agent such as cyanate ester resins, and the curing agent of acid anhydrides etc. second is due to relatively low polarity,
Therefore the reactivity of three keys of cyanate ester resin is reduced, is changed into gentle reaction, thus obtains near the fusing point of solder
The effect solidified at a temperature of 100 DEG C~150 DEG C, preferably 100 DEG C~130 DEG C.
Industrial applicability
For the resin combination of the present invention, such as thermo-compression bonding can be utilized to make it in a low temperature of 100 DEG C~150 DEG C
Solidification can provide sufficient adhesive strength, electric conductivity so as to form good electrical connection.Therefore, resin of the invention
Composition is beneficial as anisotropically conducting adhesive, such as can be suitable for the skill for being connected electronic unit with circuit board
In art, more specifically, it can be used in the various electronic equipments such as LCD module.
Symbol description
1 includes the resin combination of electroconductive particle
2 electroconductive particles
3 resin components
4 flexible base boards
5 plating Au portions
6 ITO
7 glass substrates
Claims (8)
1. a kind of resin combination, it is the resin combination for including electroconductive particle, and the resin combination includes semiconductor particles
As the electroconductive particle, and epoxy resin, phenoxy resin and curing agent are also included, the curing agent, which includes, is used as the
The cyanate ester resin of one curing agent and as the second curing agent in acid anhydrides, phenolic resin, imidazolium compounds and dicyandiamide
Curing agent, the contents of the semiconductor particles is the mass % of 1 mass %~40 on the basis of the gross mass of the resin combination
In the range of.
2. resin combination according to claim 1, wherein, the semiconductor particles include the alloy of Bi-In systems.
3. resin combination according to claim 2, wherein, the content of the Bi in the semiconductor particles is relative to Bi and In
Total 100 mass % be in more than 33 mass % and below 85 mass % scope.
4. according to resin combination according to any one of claims 1 to 3, it is relative to the epoxy resin, the benzene oxygen
Total 100 mass parts of base resin and the curing agent, comprising 15 mass parts~30 phenoxy group in the range of mass parts
Resin.
5. according to resin combination according to any one of claims 1 to 4, it is relative to the epoxy resin, the benzene oxygen
Total 100 mass parts of base resin and the curing agent, comprising 25 mass parts~45 described first solid in the range of mass parts
Agent.
6. according to resin combination according to any one of claims 1 to 5, it is relative to the epoxy resin, the benzene oxygen
Total 100 mass parts of base resin and the curing agent, comprising 1.0 mass parts~7.0 in the range of mass parts described second
Curing agent.
7. according to resin combination according to any one of claims 1 to 6, it is relative to the epoxy resin, the benzene oxygen
Total 100 mass parts of base resin and the curing agent, comprising 30 mass parts~50 asphalt mixtures modified by epoxy resin in the range of mass parts
Fat.
8. a kind of electronic equipment, it includes resin combination according to any one of claims 1 to 7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016095506A JP2017203109A (en) | 2016-05-11 | 2016-05-11 | Resin composition containing conductive particle and electronic device including the resin composition |
| JP2016-095506 | 2016-05-11 |
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| CN107365491A true CN107365491A (en) | 2017-11-21 |
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| CN201710164744.0A Pending CN107365491A (en) | 2016-05-11 | 2017-03-17 | Resin combination comprising electroconductive particle and the electronic equipment comprising the resin combination |
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| Country | Link |
|---|---|
| JP (1) | JP2017203109A (en) |
| KR (1) | KR20170127355A (en) |
| CN (1) | CN107365491A (en) |
| TW (1) | TW201807054A (en) |
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| JP6584543B2 (en) * | 2018-01-23 | 2019-10-02 | 田中貴金属工業株式会社 | Conductive adhesive composition |
| JP2019156964A (en) * | 2018-03-13 | 2019-09-19 | パナソニックＩｐマネジメント株式会社 | Resin composition, anisotropic conductive film containing the same, and electronic device |
| DE102022110838B3 (en) | 2022-05-03 | 2023-10-12 | Infineon Technologies Ag | Method for producing a chip arrangement, method for producing a chip card |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09279121A (en) * | 1996-04-15 | 1997-10-28 | Hitachi Chem Co Ltd | Adhesive composition and connection member consisting of the composition |
| JPH09291268A (en) * | 1996-04-26 | 1997-11-11 | Hitachi Chem Co Ltd | Adhesive composition and connecting member comprising the same composition |
| CN102737752A (en) * | 2011-03-30 | 2012-10-17 | 株式会社田村制作所 | Anisotropic conducting paste and connecting method of electronic part using same |
| CN104540913A (en) * | 2012-08-14 | 2015-04-22 | 汉高股份有限及两合公司 | Curable compositions comprising composite particles |
| CN104822789A (en) * | 2012-12-25 | 2015-08-05 | 住友金属矿山株式会社 | Conductive adhesive composition and electronic element using same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5705565B2 (en) * | 2011-01-28 | 2015-04-22 | 京セラ株式会社 | Mounting structure |
| JP5964597B2 (en) * | 2011-03-30 | 2016-08-03 | 株式会社タムラ製作所 | Anisotropic conductive paste and method of connecting electronic parts using the same |
-
2016
- 2016-05-11 JP JP2016095506A patent/JP2017203109A/en active Pending
-
2017
- 2017-02-14 TW TW106104738A patent/TW201807054A/en unknown
- 2017-03-17 CN CN201710164744.0A patent/CN107365491A/en active Pending
- 2017-03-22 KR KR1020170036023A patent/KR20170127355A/en not_active Application Discontinuation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09279121A (en) * | 1996-04-15 | 1997-10-28 | Hitachi Chem Co Ltd | Adhesive composition and connection member consisting of the composition |
| JPH09291268A (en) * | 1996-04-26 | 1997-11-11 | Hitachi Chem Co Ltd | Adhesive composition and connecting member comprising the same composition |
| CN102737752A (en) * | 2011-03-30 | 2012-10-17 | 株式会社田村制作所 | Anisotropic conducting paste and connecting method of electronic part using same |
| CN104540913A (en) * | 2012-08-14 | 2015-04-22 | 汉高股份有限及两合公司 | Curable compositions comprising composite particles |
| CN104822789A (en) * | 2012-12-25 | 2015-08-05 | 住友金属矿山株式会社 | Conductive adhesive composition and electronic element using same |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201807054A (en) | 2018-03-01 |
| JP2017203109A (en) | 2017-11-16 |
| KR20170127355A (en) | 2017-11-21 |
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