CN104093799B - Circuit connection material, connection structural bodies and its manufacturing method - Google Patents

Circuit connection material, connection structural bodies and its manufacturing method Download PDF

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Publication number
CN104093799B
CN104093799B CN201380008376.0A CN201380008376A CN104093799B CN 104093799 B CN104093799 B CN 104093799B CN 201380008376 A CN201380008376 A CN 201380008376A CN 104093799 B CN104093799 B CN 104093799B
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circuit
mercaptan
structural bodies
connection
equal
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CN104093799A (en
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中泽孝
竹村贤三
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Lishennoco Co ltd
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Hitachi Chemical Co Ltd
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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/321—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives
    • H05K3/323—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by conductive adhesives by applying an anisotropic conductive adhesive layer over an array of pads
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0206—Materials
    • H05K2201/0221—Insulating particles having an electrically conductive coating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/36—Assembling printed circuits with other printed circuits
    • H05K3/361—Assembling flexible printed circuits with other printed circuits

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Combinations Of Printed Boards (AREA)

Abstract

A kind of circuit connection material, it is the circuit connection material for will be formed with the first circuit member of the first circuit electrode on the interarea of first substrate and be attached in the state of making the first circuit electrode and second circuit electrode is oppositely disposed in the second circuit component for being formed with second circuit electrode on the interarea of the second substrate, the circuit connection material contains radical polymerization initiator, free-radical polymerised substance and mercaptan compound, the mercaptan compound has mercapto, and being connected to the number of hydrogen atoms on the carbon atom that the mercapto is connected is 1 or 0, the content of mercaptan compound is 7~17 mass parts relative to free-radical polymerised 100 mass parts of substance.

Description

Circuit connection material, connection structural bodies and its manufacturing method
Technical field
The present invention relates to a kind of between opposite circuit electrode, by pressurization side and pressurizeing to opposite circuit electrode To electrode between the circuit connection material that is electrically connected and connection structural bodies and its manufacturer using the circuit connection material Method.
Background technique
As semiconductor element, circuit connection material used for liquid crystal display element, it is therefore known to use for high adhesiveness and show Show the thermosetting resin of the epoxy resin of high reliability (for example, referring to patent document 1).As the constituent of resin, usually There are the curing agent such as reactive phenolic resin using epoxy resin, with epoxy resin, epoxy resin is promoted to react with curing agent Potentiality curing agent.Potentiality curing agent is an important factor for determining solidification temperature and curing rate, from storage at room temperature Various compounds have been used from the viewpoint of curing rate when stability and heating.
In addition, recently and with acrylate derivative and/or methacrylate derivative (below collectively referred to as " (methyl) Acrylate derivative ".) and the radical-curable bonding agent of the peroxide as radical polymerization initiator closed Note.Since the free radical as reactivity kind is rich in reactivity, radically curing can solidify (for example, ginseng the short time According to patent document 2,3).
Therefore, the short time curing type bonding agent for being conducive to the shortening production time at present is gaining popularity.In addition, further Under the reactive purpose for improving radical-curable bonding agent, the application of chain-transferring agent is studied (for example, referring to special Sharp document 4,5).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 1-113480 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2002-203427 bulletin
Patent document 3: International Publication WO98/044067 pamphlet
Patent document 4: Japanese Unexamined Patent Publication 2003-221557 bulletin
Patent document 5: International Publication WO2009/057376 pamphlet
Summary of the invention
Problems to be solved by the invention
Then, in recent years the compact packages such as mobile phone use on the way, from can by component be thinned in this way from the viewpoint of, To being studied instead of the circuit connection material of component as connector.Due to the circuit member in this compact package Connect the connection spacing (e.g., less than or equal to 0.4mm) of circuit member of the spacing than applying circuit connection material in the past more Greatly, therefore as circuit connection material, it is desirable that from characteristics different in the past.
For example, for the circuit connection material instead of component for being used as connector, due to (partly being led with pervious field Volume elements part purposes, way used for liquid crystal display element etc.) it is shorter compared to the length of interconnecting piece, therefore it is required that higher bonding force.As Example, former purposes liquid crystal display panel using surrounding member connection in, as long as usually be greater than or equal to 6N/cm bonding force , but component is replaced as connector, sometimes require that the bonding force more than or equal to 12N/cm.
On the other hand, the connection about thick spacing (for example, connection spacing is greater than or equal to 0.5mm), the company with thin space It connects and compares, have the tendency that bonding force reduction in the case where having used same circuits connecting material.This be considered as because Are as follows: the electrode radical of every element length is reduced, therefore the shear direction generated on the interface of electrode wall and circuit connection material Bonding force reduce.
Therefore, the purpose of the present invention is to provide one kind can obtain sufficiently high glue in the connection in thick spacing Relay and the excellent circuit connection material of connection reliability and the connection structural bodies and its system that have used the circuit connection material Make method.
Solution to the problem
The inventors of the present invention have made intensive studies to achieve the goals above, as a result, it has been found that: by containing specific quantity Specific chain-transferring agent can obtain showing high bonding force and display good connection reliability in the connection of thick spacing Circuit connection material, so as to complete the present invention.
I.e. the present invention provides a kind of circuit connection material, for for will be formed with the first electricity on the interarea of first substrate First circuit member of path electrode makes with the second circuit component for being formed with second circuit electrode on the interarea of the second substrate The circuit connection material being attached in the state of above-mentioned first circuit electrode and above-mentioned second circuit electrode relative configuration, it is described Circuit connection material contains radical polymerization initiator, free-radical polymerised substance and mercaptan compound, the mercaptan chemical combination Object has mercapto, and the number of hydrogen atoms being connected on the carbon atom that the mercapto is connected is 1 or 0, above-mentioned Thiolation The content of conjunction object is 7~17 mass parts relative to above-mentioned free-radical polymerised 100 mass parts of substance.
According to this circuit connection material, bonding force sufficiently high can be obtained in the connection in thick spacing.In addition, For being used as the circuit connection material instead of component of connector, it is desirable that the connection connected using the circuit connection material Structural body has good connection reliability.Circuit connection material according to the present invention, can be in the connection of thick spacing simultaneously Realize bonding force sufficiently high and good connection reliability.Further, circuit connection material according to the present invention, due to mercaptan Compound works as chain-transferring agent, therefore curing rate is fast and can be realized and connects between low-temperature short-time, can effectively obtain It is improved and other effects to the closing force of the inorganic matters such as metal.
In circuit connection material of the invention, the molecular weight of above-mentioned mercaptan compound is preferably greater than or equal to 400.This Kind circuit connection material bonding force in the connection of thick spacing further increases, and connection reliability becomes more excellent.
In addition, in circuit connection material of the invention, above-mentioned first circuit member (or above-mentioned second circuit component) It is preferred that having on the interarea of above-mentioned first substrate (or above-mentioned the second substrate) to be greater than or equal to the connection spacing shape of 0.5mm At the region for having above-mentioned first circuit electrode (or above-mentioned the second substrate).Even if circuit connection material of the invention is due to thick Also bonding force sufficiently high can be obtained in the connection of spacing, therefore can be suitably used for the company of circuit member as described above It connects.
In addition the present invention also provides a kind of connection structural bodies, comprising: the first circuit is formed on the interarea of first substrate First circuit member of electrode is formed with second circuit electrode and according to above-mentioned second circuit electrode on the interarea of the second substrate Second circuit component that the mode opposite with above-mentioned first circuit electrode configures and setting above-mentioned first circuit member with it is upper The adhesive layer being electrically connected between second circuit component, by above-mentioned first circuit member with above-mentioned second circuit component is stated, it is above-mentioned viscous Layer is connect by heating foregoing circuit connecting material between above-mentioned first circuit member and above-mentioned second circuit component It is formed with pressurization.
This connection structural bodies is due to having used circuit connection material of the invention, the first circuit member and the second electricity Road component is glued with high bonding force.And first circuit member and second circuit component connected with good connection reliability It connects.Therefore, the durability of connection structural bodies of the invention, heat resistance and moisture-proof are excellent.
The present invention further provides a kind of manufacturing methods of connection structural bodies, have following process: will be in first substrate It is formed with the first circuit member of the first circuit electrode on interarea, is formed with second circuit electrode on the interarea of the second substrate Second circuit component and foregoing circuit connecting material are in above-mentioned first circuit electrode with above-mentioned second circuit electrode across upper It states in the state that the opposite mode of circuit connection material configures and is heated and pressurizeed, thus by above-mentioned first circuit electrode and upper State the electrical connection of second circuit electrode.According to this manufacturing method, connection structural bodies of the invention can be readily derived.
The effect of invention
In accordance with the invention it is possible to which bonding force sufficiently high and company can be obtained in the connection in thick spacing by providing one kind It connects circuit connection material excellent in reliability and has used the connection structural bodies and its manufacturing method of the circuit connection material.
Detailed description of the invention
Fig. 1 is the schematic section for indicating an embodiment of connection structural bodies of the invention.
Specific embodiment
A suitable embodiment for circuit connection material and connection structural bodies of the invention is illustrated below.
The circuit connection material of present embodiment contains radical polymerization initiator, free-radical polymerised substance and mercaptan Compound, the mercaptan compound have mercapto, and the number of hydrogen atoms being connected on the carbon atom that the mercapto is connected It is 1 or 0.The content of mercaptan compound is 7~17 mass parts relative to free-radical polymerised 100 mass parts of substance.
The circuit connection material of present embodiment can suitably be used as will be formed on the interarea of first substrate First circuit member of the first circuit electrode and the second circuit structure that second circuit electrode is formed on the interarea of the second substrate The circuit connection material that part is attached in the state of making the first circuit electrode and second circuit electrode is oppositely disposed.
Circuit connection material according to the present embodiment can obtain sufficiently high glue in the connection in thick spacing Relay.In addition, circuit connection material according to the present embodiment, even if can also be obtained for the connection of thick spacing Connection structural bodies with excellent connection reliability.Therefore, the circuit connection material of present embodiment can be used with being particularly suitable for In the connection of the circuit member with thick spacing (connection spacing is greater than or equal to 0.5mm).
Radical polymerization initiator is the compound for generating free free radical, is referred to as free free-radical generating agent. As radical polymerization initiator, preferably peroxide compound, azo compound etc. decompose generating by heating The compound of free free radical.Radical polymerization initiator can connect the appropriate selection such as temperature, Connection Time according to target.
The content of radical polymerization initiator in circuit connection material is preferably 0.05~10 mass %, more preferably 0.1~5 mass %.
Radical polymerization initiator can enumerate diacyl peroxide class, peroxy dicarbonates, peroxyesters, mistake Aoxidize ketal class, dialkyl peroxide class, hydroperoxide kind etc..
As diacyl peroxide class, 2,4- dichlorobenzoyl peroxide, 3,5,5- trimethyl acetyls can be enumerated Base peroxide, sim peroxides, lauroyl peroxide, stearyl peroxide, succinyl group peroxide, Benzoylperoxy toluene, benzoyl peroxide etc..
As peroxy dicarbonates, two-n-propyl peroxy dicarbonates, two carbon of diisopropyl peroxidating can be enumerated Acid esters, bis- (4- tert-butylcyclohexyl) peroxy dicarbonates, two -2- ethoxymethyl) epoxide peroxy dicarbonates, two (2- second The peroxidating of base hexyl) two carbonic esters, dimethoxybutyl peroxy dicarbonate, two (3- methyl -3- methoxybutyl peroxides Change) two carbonic esters etc..
As peroxyesters, 1,1,3,3- tetramethyl butyl new decanoate ester peroxide, 1- cyclohexyl -1- methyl can be enumerated Ethyl new decanoate ester peroxide, tert-hexyl peroxide neodecanoic acid ester, t-butylperoxy pivarate, 1,1,3,3- tetramethyl fourth Base peroxidating -2 ethyl hexanoic acid ester, 2,5- dimethyl -2,5- two (2- ethylhexanoyl-peroxy) hexane, 1- cyclohexyl -1- first Base ethyl peroxidating -2 ethyl hexanoic acid ester, tert-hexyl peroxide -2 ethyl hexanoic acid ester, tert-butyl hydroperoxide -2 ethyl hexanoic acid Bis- (tert-butyl hydroperoxide) hexamethylenes of ester, tert-butyl hydroperoxide isobutyrate, 1,1-, tert-hexyl peroxide isopropyl single carbon acid Ester, tert-butyl hydroperoxide -3,5,5 Trimethylhexanoic acid ester, tert-butyl hydroperoxide laurate, 2,5- dimethyl -2,5- two ( Toluyl peroxidating) hexane, t-butylperoxyisopropyl monocarbonate, tert-butyl hydroperoxide -2- ethylhexyl single carbon acid Ester, tert-hexyl peroxide benzoic ether, tert-butyl hydroperoxide acetic acid esters etc..
As ketal peroxide class, bis- (tert-hexyl peroxide) -3 1,1- can be enumerated, 3,5- trimethyl-cyclohexanes, 1,1- are bis- Bis- (the tert-butyl hydroperoxide) -3,3,5- trimethyl-cyclohexanes of (tert-hexyl peroxide) hexamethylene, 1,1-, bis- (the tert-butyl mistakes of 1,1- Oxidation) cyclododecane, bis- (tert-butyl hydroperoxide) decane of 2,2- etc..
As dialkyl peroxide class, α, bis- (tert-butyl hydroperoxide) diisopropyl benzenes of α '-, dicumyl peroxide can be enumerated Compound, 2,5- dimethyl -2,5- two (tert-butyl hydroperoxide) hexane, tert-butyl cumyl peroxide etc..
As hydroperoxide kind, diisopropyl benzene hydrogen peroxide, cumene hydroperoxide etc. can be enumerated.
These radical polymerization initiators can be used alone or be used in mixed way, can also be with mixed decomposition promotor, suppression Preparation etc. uses.In addition, these radical polymerization initiators polyurethane series, polymer substance of Polyester etc. are coated And the resulting substance of microencapsulation, since keeping quality extends, preferably.
Free-radical polymerised substance is the compound with free-radical polymerised functional group, as free-radical polymerised function Group, preferably vinyl, acryloyl group, methylacryloyl etc..In these, more preferably there is acryloyl group and/or methyl The compound of acryloyl group.
As free-radical polymerised substance, aftermentioned compound can be used with any state in monomer, oligomer, Monomer and oligomer can be used together.
As free-radical polymerised substance, ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) third can be enumerated Olefin(e) acid ester, trimethylolpropane tris (methyl) acrylate, tetramethylol methane four (methyl) acrylate, 2- hydroxyl -1,3- Two (methyl) acryloxy propane, 2,2- bis- [4- ((methyl) acryloyl-oxy ylmethoxy) phenyl] propane, the bis- [4- of 2,2- ((methyl) acryloxy polyethoxy) phenyl] propane, (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid tricyclic last of the ten Heavenly stems Ester, three ((methyl) acryloyl-oxyethyl) isocyanuric acid esters, carbamate (methyl) acrylate, the dihydroxymethyl tricyclic last of the ten Heavenly stems Alkane two (methyl) acrylate, isocyanuric acid EO (ethylene oxide) modified diacrylate, 2- methacryloxyethyl acid Formula phosphate etc..They can be used alone or in combination with.
In addition, preferably having from by bicyclopentane skeleton, tricyclodecane skeleton and three as free-radical polymerised substance The substance of at least one part-structure selected in group composed by piperazine ring.By using the free radical with this part-structure Polymeric agents, the heat resistance of the solidfied material of circuit connection material become excellent.
Further, as free-radical polymerised substance, also can be used polystyrene, polyethylene, polyvinyl butyral, Polyvinyl formal, polyimides, polyamide, polyester, polyvinyl chloride, polyphenylene oxide, urea resin, melamine resin, phenol The polymer such as urea formaldehyde, xylene resin, epoxy resin, polyisocyanate resin, phenoxy resin.In addition, being used as radical polymerization The functional group that the polymer of conjunction property substance has at least one free-radical polymerised in the molecule.
When containing the polymer as free-radical polymerised substance, stress when operability might as well and solidify mitigates excellent Different, therefore preferably, polymer has in the case where the functional groups such as hydroxyl since cementability improves, more preferably.More preferably make With free-radical polymerised functional group by the resulting substance of each polymer modification.
The weight average molecular weight of these polymer is preferably greater than or equal to 1.0 × 104, from the viewpoint of Combination more preferably More than or equal to 1.0 × 104And it is less than or equal to 1.0 × 106.Weight average molecular weight specified in the application refers to: according to following item Part uses value obtained from being measured as the standard curve that standard polystyren obtains as gel permeation chromatography (GPC).
[GPC condition]
Use equipment: Hitachi's L-6000 type [Hitachi Co., Ltd], column: GelpackGL-R420+ GelpackGL-R430+GelpackGL-R440 (3 total) [Hitachi Chemical Co., Ltd.'s system], eluent: tetrahydrofuran, survey Determine temperature: 40 DEG C, flow: 1.75ml/min, detector: L-3300RI [Hitachi Co., Ltd]
Mercaptan compound is with mercapto and the number of hydrogen atoms that is connected on the carbon atom that the mercapto is connected is 0 Or 1 compound.As mercaptan compound, such as aromatic mercaptans and secondary mercaptan compound can be enumerated.
Aromatic mercaptans are that the compound with the mercapto being connected on aromatic rings can be enumerated as aromatic mercaptans Allyl benzene mercaptan sulphonic acid ester, benzenethiol, O-ethoxyl mercaptan, to ethoxybenzenethiol, 2- benzimidazole mercaptan, adjacent sulfydryl Benzoic acid, o-mercaptobenzoic acid methyl esters, 2-[4-morpholinodithio mercaptan, mercaptobenzoxazole, naphthyl mercaptan, toluenethiol, thiobis benzene Mercaptan, to methoxyl group-toluenethiol etc..
Secondary mercaptan compound, which is the compound with secondary mercapto as secondary mercaptan compound, can enumerate sec-butyl thioalcohol, 2, 3- succinimide mercaptans, hex- 5- alkene -3- mercaptan, secondary lauryl mercaptan, secondary heptanthiol, secondary hexyl mercaptan, secondary stearylmercaptan, secondary spicy thioalcohol, 2- Methyl -2- propanethiol etc..For secondary mercaptan compound compared with alcohols, the reactivity as chain-transferring agent is high, excellent at practical aspect.
In addition, as secondary mercaptan compound, preferred compound represented by following formula (1)~(5).
[changing 1]
[changing 2]
[changing 3]
[changing 4]
[changing 5]
The content of mercaptan compound in circuit connection material is preferably with respect to free-radical polymerised 100 mass parts of substance 7~17 mass parts, more preferably 9~12 mass parts.If the content of free-radical polymerised substance is few, in the connection of thick spacing It is difficult to obtain the effect of high bonding force, if the content of free-radical polymerised substance is more, crosslink density is reduced, and has circuit connection The tendency that the resistance reliability of material is deteriorated.
The molecular weight of mercaptan compound is preferably greater than or equal to 90, and more preferably greater than or equal to 150, further preferably For more than or equal to 400.In addition, the molecular weight of mercaptan compound is preferably less than or equal to 5000, more preferably less than or wait In 2000, further preferably less than or equal to 1000.In the case where molecular weight is less than 90, due to connection when heating, meeting Reach the boiling point of compound and cause to evaporate, has the tendency that an adequate amount of mercaptan compound cannot be made to facilitate reaction.Another party Face, in the case where molecular weight is greater than 5000, the removing property of resin is deteriorated, and has the tendency that connecting resistance rises.
In addition, the operational aspect of workability, product when manufacture, the molecular weight of mercaptan compound are more preferably More than or equal to 400.If molecular weight is less than 400, in compounding ingredient, when product operation, there is that foul smell is strong, workability, The tendency that operability reduces.On the other hand, in the case where molecular weight is greater than or equal to 400, foul smell is suppressed, and does not interfere operation Property, operability.
In addition, the mercaptan equivalent as mercaptan compound, preferably greater than or equal to 50 and it is less than or equal to 500, more preferably More than or equal to 120 and it is less than or equal to 400.In the case where mercaptan equivalent is less than 50, crosslink density is reduced, and has circuit connection The tendency that the resistance reliability of material reduces.On the other hand, if mercaptan equivalent is less than or equal to 500, there is bonding force into one Walk the tendency improved.
The circuit connection material of present embodiment can only include radical polymerization initiator, free-radical polymerised substance with And mercaptan compound, it can according to need and further contain following component.
The circuit connection material of present embodiment can be further containing in the molecule with 1 or more nitrogen oxygroup (aminoxyl) compound of structure.It, can be into one if circuit connection material contains the compound with nitrogen oxygroup structure Step improves the storage stability of circuit connection material.
In addition the circuit connection material of present embodiment can further contain thermoplastic resin.As thermoplastic resin, Polyvinyl butyral resin, vinyl-formal resin, polyamide, polyester resin, phenolic resin, ring can be used Oxygen resin, phenoxy resin, polystyrene resin, xylene resin, polyurethane resin, polyester urethane resin etc..About The weight average molecular weight of these thermoplastic resins considers to be preferably greater than or equal to 1.0 × 10 from viewpoints such as film formation propertys4, from mixing Property from the viewpoint of more preferably greater than or equal to 1.0 × 104And less than 1.0 × 106.The weight average molecular weight of thermoplastic resin with The poly- average molecular weight for the polymer that may include in free-radical polymerised substance is carried out similarly measurement.
In addition, be greater than or equal to 40 DEG C it is preferable to use Tg (glass transition temperature) as thermoplastic resin and divide equally again Son amount is greater than or equal to 1.0 × 104Hydroxyl resin (such as phenoxy resin).The resin of hydroxyl can also be by containing ring The elastomer of oxygroup, free-radical polymerised functional group are modified.The substance obtained with free-radical polymerised functional group modification is resistance to Hot raising, therefore preferably.
Phenoxy resin can be by making two function phenols react to high molecular weight with epoxyhalopropane or make two function rings Oxygen resin carries out sudden reaction with two function phenols and obtains.
In addition, as thermoplastic resin, it is also preferred that using polyester urethane resin.By containing Amino-Polyester formic acid Ester resin has the tendency that the bonding force when connection of thick spacing further increases.
Further, the circuit connection material of present embodiment can also be containing packing material, softening agent, promotor, anti-ageing Agent, colorant, fire retardant, thixotropic agent, coupling agent and phenolic resin, melamine resin, isocyanates etc..
From the aspect of improving cementability, preferably there is vinyl, acrylic, amino, epoxy group as coupling agent Or at least one kind of compound in isocyanate group.
In addition, in the case where containing packing material, since the raising of connection reliability etc. can be obtained, preferably. As packing material, material of the maximum diameter less than the partial size of aftermentioned electroconductive particle can be used.In addition, with circuit connection material Total volume on the basis of, the content of packing material is preferably the range of 5~60 volume %.Then if it is greater than or equal to 60 volume % The effect saturation that reliability improves.
The circuit connection material of present embodiment can pass through opposite electricity in connection being free of electroconductive particle The direct contact of path electrode but if further containing electroconductive particle, then can obtain more stable connection to be connected.
As electroconductive particle, the metallics such as Au, Ag, Ni, Cu, solder, carbon etc. can be enumerated.Alternatively, it is also possible to be use Particle obtained from the surface of the transition metal-types such as Ni is coated by the precious metals such as Au.The sufficient up time in order to obtain, It is preferred that surface layer is not the transition metal-types such as Ni, Cu but the precious metal of Au, Ag, platinum family, more preferable Au.In addition, by using The conductive material stated carries out coating etc. method to the surface of the non-conductive particles such as glass, ceramics, plastics and non-conductive Property particle surface form conductting layer and further with the feelings of the obtained particle of precious metal composition outermost layer, fuse metal particle Under condition, since there is morphotropism by heating pressurization, increase in connection with the contact area of electrode, reliability mentions Height, thus preferably.
The use level of electroconductive particle is suitably set depending on the application, usually relative to the resin component in circuit connection material 100 parts by volume are the range of 0.1~30 parts by volume.The adjacent short circuit as caused by superfluous electroconductive particle in order to prevent Deng more preferably 0.1~10 parts by volume.
In addition, circuit connection material is divided into 2 layers or more, be separated into the layer containing curing agent and contains electroconductive particle Layer in the case where, the raising of up time can be obtained.
Further, the circuit connection material of present embodiment, which can according to need, suitably contains quinhydrones, methylether hydroquinone class Equal polymerization inhibitors.
Then, the connection structural bodies of present embodiment and its manufacturing method are illustrated.
Fig. 1 is the summary sectional view for indicating an embodiment of connection structural bodies.Connection structural bodies 1 shown in FIG. 1 has It is standby: first with the first circuit substrate 21 and the first circuit electrode (the first connection terminal) 22 being formed on its interarea 21a Circuit member 20, with second circuit substrate 31 and the second circuit electrode being formed on its interarea 31a (second connection end) 32 second circuit component 30 and between the first circuit member 20 and second circuit component 30 and they are Nian Jie viscous Connect layer 10.Second circuit component 30 is according to the mode opposite with the first circuit electrode 22 of second circuit electrode 32 and the first circuit structure Part 20 is oppositely disposed.
Adhesive layer 10 by making foregoing circuit connecting material between the first circuit member 20 and second circuit component 30, And it is pressurizeed and is formed in this state.The circuit containing electroconductive particle is used in addition, showing in the present embodiment Connecting material forms the example of the case where adhesive layer 10, and adhesive layer 10 is by insulating layer 11 and is dispersed in insulating layer 11 Electroconductive particle 7 is constituted.Ingredient of the insulating layer 11 in bonding agent in addition to electroconductive particle, to pass through free radical polymerization The free radical polymerization of property substance and the solidfied material formed.
The first opposite circuit electrode 22 and second circuit electrode 32 are electrically connected by electroconductive particle 7.It is another Aspect, the first circuit electrode 22 being formed on same circuits substrate are insulated from each other with second circuit electrode 32 each other.
The connection spacing of first circuit electrode 22 and/or second circuit electrode 32 can be for more than or equal to 0.4mm, can also Think and is greater than or equal to 0.45mm.In addition, the upper limit of the connection spacing of the first circuit electrode 22 and/or second circuit electrode 32 does not have There is special limitation, such as can be for less than or equal to 1.0mm, or be less than or equal to 0.9mm.
In addition, from the viewpoint of the effect for further significantly obtaining foregoing circuit connecting material, preferably the first circuit electricity Pole 22 and/or at least part of it of second circuit electrode 32 are formed with the connection spacing (thick spacing) more than or equal to 0.5mm (that is, the first circuit member 20 and/or second circuit component 30, which have, is formed with the with the connection spacing more than or equal to 0.5mm The region of one circuit electrode 22 and/or second circuit electrode 32).
In addition, the 1st circuit electrode 22 and second circuit electrode 32, such as can be for part of it or all with L/S (Line/Space) electrode that the mode for 4/6~9/1 is formed, L/S may be 5/5~9/1.That is, the first circuit member 20 And/or second circuit component 30 can have and be formed with the first circuit electrode 22 and/or second in such a way that L/S is 4/6~9/1 The region of circuit electrode 32.In addition, connection structural bodies 1 preferably has the 1st from the viewpoint of being easy to get more good conducting The L/S of the L/S of circuit electrode 22 and the 2nd circuit electrode 32 adds up to 5/5~1/9 region.
As the first circuit substrate 31 and second circuit substrate 21, semiconductor chip, resistor body chip, capacitor can be enumerated Substrates such as the chip parts such as chip, printed base plate etc..Usually on circuit member be equipped with multiple connection terminals, connection terminal according to Situation may be single.
More specifically, can be used substrate, plastic base or the glass of the inorganic material such as semiconductor, glass and ceramics/ Epoxy substrate.As plastic base, polyimide film, polycarbonate membrane and polyester film can be enumerated.First circuit electrode and Two circuit electrodes are formed by metals such as copper.More good electrical connection in order to obtain preferably makes the first circuit electrode and second circuit The surface of at least one party of electrode is the metal selected from gold, silver, tin and platinum family.Superficial layer is selected from gold, silver, platinum family or tin It is any, they can also be applied in combination.It is formed more alternatively, it is also possible to combine various metals as copper/ni au Layer structure.
In addition, the side in the first circuit member 20 and second circuit component 30 can think with glass substrate or plastics Substrate has as circuit substrate by the liquid crystal display panel of the connection terminal of the formation such as ITO.In addition, the first circuit member 20 and second circuit component 30 in a side may be flexible printing patch panel with polyimide film as circuit substrate (FPC), carrier package (TCP) or flip chip (COF) or the semiconductor silicon with semiconductor substrate as circuit substrate Chip.It can according to need and constitute connection structural bodies for these various circuit members are appropriately combined.
In addition, for the substrate for being equipped with circuit electrode, volatile ingredient pair caused by heating when in order to exclude as connecting The influence of connection is preferably heated before the connection process using circuit connection material in advance.
Connection structural bodies 1 is for example by by the first circuit member 20, film-like circuit connecting material and second circuit component 30 are sequentially overlapped according to this in the sub 32 opposite modes of the first connection terminal 22 and second connection end, in this state plus Pressure or further heating are to form.Pressure is led to as long as adherend is not particularly limited as long as the range for generating damage Often preferably 0.1~10MPa.Heating temperature is not particularly limited, and preferably 100~200 DEG C.These pressurizations and heating preferably exist It carries out, can also be bonded under 130~180 DEG C, 3MPa, heating in 10 seconds in the range of 0.5 second~100 seconds.
The preferred embodiment of the present invention is illustrated above, but the present invention is not limited to the above embodiments.
Embodiment
The present invention is further specifically described below according to embodiment and comparative example, but the present invention is not by following embodiment Any restrictions.
[synthesis of (3- sulfydryl butoxyethyl group) -1,3,5- triazine -2,4,6 (1H, 3H, the 5H)-triketone of 1,3,5- tri-]
By 1,3,5- tri- (2- hydroxyethyl) -1,3,5- triazine -2,4,6- (1H, 3H, 5H)-triketone 120mmol (31.35g), 3- mercaptobutyric acid (shallow lake Chemical Co., Ltd. system) 378mmol (45.42g), 1 hydrate of p-methyl benzenesulfonic acid are (pure Chemical Co., Ltd. system) 8.1mmol (1.51g) and toluene 63g be packed into 100ml eggplant type flask, Dean-Stark device is installed And cooling tube.With while stirring content 140 DEG C of oil bath temperature heat and react 4 hours.Cooling is placed later, with 10% Sodium bicarbonate aqueous solution 100ml neutralization reaction liquid.After reaction solution is further cleaned 3 times with ion exchange water, anhydrous slufuric acid is used Magnesium (Junsei Chemical Co., Ltd.'s system) is dehydrated, is dried.Then toluene distillation is removed, obtains 1,3,5- tri- (3- sulfydryl fourths Oxygroup ethyl) -1,3,5- triazine -2,4,6 (1H, 3H, 5H)-triketone (chemical combination with mercapto represented by above-mentioned formula (1) Object).Obtained compound is highly viscous colourless transparent liquid.Below referred to mercaptan A.
[synthesis of pentaerythrite four (3- mercaptobutylate)]
By bis- (hydroxymethyl) the 1,2- propylene glycol of 2,2- (pentaerythrite, Koei Chemical Co., Ltd.'s system) 60mmol (8.17g), 3- mercaptobutyric acid (shallow lake Chemical Co., Ltd. system) 252mmol (30.28g), 1 hydrate of p-methyl benzenesulfonic acid are (pure Chemical Co., Ltd. system) 5.2mmol (0.98g) and toluene 40g be fitted into 100ml eggplant type flask, installation Dean-Stark dress It sets and cooling tube.With while stirring content 140 DEG C of oil bath temperature heat and react 4 hours.Cooling is placed later, is used 10% sodium bicarbonate aqueous solution 100ml neutralization reaction liquid.After reaction solution is further cleaned 3 times with ion exchange water, use is anhydrous Magnesium sulfate (Junsei Chemical Co., Ltd.'s system) is dehydrated, is dried.Then toluene distillation is removed, obtains four (3- of pentaerythrite Mercaptobutylate) (compound with mercapto represented by above-mentioned formula (2)).Obtained compound is highly viscous colourless Transparency liquid.Below referred to mercaptan B.
[embodiment 1]
By the polyester urethane resin (UR- as thermoplastic resin of 40 mass parts using in terms of nonvolatile component conversion 8200, Co. Ltd. system, 30% solution spin in Japan), 10 mass parts by polyurethane resin (T- in terms of nonvolatile component conversion 6075N, DIC bayer polymer Co. Ltd. system) be dissolved in methyl ethyl ketone obtained from 15 mass % solution, with non-volatile Ingredient conversion 10 mass parts of meter by ethylene vinyl acetate copolymer (EV40W, three well Du Pont polymeric chemical Co. Ltd. systems) 20 mass % solution obtained from being dissolved in toluene, 25 mass parts as free-radical polymerised using in terms of nonvolatile component conversion The toluene of the urethane acrylate oligomer (village UA5500T, Xin Zhong chemical industry Co. Ltd. system) of substance dissolves product 70 mass % solution, dicyclopentadiene-type diacrylate (DCP-A, Toagosei Co., Ltd's system) 5 mass parts, isocyanuric acid EO modified diacrylate (Toagosei Co., Ltd's system, M-215) 5 mass parts and 2- methacryloxyethyl acid Phosphate (P-2M, Kyoeisha Chemical Co., Ltd.'s system) 3 mass parts, the mercaptan A (molecule as the compound with secondary mercapto Measure 567.7) 4 mass parts, 2,5- dimethyl -2,5- two (2- ethyl hexyl) hexane as radical polymerization initiator (PERHEXA 250, Japan Oil Co's system) 4 mass parts are (since PERHEXA 250 is 50% solution, the cooperation of product Amount be 8 mass parts), two-(3- methyl benzoyl) peroxide, benzoyl (3- methyl benzoyl) peroxide and Mixture (NYPER BMT-K40, Japan Oil Co's system) 3 mass parts of dibenzoyl peroxide are (due to NYPER BMT For 40% solution, therefore the use level of product is 7.5 mass parts) cooperation, and then cooperate using polystyrene as the particle table of core Face is equipped with 0.2 μm of thickness of nickel layer and in average grain diameter 10 μm of conduction of the outside of the nickel layer equipped with 0.04 μm of thickness of layer gold Property 6 mass parts of particle, and mixed.Using applicator by the mixed solution be coated on a pet film, by 70 DEG C 10 minutes Heated-air drying obtains 35 μm of thickness of circuit connection material of adhesive layer.In the embodiment 1, relative to free radical polymerization Property substance (this refers to UA5500, DCP-A, M-215 and P-2M) 100 mass parts, with secondary mercapto compound cooperation Amount is 10.5 mass parts.
[embodiment 2]
Other than the use level of mercaptan A (molecular weight 567.7) is set as 3 mass parts, operate similarly with example 1, Obtain circuit connection material.In the embodiment 2, relative to free-radical polymerised substance, (this refers to UA5500, DCP-A, M- 215 and P-2M) 100 mass parts, the use level of the compound with secondary mercapto is 7.89 mass parts.
[embodiment 3]
Other than the use level of mercaptan A (molecular weight 567.7) is set as 6 mass parts, operate similarly with example 1, Obtain circuit connection material.In the embodiment 3, relative to free-radical polymerised substance, (this refers to UA5500, DCP-A, M- 215 and P-2M) 100 mass parts, the use level of the compound with secondary mercapto is 15.8 mass parts.
[embodiment 4]
In addition to the use level of polyester urethane resin (UR8240) is set as 34 mass in terms of nonvolatile component conversion Part, the use level of dicyclopentadiene-type diacrylate (DCP-A) be set as 8 mass parts, isocyanuric acid EO modified diacrylate The use level of (Toagosei Co., Ltd's system, M-215) is set as other than 8 mass parts, is operated similarly with example 1, is obtained electricity Road connecting material.In the embodiment 4, relative to free-radical polymerised substance (this refers to UA5500, DCP-A, M-215 with And P-2M) 100 mass parts, the use level of the compound with secondary mercapto is 9.09 mass parts.
[embodiment 5]
In addition to use mercaptan B (molecular weight: 544.77) 3 mass parts replace mercaptan A other than, operate similarly with example 1, Obtain circuit connection material.In the embodiment 5, relative to free-radical polymerised substance, (this refers to UA5500, DCP-A, M- 215 and P-2M) 100 mass parts, the use level of the compound with secondary mercapto is 7.89 mass parts.
[embodiment 6]
In addition to use mercaptan B (molecular weight: 544.77) 6 mass parts replace mercaptan A other than, operate similarly with example 1, Obtain circuit connection material.In the embodiment 6, relative to free-radical polymerised substance, (this refers to UA5500, DCP-A, M- 215 and P-2M) 100 cooperation parts, the use level of the compound with secondary mercapto is 15.8 mass parts.
[comparative example 1]
Other than the use level of mercaptan A (molecular weight 567.7) is set as 2 mass parts, operate similarly with example 1, Obtain circuit connection material.In the comparative example 1, relative to free-radical polymerised substance, (this refers to UA5500, DCP-A, M- 215 and P-2M) 100 mass parts, the use level of the compound with secondary mercapto is 5.26 mass parts.
[comparative example 2]
Other than the use level of mercaptan A (molecular weight 567.7) is set as 8 mass parts, operate similarly with example 1, Obtain circuit connection material.In the comparative example 1, relative to free-radical polymerised substance, (this refers to UA5500, DCP-A, M- 215 and P-2M) 100 mass parts, the use level of the compound with secondary mercapto is 21.1 mass parts.
[comparative example 3]
Other than the use level of mercaptan A (molecular weight 567.7) is set as 2 mass parts, operate similarly to Example 4, Obtain circuit connection material.In the comparative example 3, relative to free-radical polymerised substance, (this refers to UA5500, DCP-A, M- 215 and P-2M) 100 mass parts, the use level of the compound with secondary mercapto is 4.55 mass parts.
[comparative example 4]
Other than the use level of mercaptan A (molecular weight 567.7) is set as 8 mass parts, operate similarly to Example 4, Obtain circuit connection material.In the comparative example 4, relative to free-radical polymerised substance, (this refers to UA5500, DCP-A, M- 215 and P-2M) 100 mass parts, the use level of the compound with secondary mercapto is 18.2 mass parts.
[comparative example 5]
In addition to use mercaptan B (molecular weight: 544.77) 8 mass parts replace mercaptan A other than, operate similarly to Example 4, Obtain circuit connection material.In the comparative example 5, relative to free-radical polymerised substance, (this refers to UA5500, DCP-A, M- 215 and P-2M) 100 mass parts, the use level of the compound with secondary mercapto is 18.2 mass parts.
[comparative example 6]
In addition to use mercaptan B (molecular weight: 544.77) 2 mass parts replace mercaptan A other than, operate similarly with example 1, Obtain circuit connection material.In the comparative example 6, relative to free-radical polymerised substance, (this refers to UA5500, DCP-A, M- 215 and P-2M) 100 mass parts, the use level of the compound with secondary mercapto is 5.26 mass parts.
By the composition of embodiment and the circuit connection material of comparative example is shown in table 1 and table 2 in.
[table 1]
[table 2]
[production (connection of COF and PWB) of connection structural bodies]
Using each circuit connection material of Examples 1 to 6 and comparative example 1~6, with 130 DEG C -2MPa-10 seconds, width Flexible circuit board (COF-TEG) is connect by 2.0mm with glass epoxide multi-layer printed circuit board (PWB-TEG), the flexible circuit Plate is formed directly with 250 μm of line width, 500 μm of spacing, the copper circuit of 8 μm of thickness and to copper table on 38 μm of thickness of polyimides Face implements 0.2 μm of thickness tin plating, the glass epoxide multi-layer printed circuit board be formed with 250 μm of line width, 500 μm of spacing, The copper circuit that 35 μm of thickness and 0.1 μm of thickness gold-plated is implemented to copper surface.At this moment, the bonding plane of circuit connection material is glued It, later, will with 70 DEG C, 1MPa, 2 seconds carry out heating pressurization and temporarily connect after being attached on glass epoxide multi-layer printed circuit board PET film is removed and realizes COF-TEG connection.
[measurement of bonding force]
Bonding for made connection structural bodies, when being removed under 90 ° with peeling rate 50mm/min measurement Power.The case where value of bonding force is greater than or equal to 12N/cm is denoted as A, is denoted as B less than the case where 12N/cm and evaluates.Will To result be shown in table 3 and table 4.
[measurement of connection resistance]
After circuit connection, using the initial stage resistance value between the adjacent circuit of FPC-PWB of the multitester measuring comprising interconnecting piece, connect , after placing connection structural bodies 5 days in the environment of 40 DEG C of temperature, humidity 60%, using between the adjacent circuit of multitester measuring Resistance value.About resistance value, the average value and maximum value of 37 resistance values between adjacent circuit are measured.By the variation of maximum value The case where rate is within 3 times be denoted as A, greater than 3 times the case where be denoted as B, evaluation 85 DEG C of 85%RH of high temperature and humidity test, processing 500 Connection reliability after hour.In addition, the more few then connection reliability of the change rate of maximum value is the better.The obtained results are shown in Table 3 and table 4.
[table 3]
[table 4]
As shown in Table 3 and Table 4, in Examples 1 to 6, it can be realized high bonding force in the connection in thick spacing With taking into account for excellent connection reliability.It on the other hand, cannot be abundant in the connection of thick spacing in comparative example 1,3,6 Bonding force.In addition, in comparative example 4,5, although having obtained high bonding force, treated that connection resistance becomes for high temperature and humidity Difference cannot get sufficient connection reliability.
In the following, the embodiment of display thin space connection and the result of comparative example are as reference data.
[production (connection of COF and PWB) of thin space connection structural bodies]
Using each circuit connection material of Examples 1 to 6 and comparative example 1~6, with 130 DEG C -2MPa-10 seconds, width Flexible circuit board (COF-TEG) is connect by 2.0mm with glass epoxide multi-layer printed circuit board (PWB-TEG), the flexible circuit Plate is formed directly with 100 μm of line width, 200 μm of spacing, the copper circuit of 8 μm of thickness and to copper table on 38 μm of thickness of polyimides Face implements 0.2 μm of thickness tin plating, the glass epoxide multi-layer printed circuit board be formed with 100 μm of line width, 200 μm of spacing, The copper circuit that 35 μm of thickness and 0.1 μm of thickness gold-plated is implemented to copper surface.At this moment, the bonding plane of circuit connection material is glued It, later, will with 70 DEG C, 1MPa, 2 seconds carry out heating pressurization and temporarily connect after being attached on glass epoxide multi-layer printed circuit board PET film is removed and realizes COF-TEG connection.
For made thin space connection structural bodies, operates as described above and measure bonding force and connection resistance. The obtained results are shown in tables 5 and table 6.
[table 5]
[table 6]
In thin space, Examples 1 to 6 shows good bonding force, but resistance is produced in connection reliability Rise.In addition, comparative example shows good bonding force in thin space, in secondary mercaptan relative to free-radical polymerised substance The ratio of 100 mass parts has obtained stable connection reliability in the comparative example 1,3,4,6 less than 7.
As it appears from the above, about bonding force, not finding big difference in embodiment and comparative example in thin space.Think Present invention serviceability in the connection circuit of thick spacing increases.
Symbol description
1: connection structural bodies, 7: electroconductive particle, 10: adhesive layer, 11: insulating layer, 20: the first circuit members, 21: the first Circuit substrate, 22: the first circuit electrodes (the first connection terminal), 30: second circuit component, 31: second circuit substrate, 32: the Two circuit electrodes (second connection end).

Claims (84)

1. a kind of application of circuit connection material, for the first of the first circuit electrode will to be formed on the interarea of first substrate Circuit member and the second circuit component that second circuit electrode is formed on the interarea of the second substrate make first circuit Electrode is attached in the state of being oppositely disposed with the second circuit electrode,
The circuit connection material contains radical polymerization initiator, free-radical polymerised substance and mercaptan compound, described Mercaptan compound has mercapto, and the number of hydrogen atoms being connected on the carbon atom that the mercapto is connected is 1 or 0,
The content of the mercaptan compound is 7~17 mass parts relative to free-radical polymerised 100 mass parts of substance,
The connection spacing of first circuit electrode and/or the second circuit electrode be more than or equal to 0.45mm,
Some or all Line/Space of first circuit electrode and/or the second circuit electrode be 4/6~ 9/1。
2. the molecular weight of application according to claim 1, the mercaptan compound is greater than or equal to 90.
3. the molecular weight of application according to claim 1, the mercaptan compound is greater than or equal to 150.
4. the molecular weight of application according to claim 1, the mercaptan compound is greater than or equal to 400.
5. the molecular weight of application according to any one of claims 1 to 4, the mercaptan compound is less than or equal to 5000。
6. the molecular weight of application according to any one of claims 1 to 4, the mercaptan compound is less than or equal to 2000。
7. the molecular weight of application according to any one of claims 1 to 4, the mercaptan compound is less than or equal to 1000。
8. application according to any one of claims 1 to 4, the radical polymerization initiator be peroxide compound or Azo compound.
9. application according to any one of claims 1 to 4, the radical polymerization initiator includes from by diacyl mistake Oxide-based, peroxy dicarbonates, peroxyesters, ketal peroxide class, dialkyl peroxide class and hydroperoxidation At least one selected in group composed by species.
10. application according to any one of claims 1 to 4, the free-radical polymerised substance includes to have acryloyl The compound of base and/or methylacryloyl.
11. application according to any one of claims 1 to 4, the mercaptan compound include from by aromatic mercaptans and At least one selected in group composed by secondary mercaptan compound.
12. application according to claim 11, the aromatic mercaptans include from by allyl benzene mercaptan sulphonic acid ester, benzene sulphur Alcohol, O-ethoxyl mercaptan, to ethoxybenzenethiol, 2- benzimidazole mercaptan, o-mercaptobenzoic acid, o-mercaptobenzoic acid first Ester, 2-[4-morpholinodithio mercaptan, mercaptobenzoxazole, naphthyl mercaptan, toluenethiol, thiobisbenzenethiol and to methoxyl group-toluene sulphur At least one selected in group composed by alcohol.
13. application according to claim 11, the secondary mercaptan compound includes from by sec-butyl thioalcohol, 2,3- dibutyl disulfide Alcohol, hex- 5- alkene -3- mercaptan, secondary lauryl mercaptan, secondary heptanthiol, secondary hexyl mercaptan, secondary stearylmercaptan, secondary spicy thioalcohol and 2- methyl -2- At least one selected in group composed by propanethiol.
14. application according to claim 11, the secondary mercaptan compound includes represented by by following formula (1)~(5) Compound composed by at least one that selects in group,
15. application according to any one of claims 1 to 4, the content of the mercaptan compound is relative to the freedom 100 mass parts of base polymeric agents are 9~12 mass parts.
16. the mercaptan equivalent of application according to any one of claims 1 to 4, the mercaptan compound is greater than or equal to 50 and be less than or equal to 500.
17. the mercaptan equivalent of application according to any one of claims 1 to 4, the mercaptan compound is greater than or equal to 120 and be less than or equal to 400.
18. application according to any one of claims 1 to 4, the circuit connection material further contains thermoplastic resin Rouge.
19. application according to claim 18, the thermoplastic resin includes from by polyvinyl butyral resin, poly- second Enol methylal resin, polyamide, polyester resin, phenolic resin, epoxy resin, phenoxy resin, polystyrene resin, two At least one selected in group composed by toluene resin, polyurethane resin and polyester urethane resin.
20. the weight average molecular weight of application according to claim 18, the thermoplastic resin is greater than or equal to 1.0 × 104And Less than 1.0 × 106。
21. the weight average molecular weight of application according to claim 19, the thermoplastic resin is greater than or equal to 1.0 × 104And Less than 1.0 × 106。
22. application according to any one of claims 1 to 4, the circuit connection material further contains conductive grain Son.
23. application according to claim 22, the use level of the electroconductive particle is relative in circuit connection material 100 parts by volume of resin component is the range of 0.1~30 parts by volume.
24. application according to claim 22, the use level of the electroconductive particle is relative in circuit connection material 100 parts by volume of resin component is the range of 0.1~10 parts by volume.
25. application according to any one of claims 1 to 4, first circuit electrode and/or second circuit electricity The connection spacing of pole is less than or equal to 1.0mm.
26. application according to any one of claims 1 to 4, first circuit electrode and/or second circuit electricity The connection spacing of pole is less than or equal to 0.9mm.
27. application according to any one of claims 1 to 4, first circuit member or the second circuit structure Part has on the first substrate or the interarea of the second substrate to be formed with the connection spacing more than or equal to 0.5mm The region of first circuit electrode or the second circuit electrode.
28. application according to any one of claims 1 to 4, first circuit electrode and/or second circuit electricity Some or all Line/Space of pole are 5/5~9/1.
29. a kind of connection structural bodies, comprising:
Be formed on the interarea of first substrate the first circuit electrode the first circuit member,
Second circuit electrode is formed on the interarea of the second substrate and according to the second circuit electrode and first circuit Second circuit component that the opposite mode of electrode configures and
It is arranged between first circuit member and the second circuit component, by first circuit member and described second The adhesive layer of circuit member electrical connection,
The adhesive layer by making circuit connection material between first circuit member and the second circuit component, into Row is heated and pressurizeed and is formed,
The circuit connection material contains radical polymerization initiator, free-radical polymerised substance and mercaptan compound, described Mercaptan compound has mercapto, and the number of hydrogen atoms being connected on the carbon atom that the mercapto is connected is 1 or 0,
The content of the mercaptan compound is 7~17 mass parts relative to free-radical polymerised 100 mass parts of substance,
The connection spacing of first circuit electrode and/or the second circuit electrode be more than or equal to 0.45mm,
Some or all Line/Space of first circuit electrode and/or the second circuit electrode be 4/6~ 9/1。
30. connection structural bodies according to claim 29, first circuit member or the second circuit component exist It is described with being formed with the connection spacing more than or equal to 0.5mm on the first substrate or the interarea of the second substrate The region of first circuit electrode or the second circuit electrode.
31. the molecular weight of connection structural bodies according to claim 29, the mercaptan compound is greater than or equal to 90.
32. the molecular weight of connection structural bodies according to claim 29, the mercaptan compound is greater than or equal to 150.
33. the molecular weight of connection structural bodies according to claim 29, the mercaptan compound is greater than or equal to 400.
34. the molecular weight of the connection structural bodies according to any one of claim 29~33, the mercaptan compound is less than Or it is equal to 5000.
35. the molecular weight of the connection structural bodies according to any one of claim 29~33, the mercaptan compound is less than Or it is equal to 2000.
36. the molecular weight of the connection structural bodies according to any one of claim 29~33, the mercaptan compound is less than Or it is equal to 1000.
37. the connection structural bodies according to any one of claim 29~33, the radical polymerization initiator is peroxide Change compound or azo compound.
38. the connection structural bodies according to any one of claim 29~33, the radical polymerization initiator include from By diacyl peroxide class, peroxy dicarbonates, peroxyesters, ketal peroxide class, dialkyl peroxide class With at least one selected in group composed by hydroperoxide type.
39. the connection structural bodies according to any one of claim 29~33, the free-radical polymerised substance includes tool There is the compound of acryloyl group and/or methylacryloyl.
40. the connection structural bodies according to any one of claim 29~33, the mercaptan compound includes from by fragrance At least one selected in group composed by race's mercaptan and secondary mercaptan compound.
41. connection structural bodies according to claim 40, the aromatic mercaptans include from by allyl benzene mercaptan sulfonic acid Ester, benzenethiol, O-ethoxyl mercaptan, to ethoxybenzenethiol, 2- benzimidazole mercaptan, o-mercaptobenzoic acid, adjacent sulfydryl benzene Methyl formate, 2-[4-morpholinodithio mercaptan, mercaptobenzoxazole, naphthyl mercaptan, toluenethiol, thiobisbenzenethiol and to methoxyl group- At least one selected in group composed by toluenethiol.
42. connection structural bodies according to claim 40, the secondary mercaptan compound includes from by sec-butyl thioalcohol, 2,3- fourth Two mercaptan, hex- 5- alkene -3- mercaptan, secondary lauryl mercaptan, secondary heptanthiol, secondary hexyl mercaptan, secondary stearylmercaptan, secondary spicy thioalcohol and 2- first At least one selected in group composed by base -2- propanethiol.
43. connection structural bodies according to claim 40, the secondary mercaptan compound includes from by following formula (1)~(5) At least one selected in group composed by represented compound,
44. the connection structural bodies according to any one of claim 29~33, the content of the mercaptan compound relative to 100 mass parts of free-radical polymerised substance are 9~12 mass parts.
45. the mercaptan equivalent of the connection structural bodies according to any one of claim 29~33, the mercaptan compound is big In or be equal to 50 and be less than or equal to 500.
46. the mercaptan equivalent of the connection structural bodies according to any one of claim 29~33, the mercaptan compound is big In or be equal to 120 and be less than or equal to 400.
47. the connection structural bodies according to any one of claim 29~33, further contains thermoplastic resin.
48. connection structural bodies according to claim 47, the thermoplastic resin includes from by polyvinyl butyral tree Rouge, vinyl-formal resin, polyamide, polyester resin, phenolic resin, epoxy resin, phenoxy resin, polystyrene At least one selected in group composed by resin, xylene resin, polyurethane resin and polyester urethane resin.
49. the weight average molecular weight of connection structural bodies according to claim 47, the thermoplastic resin is greater than or equal to 1.0 ×104And less than 1.0 × 106。
50. the weight average molecular weight of connection structural bodies according to claim 48, the thermoplastic resin is greater than or equal to 1.0 ×104And less than 1.0 × 106。
51. the connection structural bodies according to any one of claim 29~33, further contains electroconductive particle.
52. connection structural bodies according to claim 51, the use level of the electroconductive particle is relative to circuit connection material 100 parts by volume of resin component in material is the range of 0.1~30 parts by volume.
53. connection structural bodies according to claim 51, the use level of the electroconductive particle is relative to circuit connection material 100 parts by volume of resin component in material is the range of 0.1~10 parts by volume.
54. the connection structural bodies according to any one of claim 29~33, first circuit electrode and/or described The connection spacing of two circuit electrodes is less than or equal to 1.0mm.
55. the connection structural bodies according to any one of claim 29~33, first circuit electrode and/or described The connection spacing of two circuit electrodes is less than or equal to 0.9mm.
56. the connection structural bodies according to any one of claim 29~33, first circuit electrode and/or described Some or all Line/Space of two circuit electrodes are 5/5~9/1.
57. a kind of manufacturing method of connection structural bodies has following process:
By the first circuit member for being formed with the first circuit electrode on the interarea of first substrate, the shape on the interarea of the second substrate At the second circuit component and circuit connection material for having second circuit electrode in first circuit electrode and second electricity Path electrode is to be heated and pressurizeed in the state of configuring across the opposite mode of the circuit connection material, thus by described One circuit electrode and second circuit electrode electrical connection,
The circuit connection material contains radical polymerization initiator, free-radical polymerised substance and mercaptan compound, described Mercaptan compound has mercapto, and the number of hydrogen atoms being connected on the carbon atom that the mercapto is connected is 1 or 0,
The content of the mercaptan compound is 7~17 mass parts relative to free-radical polymerised 100 mass parts of substance,
The connection spacing of first circuit electrode and/or the second circuit electrode be more than or equal to 0.45mm,
Some or all Line/Space of first circuit electrode and/or the second circuit electrode be 4/6~ 9/1。
58. the manufacturing method of connection structural bodies according to claim 57, first circuit member or described second Circuit member has on the first substrate or the interarea of the second substrate to be greater than or equal to the connection spacing of 0.5mm It is formed with the region of first circuit electrode or the second circuit electrode.
59. the molecular weight of the manufacturing method of connection structural bodies according to claim 57, the mercaptan compound be greater than or Equal to 90.
60. the molecular weight of the manufacturing method of connection structural bodies according to claim 57, the mercaptan compound be greater than or Equal to 150.
61. the molecular weight of the manufacturing method of connection structural bodies according to claim 57, the mercaptan compound be greater than or Equal to 400.
62. the manufacturing method of the connection structural bodies according to any one of claim 57~61, the mercaptan compound Molecular weight is less than or equal to 5000.
63. the manufacturing method of the connection structural bodies according to any one of claim 57~61, the mercaptan compound Molecular weight is less than or equal to 2000.
64. the manufacturing method of the connection structural bodies according to any one of claim 57~61, the mercaptan compound Molecular weight is less than or equal to 1000.
65. the manufacturing method of the connection structural bodies according to any one of claim 57~61, the free radical polymerization is drawn Sending out agent is peroxide compound or azo compound.
66. the manufacturing method of the connection structural bodies according to any one of claim 57~61, the free radical polymerization is drawn Sending out agent includes from by diacyl peroxide class, peroxy dicarbonates, peroxyesters, ketal peroxide class, dialkyl group At least one selected in group composed by peroxide and hydroperoxide type.
67. the manufacturing method of the connection structural bodies according to any one of claim 57~61, described free-radical polymerised Substance includes the compound with acryloyl group and/or methylacryloyl.
68. the manufacturing method of the connection structural bodies according to any one of claim 57~61, the mercaptan compound packet Containing at least one selected from the group as composed by aromatic mercaptans and secondary mercaptan compound.
69. the manufacturing method of connection structural bodies according to claim 68, the aromatic mercaptans include from by allyl Benzenethiol sulphonic acid ester, benzenethiol, O-ethoxyl mercaptan, to ethoxybenzenethiol, 2- benzimidazole mercaptan, adjacent sulfydryl benzene first Acid, o-mercaptobenzoic acid methyl esters, 2-[4-morpholinodithio mercaptan, mercaptobenzoxazole, naphthyl mercaptan, toluenethiol, thiobisbenzenethiol With at least one selected in group composed by methoxyl group-toluenethiol.
70. the manufacturing method of connection structural bodies according to claim 68, the secondary mercaptan compound includes from by Zhong Ding Mercaptan, 2,3- succinimide mercaptans, hex- 5- alkene -3- mercaptan, secondary lauryl mercaptan, secondary heptanthiol, secondary hexyl mercaptan, secondary stearylmercaptan, Zhong Xin At least one selected in group composed by mercaptan and 2- methyl -2- propanethiol.
71. the manufacturing method of connection structural bodies according to claim 68, the secondary mercaptan compound includes from by following At least one selected in group composed by compound represented by formula (1)~(5),
72. the manufacturing method of the connection structural bodies according to any one of claim 57~61, the mercaptan compound Content is 9~12 mass parts relative to free-radical polymerised 100 mass parts of substance.
73. the manufacturing method of the connection structural bodies according to any one of claim 57~61, the mercaptan compound Mercaptan equivalent is greater than or equal to 50 and is less than or equal to 500.
74. the manufacturing method of the connection structural bodies according to any one of claim 57~61, the mercaptan compound Mercaptan equivalent is greater than or equal to 120 and is less than or equal to 400.
75. the manufacturing method of the connection structural bodies according to any one of claim 57~61, further contains thermoplasticity Resin.
76. the manufacturing method of the connection structural bodies according to claim 75, the thermoplastic resin includes from by polyethylene Polyvinyl butyral resin, vinyl-formal resin, polyamide, polyester resin, phenolic resin, epoxy resin, phenoxy Selected in group composed by rouge, polystyrene resin, xylene resin, polyurethane resin and polyester urethane resin to Few one kind.
77. the weight average molecular weight of the manufacturing method of the connection structural bodies according to claim 75, the thermoplastic resin is big In or equal to 1.0 × 104And less than 1.0 × 106。
78. the weight average molecular weight of the manufacturing method of the connection structural bodies according to claim 76, the thermoplastic resin is big In or equal to 1.0 × 104And less than 1.0 × 106。
79. the manufacturing method of the connection structural bodies according to any one of claim 57~61, further containing conductive Particle.
80. the manufacturing method of the connection structural bodies according to claim 79, the use level of the electroconductive particle relative to 100 parts by volume of resin component in circuit connection material is the range of 0.1~30 parts by volume.
81. the manufacturing method of the connection structural bodies according to claim 79, the use level of the electroconductive particle relative to 100 parts by volume of resin component in circuit connection material is the range of 0.1~10 parts by volume.
82. the manufacturing method of the connection structural bodies according to any one of claim 57~61, first circuit electrode And/or the connection spacing of the second circuit electrode is less than or equal to 1.0mm.
83. the manufacturing method of the connection structural bodies according to any one of claim 57~61, first circuit electrode And/or the connection spacing of the second circuit electrode is less than or equal to 0.9mm.
84. the manufacturing method of the connection structural bodies according to any one of claim 57~61, first circuit electrode And/or some or all Line/Space of the second circuit electrode are 5/5~9/1.
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