CN106715622B - Radical polymerization type adhesive composition and method for producing electric connection body - Google Patents
Radical polymerization type adhesive composition and method for producing electric connection body Download PDFInfo
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- CN106715622B CN106715622B CN201580048969.9A CN201580048969A CN106715622B CN 106715622 B CN106715622 B CN 106715622B CN 201580048969 A CN201580048969 A CN 201580048969A CN 106715622 B CN106715622 B CN 106715622B
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- 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
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- 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
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- 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- 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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
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- 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
- C09J7/00—Adhesives in the form of films or foils
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R43/00—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
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- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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Abstract
The radical polymerizable adhesive composition of the present invention contains a radical polymerizable compound, a thermal radical polymerization initiator, a cation polymerizable compound, and a photoacid generator. The photoacid generator has a property of accelerating a thermal radical polymerization reaction of the radical polymerization adhesive composition, and the content of the cationic polymerizable compound in the radical polymerization adhesive composition is 0.25 to 3.75 parts by mass relative to 1 part by mass of the photoacid generator. The content of the photoacid generator in the radical polymerization adhesive composition is 1.0 to 30 parts by mass relative to 100 parts by mass of the thermal radical polymerization initiator.
Description
Technical Field
The present invention relates to a radical polymerizable adhesive composition containing a radical polymerizable compound, a thermal radical polymerization initiator, a photoacid generator, and a cation polymerizable compound.
Background
The following electric connectors are widely manufactured: an electronic device such as a liquid crystal panel or an organic EL panel is laminated with another electronic device such as an IC chip or a flexible substrate via an uncured adhesive layer formed of a curable adhesive composition, and then the uncured adhesive layer is cured to form a cured adhesive layer, thereby producing an electrical connector. In this case, if the uncured adhesive layer is heated excessively to cure it, the electric connector may warp and the electronic component may be damaged. Therefore, as the curable adhesive composition, a photo cation polymerizable adhesive composition in which a photo acid generator as a photo cation polymerization initiator is mixed with a cation polymerizable compound such as an epoxy compound has been used.
However, if a light-shielding portion such as a metal wiring is present in an electronic device, light cannot be sufficiently irradiated to an uncured adhesive layer due to the light-shielding portion, and a problem arises in that the wafer shear strength (die shear strength) of a bonding portion is reduced. Therefore, it has been proposed to add a thermal radical polymerizable compound such as an acrylate monomer or oligomer and a thermal radical polymerization initiator such as an organic peroxide to a photo cation polymerizable adhesive composition to impart thermosetting properties (patent document 1).
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 4469089
Disclosure of Invention
Problems to be solved by the invention
However, in the case of conducting electrical connection using the curable adhesive composition disclosed in patent document 1, the heating temperature in the thermocompression bonding operation is generally 130 to 180 ℃, in order to achieve a low on-resistance value and a good chip shear strength of an electrical connector produced using the curable adhesive composition.
However, if the thermocompression bonding process is performed at such a temperature, warpage that cannot be ignored in practice may occur in the electric connector. Therefore, it is considered that the heating temperature is lowered to about 100 ℃, but the thermosetting reaction becomes insufficient, and as a result, the curing of the light-shielding portion becomes insufficient, and there is a risk that the on-resistance value increases or the wafer shear strength decreases.
The present invention has been made to solve the above-described problems of the prior art, and an object of the present invention is to provide an electrical connector which can achieve sufficient chip shear strength and low on-resistance without causing practically negligible warpage in the electrical connector even when a light-shielding portion such as a metal wiring is present in an electronic device to be bonded, in the case of manufacturing the electrical connector by laminating an electronic device such as a liquid crystal panel or an organic EL panel and another electronic device such as an IC chip or a flexible substrate with an uncured adhesive layer formed of a curable adhesive composition interposed therebetween and then curing the uncured adhesive layer to form a cured adhesive layer.
Means for solving the problems
The present inventors have found that when a polymerizable composition containing a radical polymerizable compound, a thermal radical polymerization initiator, a cation polymerizable compound and a photoacid generator is used for producing an electrical connector, the use of a substance having an action of promoting a radical polymerization reaction as a photoacid generator and the amount of the cation polymerizable compound added to the photoacid generator is limited to a specific range so that sufficient wafer shear strength and low on-resistance can be achieved without warping that cannot be practically ignored, and the present invention has been completed.
That is, the present invention provides a radical polymerizable adhesive composition comprising a radical polymerizable compound, a thermal radical polymerization initiator, a cation polymerizable compound and a photoacid generator; the photoacid generator has a property of accelerating a thermal radical polymerization reaction of the radical polymerization adhesive composition, and the content of the cationic polymerizable compound in the radical polymerization adhesive composition is 0.25 to 3.75 parts by mass relative to 1 part by mass of the photoacid generator.
Further, the present invention provides a method for manufacturing an electrical connector, including:
a step of disposing an adhesive layer on a terminal of one of two electronic components to be disposed facing each other,
a step of disposing a terminal of another electronic component on the adhesive layer, and
a step of pressing one of the two electronic components arranged in an opposed manner against the other of the two electronic components, and curing the adhesive layer by heating and irradiating the adhesive layer with light, thereby electrically connecting the two electronic components arranged in an opposed manner to each other;
the adhesive layer is formed from the radical polymerizable adhesive composition;
when the adhesive layer is cured, acid is generated from the photoacid generator by light irradiation, thereby promoting the thermal radical polymerization reaction of the radical polymerizable adhesive composition to cure the adhesive layer.
Further, the present invention provides a method for manufacturing an electrical connector, comprising:
a step of disposing an adhesive layer on a terminal of one of two electronic components to be disposed facing each other,
a step of disposing a terminal of another electronic component on the adhesive layer, and
a step of pressing one of the two electronic components arranged in an opposed manner against the other of the two electronic components, and curing the adhesive layer by heating and irradiating the adhesive layer with light, thereby electrically connecting the two electronic components arranged in an opposed manner to each other;
the adhesive layer is formed from the radical polymerizable adhesive composition;
the heating of the adhesive layer is performed at a temperature lower than the thermal radical polymerization reaction temperature of a radical polymerization type control composition corresponding to a composition from which the photoacid generator is removed from the radical polymerization type adhesive composition.
Effects of the invention
The radical polymerization type adhesive composition of the present invention contains a radical polymerizable compound, a thermal radical polymerization initiator, a photoacid generator having a property of promoting a thermal radical polymerization reaction of the radical polymerization type adhesive composition, and a cation polymerizable compound, and the amount of the cation polymerizable compound blended with the photoacid generator is limited to a specific range. Therefore, although cationic polymerization of the cationically polymerizable compound proceeds, the acid generated by the photoacid generator by light irradiation is not completely consumed by cationic polymerization of the cationically polymerizable compound, and as a result, thermal radical polymerization reaction of the radical-polymerizable adhesive composition can be promoted. Therefore, even when a light shielding portion such as a metal wiring is present in an electronic device to be bonded, a practically unnoticeable warpage is not generated in the electric connector, and a sufficient wafer shear strength and a low on-resistance value can be realized.
Detailed Description
Free radical polymerization type adhesive composition
The radical polymerizable adhesive composition of the present invention contains a radical polymerizable compound, a thermal radical polymerization initiator, a photoacid generator, and a cation polymerizable compound. As the photoacid generator, a substance having a property of promoting a thermal radical polymerization reaction of the radical polymerization type adhesive composition is used. The content of the cationic polymerizable compound in the radical polymerizable adhesive composition is 0.25 to 3.75 parts by mass relative to 1 part by mass of the photoacid generator.
< radically polymerizable Compound >
The radical polymerizable compound constituting the radical polymerizable adhesive composition of the present invention is a compound capable of undergoing a radical polymerization reaction by an active radical generated by thermal decomposition of a thermal radical polymerization initiator, and is preferably a compound having one or more carbon unsaturated bonds in the molecule, and includes so-called monofunctional radical polymerizable compounds and polyfunctional radical polymerizable compounds. When the radical polymerizable compound contains a polyfunctional radical polymerizable compound, the wafer shear strength of a cured product of the radical polymerizable adhesive composition can be further improved. Therefore, the radical polymerizable compound preferably contains 30% by mass or more of the polyfunctional radical polymerizable compound, and more preferably 50% by mass or more.
Examples of the monofunctional radical polymerizable compound include monofunctional vinyl compounds such as styrene and methylstyrene, and monofunctional (meth) acrylate compounds such as butyl acrylate and butyl methacrylate. Here, "(meth) acrylate" is a term including both acrylate and methacrylate. Examples of the polyfunctional radical polymerizable compound include polyfunctional vinyl compounds such as divinylbenzene, polyfunctional (meth) acrylate compounds such as 1, 6-hexanediol diacrylate, trimethylolpropane trimethacrylate, bisphenol a glycidyl methacrylate (EA-1020, shinkamura chemical corporation), and isocyanurate EO-modified diacrylate (M-215, east asian synthesis corporation). These may be monomeric or oligomeric. Among these, polyfunctional (meth) acrylate compounds are preferable from the viewpoint of heat resistance, and bisphenol a glycidyl methacrylate and isocyanurate EO-modified diacrylate are particularly preferable.
The polyfunctional radical polymerizable compound may be composed of a polyfunctional vinyl compound and a polyfunctional (meth) acrylate compound. By using these compounds in combination, the control of the thermal responsiveness can be performed, and a reactive functional group can be introduced.
< thermal radical polymerization initiator >
The thermal radical polymerization initiator constituting the radical polymerizable adhesive composition of the present invention generates active radicals for radical polymerization of the radical polymerizable compound by thermal decomposition, and a known thermal radical polymerization initiator such as an organic peroxide or an azo compound can be preferably used. Among them, organic peroxides can be preferably used from the viewpoint of achieving excellent storage stability and low-temperature rapid curability.
As the organic peroxide, known organic peroxides as a thermal radical polymerization initiator can be exemplified, and for example, diacyl peroxides, peroxydicarbonates, peroxyesters, peroxyketals, dialkyl peroxides, hydroperoxides, silyl peroxides, and the like can be exemplified from the viewpoint of chemical structure classification. Among them, peroxyesters and diacylperoxides are preferably used in view of less generation of organic acids after thermal decomposition. Further, from the viewpoint of the 1-minute half-life temperature, from the viewpoint of reactivity, an organic peroxide having a 1-minute half-life temperature of 80 to 170 ℃ is preferable, and from the viewpoint of the molecular weight, an organic peroxide having a molecular weight of 180 to 1000 is preferable.
As the azo compound, an azo compound known as a thermal radical polymerization initiator can be used.
The amount of the thermal radical polymerization initiator to be added to the radical polymerizable adhesive composition is preferably 0.5 to 30 parts by mass, more preferably 1.0 to 20 parts by mass, per 100 parts by mass of the radical polymerizable compound, in order to sufficiently cure the radical polymerizable adhesive composition and prevent foaming.
< photoacid generator >
The photoacid generator constituting the radical polymerization type adhesive composition of the present invention is a substance which generates an acid upon irradiation with light such as ultraviolet rays to initiate cationic polymerization of the cationically polymerizable compound, and also a substance which promotes decomposition of the thermal radical polymerization initiator. In other words, the photoacid generator is a substance having a property of promoting a thermal radical polymerization reaction of the radical polymerizable adhesive composition. More specifically, the thermal radical polymerization reaction of the radical-polymerizable adhesive composition is more accelerated than the thermal radical polymerization reaction of the radical-polymerizable control composition in which the photoacid generator is further removed from the radical-polymerizable adhesive composition.
Therefore, the thermal radical polymerization reaction temperature T with the radical polymerization type control composition containing no photoacid generator0In contrast, the thermal radical polymerization reaction temperature T of the radical-polymerizable adhesive composition containing a photoacid generator1And lower. Here, the thermal radical polymerization reaction temperature is a reaction temperature necessary for achieving desired characteristics of the polymer, and is a polymerization reaction temperature set according to the kind of components of the polymerization system, the mixing ratio thereof, the desired characteristics, and the like.
In the present invention, the thermal radical polymerization reaction temperature T of the radical polymerization type control composition containing no photoacid generator0Preferably in the range of 100 to 130 ℃. On the other hand, the thermal radical polymerization reaction temperature T of the radical polymerization type adhesive composition containing the photoacid generator1Preferably the ratio T0The temperature is lower by more than 10 ℃.
As such photoacid generators, those which can be used as photocationic polymerization initiatorsThe photoacid generator is suitably selected from the group consisting of
Onium salts, e.g. aromatic diazonium salts, aromatic sulfonium salts, aliphatic sulfonium salts, and the like sulfonium salts, pyridines
Salt, selenium
Salt, aromatic iodine
Iodine such as salt
Salts, complexes represented by metal-aromatic hydrocarbon complexes such as iron-aromatic hydrocarbon complexes, and toluenesulfonic acid compounds such as benzoin tosylate and benzyl o-nitrotosylate. Among them, preferable examples of the sulfonium salt and the iodonium salt include sulfonium salts and iodonium salts in view of improving the generation efficiency of cation species
Salts, iron arene complexes. In particular, aromatic sulfonium salts that react with high sensitivity to I-line (365nm) from an LED light source as light, specifically triarylsulfonium salts, can be preferably used.
When the photoacid generator is a salt, hexafluoroborate, hexafluorophosphate, tetrafluoroborate, tetrakis (pentafluorophenyl) borate, or the like can be preferably used as a counter anion constituting the salt from the viewpoint of improving reactivity. Among them, tetrakis (pentafluorophenyl) borate can be preferably used.
The amount of the photoacid generator to be incorporated in the radical polymerization adhesive composition is preferably 1.0 to 30 parts by mass, more preferably 2 to 20 parts by mass, per 100 parts by mass of the thermal radical polymerization initiator. Within this range, an effect of promoting decomposition of the thermal radical polymerization initiator can be obtained.
< cationically polymerizable Compound >
The cationic polymerizable compound constituting the radical polymerizable adhesive composition of the present invention is preferably a cyclic ether compound in view of low-temperature rapid curing properties. Among them, a cyclic ether compound which is liquid at room temperature is preferable from the viewpoint of compatibility with other components and fluidity. Examples of such a cyclic ether compound include an epoxy compound and an oxetane compound. An epoxy compound can be preferably used from the viewpoint of cost, availability, and the like.
The epoxy compound is preferably a polyfunctional glycidyl ether type epoxy compound or an alicyclic epoxy compound. Among these, a polyfunctional glycidyl ether type epoxy compound can be preferably used.
Examples of the polyfunctional glycidyl ether-type epoxy compound include bisphenol a-type diglycidyl ether and a prepolymer (condensate) thereof, bisphenol F-type diglycidyl ether and a prepolymer (condensate) thereof, phenol novolac-type diglycidyl ether, di (β -alkylglycidyl) resorcinol ether, bisphenol a-type di (β -alkylglycidyl) ether, and bisphenol F-type di (β -alkylglycidyl) ether.
The epoxy equivalent of the epoxy compound is preferably 100 to 500, more preferably 140 to 300.
The amount of the cationic polymerizable compound such as an epoxy compound to be blended in the radical polymerizable adhesive composition is 1 to 15 parts by mass, preferably 1 to 3 parts by mass, based on 1 part by mass of the photoacid generator. Within this range, the photoacid generator has an effect of promoting a radical polymerization reaction and is capable of reacting with the cationically polymerizable compound.
< other ingredients >
The radical polymerizable adhesive composition of the present invention may further contain a thermoplastic resin such as a phenoxy resin as a film-forming resin. The amount of the thermoplastic resin is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass, per 100 parts by mass of the radical polymerizable compound.
The radical polymerizable adhesive composition of the present invention may further contain a known silane coupling agent. The amount of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the radical polymerizable compound. Within this range, the effect of improving the adhesion to the inorganic material or the metallic material can be obtained.
The radical polymerizable adhesive composition of the present invention may further contain a known photo radical polymerization initiator, an inorganic filler, an organic filler, a conductive filler, an insulating filler, and the like, as required.
< preparation of radical polymerizable adhesive composition >
The radical polymerizable adhesive composition of the present invention can be prepared by uniformly mixing a radical polymerizable compound, a thermal radical polymerization initiator, a photoacid generator, a cation polymerizable compound, and if necessary, other components such as a thermoplastic resin by a known mixing method.
A method for manufacturing an electrical connector: one of (A)
The method (1) for producing an electrical connector of the present invention comprises the following steps (A) to (C). Each step will be described below.
< Process (A) >
An adhesive layer is disposed on a terminal of one of two electronic components to be disposed facing each other by a known method. Here, as one of the two electronic components to be arranged to face each other, a rigid wiring board, a flexible wiring board, and the like can be cited. Examples of the terminals include pad electrodes, wire electrodes, and bump electrodes formed of an electrode material such as copper, aluminum, silver, gold, and ITO. The adhesive layer is formed from the radical polymerizable adhesive composition of the present invention. The adhesive layer can be formed by a known method, for example, various coating methods, printing methods, and further a photolithography technique.
< Process (B) >
Next, terminals of another electronic component are arranged on the adhesive layer formed in step (a) by a known method. As another electronic device, an IC chip, a liquid crystal panel, an organic EL panel, an IC module, a solar cell module, and the like can be cited. Examples of the terminals include pad electrodes, wire electrodes, and bump electrodes formed of an electrode material such as copper, aluminum, silver, gold, and ITO.
< Process (C) >
The adhesive layer is heated while pressing one of the two electronic components arranged opposite to each other in the step (B) against the other by using a known heating and pressing tool. Simultaneously with this heating, or preferably 2 to 3 seconds while continuing the heating after the composition is softened or melted and the heating is started, the adhesive layer is cured by irradiating the adhesive layer with light such as ultraviolet light, preferably an I-line of an LED light source. Here, in the case where at least one electronic component has a metal terminal capable of serving as a light shielding portion formed on one surface of a transparent substrate, light irradiation to the adhesive layer is preferably performed from the other surface side of the transparent substrate of the electronic component. By performing such curing, an electrical connector is obtained. In this case, the acid is generated from the photoacid generator by irradiation with light, whereby the cationically polymerizable compound is cationically polymerized, and the thermal radical polymerization of the radical-polymerizable adhesive composition is further promoted and the adhesive layer is cured as compared with the thermal radical polymerization of a radical-polymerizable control composition in which the photoacid generator is removed from the radical-polymerizable adhesive composition. Thus, even if the light shielding portion is present, the adhesive layer can be sufficiently cured, and the two electronic components arranged opposite to each other can be connected to each other with a low conductive resistance value. Further, good wafer shear strength can be achieved, and moreover, generation of warpage in the electrical connector can be suppressed.
A method for manufacturing an electrical connector: second (2)
The method (2) for producing an electrical connector of the present invention has the same steps as the steps (a) to (C) of the method (1), but differs in the step (C) in the following points: specific heating conditions are clearly indicated, i.e., at a temperature equivalent to the removal of the adhesive from the radical polymerizable adhesive compositionThe heating of the adhesive layer was performed at a temperature lower than the thermal radical polymerization reaction temperature of the radical polymerization type control composition of the photoacid generator. Because the temperature is higher than the thermal free radical polymerization reaction temperature T0The heat curing is carried out at a lower temperature, so that the generation of warpage of the electric bonded body can be suppressed, and the thermal radical polymerization reaction temperature T of the radical polymerizable adhesive composition can be set by the acid generated by the photoacid generator1Ratio T0Further, the curing can be sufficiently performed, and the two electronic devices arranged in opposition to each other can be connected to each other with a low conductive resistance value. Further, good wafer shear strength can be achieved, and moreover, generation of warpage in the electrical connector can be suppressed.
Examples
The present invention will be specifically described below with reference to examples.
Examples 1 to 5 and comparative examples 1 to 4
The mixture (adhesive composition) obtained by mixing the components having the formulation shown in table 1 by a conventional method was applied to a release polyester film, and dried at 70 ℃ to obtain an adhesive sheet having a thickness of 20 μm.
< production of Electrical connector for measuring on-resistance, chip shear Strength, and warpage >
The obtained adhesive sheet was sandwiched between an IC (external dimension: 1.8mm × 20mm, bump height 15 μm) as an evaluation substrate and ITO-coated glass (glass thickness 0.5mm, ITO thickness 200nm) as a base glass substrate having 200 μm wide and 500nm thick aluminum wire electrodes (light-shielding portions) provided on the back surface at a pitch of 200 μm, the IC was heated and pressed under conditions of a pressure bonding temperature of 100 ℃, a pressure bonding pressure of 80MPa, and a pressure bonding time of 5 seconds, and 2 seconds after the start of heating, UV irradiation was performed for 3 seconds from the back surface side (aluminum wire electrode-forming surface side) of the glass substrate under the UV irradiation conditions (UV light source: UV irradiator ZUV-C30H (ohron) of table 1, thereby producing an electrical connector for test evaluation.
< measurement of on resistance value of Electrical connector >
The electric connector thus produced was subjected to an aging test in a high-temperature and high-humidity bath at 85 ℃ and 85% RH for 500 hours. Before and after the aging test, the on-resistance value of the electric connector when a current of 2mA was passed through the electric connector was measured by a 4-terminal method using a resistance measuring instrument (digital multimeter 7555, manufactured by yokogawa electric corporation). The results are shown in Table 1. In practical use, it is preferably 1.0 Ω or less before the aging test, and 10 Ω or less after the aging test.
< measurement of wafer shear Strength of Electrical connector >
The wafer shear strength of the fabricated electrical connector was measured using a wafer shear tester (Universal bond tester series 4000, Noxin DAGE Japan, Ltd.) at a tool speed of 100 μm/sec. The results are shown in Table 1. In practice, 130kgf or more is preferable.
< measurement of warpage amount of Electrical connector >
The surface of the glass substrate on which the aluminum wire electrode was formed of the prepared electric connector was scanned with a probe of a stylus type surface roughness meter (SE-3H, Kyowa institute), and the warpage (. mu.m) was measured. The results are shown in Table 1. Practically, it is preferably 10 μm or less.
[ Table 1]
< examination of the results of Table 1 >
(1) As is clear from a comparison of comparative example 4 containing 8 parts by mass of an organic peroxide as a radical polymerization initiator without a photoacid generator and comparative example 1 containing 4 parts by mass of an organic peroxide and 4 parts by mass of a photoacid generator, if half the amount of the organic peroxide as a radical polymerization initiator is replaced with the photoacid generator, the curing reaction is accelerated. Therefore, it is understood that the photoacid generators used in examples 1 to 5 have a property of accelerating the thermal radical polymerization reaction of the radical-polymerizable adhesive composition.
(2) It is found that the radical polymerizable adhesive compositions of examples 1 to 5, which contain a radical polymerizable compound, a radical polymerization initiator (organic peroxide), a photoacid generator having a property of accelerating the thermal radical polymerization reaction of the radical polymerizable adhesive composition, and a cation polymerizable compound, showed "on resistance values" that were practically free from problems before and after the aging test. Further, the "chip shear strength" and "warpage amount" showed no practical problem.
(3) Further, as can be seen from comparison of examples 1 to 5 with comparative example 1 in which no cationic polymerizable compound is blended and comparative example 2 in which 20 parts by mass of a cationic polymerizable compound is blended, the preferable blending amount of the cationic polymerizable compound is 1 to 15 parts by mass with respect to 1 part by mass of the photoacid generator.
(4) It is understood that comparative example 3 does not contain a radical polymerization initiator (organic peroxide) and a cationically polymerizable compound, and therefore the curing reaction does not proceed.
Industrial applicability of the invention
The radical polymerizable adhesive composition of the present invention contains a radical polymerizable compound, a thermal radical polymerization initiator, a photoacid generator having a property of promoting a thermal radical polymerization reaction of the radical polymerizable adhesive composition, and a cation polymerizable compound, and the amount of the cation polymerizable compound blended with the photoacid generator is limited to a specific range. Therefore, even when a light shielding portion such as a metal wiring is present in an electronic device to be bonded, warpage that cannot be ignored in practical use does not occur in the electric connector, and sufficient wafer shear strength and low on-resistance value can be achieved. Therefore, the radical polymerizable adhesive composition of the present invention is useful for achieving a low conductive resistance value, a good wafer shear strength, and a small amount of warpage when electronic devices having a light shielding portion in a joint portion are connected to each other to produce an electrical connector.
Claims (12)
1. A radical polymerization type adhesive composition comprising a radical polymerizable compound, a thermal radical polymerization initiator, a cation polymerizable compound and a photoacid generator,
the photoacid generator has a property of accelerating a thermal radical polymerization reaction of the radical polymerizable adhesive composition,
the content of the cationic polymerizable compound in the radical polymerizable adhesive composition is 0.25 to 3.75 parts by mass relative to 1 part by mass of the photoacid generator.
2. The radical polymerizable adhesive composition according to claim 1,
the content of the photoacid generator in the radical polymerization type adhesive composition is 1.0-30 parts by mass relative to 100 parts by mass of the thermal radical polymerization initiator.
3. The radical polymerizable adhesive composition according to claim 1 or 2,
the cationically polymerizable compound is an epoxy compound.
4. The radical polymerizable adhesive composition according to claim 3,
the epoxy compound has an epoxy equivalent of 100 to 500.
5. The radical polymerizable adhesive composition according to claim 1 or 2,
the thermal radical polymerization initiator is organic peroxide, and the photoacid generator is sulfonium salt or iodine
Salts or iron arene complexes.
6. The radical polymerizable adhesive composition according to claim 5,
the organic peroxide used as the thermal free radical polymerization initiator is peroxyester or diacyl peroxide with the half-life temperature of 80-170 ℃ in 1 minute and the molecular weight of 180-1000, and the photoacid generator is triarylsulfonium salt.
7. A method of manufacturing an electrical connector, comprising:
a step of disposing an adhesive layer on a terminal of one of two electronic components to be disposed facing each other,
a step of disposing a terminal of another electronic component on the adhesive layer, and
a step of pressing one of the two electronic components arranged in an opposed manner against the other of the two electronic components, and curing the adhesive layer by heating and irradiating the adhesive layer with light, thereby electrically connecting the two electronic components arranged in an opposed manner to each other;
the adhesive layer is formed by the free radical polymerization type adhesive composition according to any one of claims 1 to 6;
when the adhesive layer is cured, acid is generated from the photoacid generator by light irradiation, thereby promoting the thermal radical polymerization reaction of the radical polymerizable adhesive composition to cure the adhesive layer.
8. A method of manufacturing an electrical connector, comprising:
a step of disposing an adhesive layer on a terminal of one of two electronic components to be disposed facing each other,
a step of disposing a terminal of another electronic component on the adhesive layer, and
a step of pressing one of the two electronic components arranged in an opposed manner against the other of the two electronic components, and curing the adhesive layer by heating and irradiating the adhesive layer with light, thereby electrically connecting the two electronic components arranged in an opposed manner to each other;
the adhesive layer is formed by the free radical polymerization type adhesive composition according to any one of claims 1 to 6;
the heating of the adhesive layer is performed at a temperature lower than the thermal radical polymerization reaction temperature of a radical polymerization type control composition corresponding to a composition from which the photoacid generator is removed from the radical polymerization type adhesive composition.
9. The manufacturing method according to claim 7 or 8,
at least one of the electronic components is an electronic component having a metal terminal formed on one surface of a transparent substrate, and light irradiation to the adhesive layer is performed from the other surface side of the transparent substrate of the electronic component.
10. The manufacturing method according to claim 7 or 8,
after the adhesive layer is heated, light irradiation is performed.
11. The manufacturing method according to claim 7 or 8,
the thermal free radical polymerization initiator is organic peroxide, and the photoacid generator is sulfonium salt or iodine
Salts or iron arene complexes.
12. The method of manufacturing as set forth in claim 11,
the organic peroxide used as the thermal free radical polymerization initiator is peroxyester or diacyl peroxide with the half-life temperature of 80-170 ℃ in 1 minute and the molecular weight of 180-1000, and the photoacid generator is triarylsulfonium salt.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2014195538A JP6384234B2 (en) | 2014-09-25 | 2014-09-25 | Radical polymerization type adhesive composition and method for producing electrical connector |
| JP2014-195538 | 2014-09-25 | ||
| PCT/JP2015/074714 WO2016047387A1 (en) | 2014-09-25 | 2015-08-31 | Radically polymerizable adhesive agent composition, and method for manufacturing electrical connector |
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| CN106715622A CN106715622A (en) | 2017-05-24 |
| CN106715622B true CN106715622B (en) | 2020-09-04 |
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| CN201580048969.9A Active CN106715622B (en) | 2014-09-25 | 2015-08-31 | Radical polymerization type adhesive composition and method for producing electric connection body |
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| JP (1) | JP6384234B2 (en) |
| KR (1) | KR102343433B1 (en) |
| CN (1) | CN106715622B (en) |
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| DE102018216868A1 (en) | 2018-10-01 | 2020-04-02 | Tesa Se | Latent reactive adhesive film |
| EP3719088A1 (en) * | 2019-04-02 | 2020-10-07 | 3M Innovative Properties Company | Curable precursor of a structural adhesive composition |
| EP3719089A1 (en) * | 2019-04-02 | 2020-10-07 | 3M Innovative Properties Company | Process of manufacturing a curable precursor of a structural adhesive composition |
| DE102020203952A1 (en) | 2020-03-26 | 2021-09-30 | Tesa Se | Latent reactive adhesive film |
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Also Published As
| Publication number | Publication date |
|---|---|
| TW201627450A (en) | 2016-08-01 |
| WO2016047387A1 (en) | 2016-03-31 |
| KR102343433B1 (en) | 2021-12-24 |
| JP2016065172A (en) | 2016-04-28 |
| TWI720950B (en) | 2021-03-11 |
| KR20170059922A (en) | 2017-05-31 |
| JP6384234B2 (en) | 2018-09-05 |
| CN106715622A (en) | 2017-05-24 |
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