WO2016047387A1 - Radically polymerizable adhesive agent composition, and method for manufacturing electrical connector - Google Patents

Radically polymerizable adhesive agent composition, and method for manufacturing electrical connector Download PDF

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Publication number
WO2016047387A1
WO2016047387A1 PCT/JP2015/074714 JP2015074714W WO2016047387A1 WO 2016047387 A1 WO2016047387 A1 WO 2016047387A1 JP 2015074714 W JP2015074714 W JP 2015074714W WO 2016047387 A1 WO2016047387 A1 WO 2016047387A1
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WIPO (PCT)
Prior art keywords
radical polymerization
adhesive composition
adhesive layer
photoacid generator
polymerizable compound
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PCT/JP2015/074714
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French (fr)
Japanese (ja)
Inventor
慎一 林
祐治 田中
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デクセリアルズ株式会社
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Application filed by デクセリアルズ株式会社 filed Critical デクセリアルズ株式会社
Priority to KR1020167035777A priority Critical patent/KR102343433B1/en
Priority to CN201580048969.9A priority patent/CN106715622B/en
Publication of WO2016047387A1 publication Critical patent/WO2016047387A1/en

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Classifications

    • 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
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a radical polymerization type adhesive composition containing a radical polymerizable compound, a thermal radical polymerization initiator, a photoacid generator, and a cationic polymerizable compound.
  • an electrical connection body After superposing an electrical component such as a liquid crystal panel or an organic EL panel and another electrical component such as an IC chip or a flexible substrate via an uncured adhesive layer formed from a curable adhesive composition, It is widely performed to manufacture an electrical connection body by curing an uncured adhesive layer to form a cured adhesive layer. In this case, if excessive heating is performed to cure the uncured adhesive layer, the electrical connection body may be warped or the electrical component may be damaged. For this reason, as a curable adhesive composition, a cationic photopolymerizable adhesive composition in which a photoacid generator is mixed as a cationic photopolymerization initiator with a cationically polymerizable compound such as an epoxy compound is used. Yes.
  • the photocation polymerization type adhesive composition is blended with a thermal radical polymerizable compound such as an acrylate monomer or oligomer and a thermal radical polymerization initiator such as an organic peroxide to impart thermosetting properties.
  • a thermal radical polymerizable compound such as an acrylate monomer or oligomer
  • a thermal radical polymerization initiator such as an organic peroxide
  • the heating temperature at the time of thermocompression bonding when conducting conductive connection using a curable adhesive composition as disclosed in Patent Document 1 is an electrical connection created using the curable adhesive composition.
  • the temperature is generally 130 to 180 ° C.
  • thermocompression treatment when thermocompression treatment is performed at such a temperature, there is a problem that warpage that cannot be ignored in practice occurs in the electrical connection body. For this reason, it is conceivable to lower the heating temperature to about 100 ° C. However, since the thermosetting reaction becomes insufficient, the light-shielding portion is not sufficiently cured, resulting in an increase in conduction resistance value or die shear strength. There is concern that it will cause a decline.
  • An object of the present invention is to solve the above-described problems of the conventional technology, and an electrical component such as a liquid crystal panel or an organic EL panel and another electrical component such as an IC chip or a flexible substrate are bonded to each other.
  • the electrical connection body is manufactured by superposing the uncured adhesive layer formed from the adhesive composition and then curing the uncured adhesive layer to form a cured adhesive layer. Even if there is a light-shielding part such as a metal wiring in an electrical component, it will not cause a warp that is not negligible in practical use in the electrical connection body, and it will be possible to realize sufficient die shear strength and low conduction resistance value. is there.
  • a polymerizable composition containing a radical polymerizable compound, a thermal radical polymerization initiator, a cationic polymerizable compound, and a photoacid generator to the production of an electrical connector, the warp cannot be ignored in practice.
  • a photoacid generator having a function of promoting a radical polymerization reaction is used, and a photoacid generator is used. The inventors have found that this can be achieved by limiting the blending amount of the cationic polymerizable compound to a specific range, and have completed the present invention.
  • the present invention is a radical polymerization type adhesive composition containing a radical polymerizable compound, a thermal radical polymerization initiator, a cationic polymerizable compound, and a photoacid generator,
  • the photoacid generator has the property of accelerating the thermal radical polymerization reaction of the radical polymerization type adhesive composition
  • a radical polymerization type adhesive composition in which the content of the cationic polymerizable compound in the radical polymerization type adhesive composition is 0.25 to 3.75 parts by mass with respect to 1 part by mass of the photoacid generator.
  • the present invention also includes a step of disposing an adhesive layer on the terminal of one of the two electrical components to be opposed to each other, Placing the terminals of the other electrical component on the adhesive layer; While pressing one of the two electrical components facing each other toward the other, heating and irradiating the adhesive layer, the adhesive layer is cured and the two electrical components disposed facing each other
  • the adhesive layer is formed from the above-mentioned radical polymerization type adhesive composition, Provided a manufacturing method for curing an adhesive layer by generating an acid from a photoacid generator by light irradiation when curing the adhesive layer, thereby promoting a thermal radical polymerization reaction of the radical polymerization type adhesive composition To do.
  • the present invention includes a step of disposing an adhesive layer on a terminal of one of the two electrical components to be opposed to each other, Placing the terminals of the other electrical component on the adhesive layer; While pressing one of the two electrical components facing each other toward the other, heating and irradiating the adhesive layer, the adhesive layer is cured and the two electrical components disposed facing each other
  • the adhesive layer is formed from the above-mentioned radical polymerization type adhesive composition, A manufacturing method in which heating to the adhesive layer is performed at a temperature lower than the thermal radical polymerization reaction temperature of the radical polymerization control composition corresponding to the radical polymerization adhesive composition from which the photoacid generator has been removed. provide.
  • the radical polymerization type adhesive composition of the present invention includes a radical polymerizable compound, a thermal radical polymerization initiator, a photoacid generator having a property of promoting the thermal radical polymerization reaction of the radical polymerization type adhesive composition, a cation
  • the compounding amount of the cationic polymerizable compound with respect to the photoacid generator is limited to a specific range. Therefore, although the cationic polymerization of the cationic polymerizable compound proceeds, the acid generated by the photoacid generator by light irradiation is not consumed for the cationic polymerization of the cationic polymerizable compound, and as a result, radical polymerization type It becomes possible to accelerate the thermal radical polymerization reaction of the adhesive composition.
  • the electric connection body does not generate a warp that cannot be ignored in practice, and a sufficient die shear strength and a low conduction resistance value are realized. be able to.
  • the radical polymerization type adhesive composition of the present invention contains a radical polymerizable compound, a thermal radical polymerization initiator, a photoacid generator, and a cationic polymerizable compound.
  • a radical polymerizable compound a thermal radical polymerization initiator
  • a photoacid generator one having a property of promoting the thermal radical polymerization reaction of the radical polymerization type adhesive composition is used.
  • the content of the cationic polymerizable compound in the radical polymerization adhesive composition is 0.25 to 3.75 parts by mass with respect to 1 part by mass of the photoacid generator.
  • the radical polymerizable compound constituting the radical polymerization type adhesive composition of the present invention is a compound capable of undergoing radical polymerization reaction with active radicals generated by thermal decomposition of a thermal radical polymerization initiator, preferably one or more in the molecule. It has a carbon unsaturated bond, and includes so-called monofunctional radical polymerizable compounds and polyfunctional radical polymerizable compounds.
  • the radical polymerizable compound contains a polyfunctional radical polymerizable compound, the die shear strength of the cured product of the radical polymerization adhesive composition can be further improved. Therefore, the radically polymerizable compound preferably contains a polyfunctional radically polymerizable compound in an amount of 30% by mass or more, 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.
  • monofunctional vinyl compounds such as styrene and methylstyrene
  • monofunctional (meth) acrylate compounds such as butyl acrylate and butyl methacrylate.
  • (meth) acrylate” is a term including acrylate and methacrylate.
  • Polyfunctional radical polymerizable compounds include polyfunctional vinyl compounds such as divinylbenzene, 1,6-hexanediol diacrylate, trimethylolpropane trimethacrylate, bisphenol A glycidyl methacrylate (EA-1020, Shin-Nakamura Chemical Co., Ltd.) And polyfunctional (meth) acrylate compounds such as isocyanuric acid EO-modified diacrylate (M-215, Toagosei Co., Ltd.). These may be monomers or oligomers. Of these, polyfunctional (meth) acrylate compounds, particularly bisphenol A-type glycidyl methacrylate and isocyanuric acid EO-modified diacrylate are preferable from the viewpoint of heat resistance.
  • the polyfunctional radically polymerizable compound may be composed of a polyfunctional vinyl compound and a polyfunctional (meth) acrylate compound.
  • the thermal radical polymerization initiator constituting the radical polymerization type adhesive composition of the present invention generates an active radical for radical polymerization of a radical polymerizable compound by thermal decomposition, and is a known thermal radical polymerization initiator.
  • an organic peroxide or an azo compound can be preferably used.
  • an organic peroxide can be preferably used from the viewpoint that excellent storage stability and low-temperature rapid curability can be realized.
  • an organic peroxide known as a thermal radical polymerization initiator for example, from the viewpoint of chemical structural classification, diacyl peroxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide.
  • examples thereof include oxides, hydroperoxides, and silyl peroxides.
  • peroxyesters and diacyl peroxides can be preferably used from the viewpoint that less organic acid is generated after thermal decomposition. From the viewpoint of half-life temperature for 1 minute, a temperature of 80 to 170 ° C. is preferable from the viewpoint of reactivity, and from the viewpoint of molecular weight, a temperature of 180 to 1000 is preferable.
  • azo compound a known azo compound can be used as a thermal radical polymerization initiator.
  • the amount of the thermal radical polymerization initiator in the radical polymerization adhesive composition is such that the radical polymerization compound 100 is sufficiently cured to prevent the radical polymerization adhesive composition from curing and cause foaming.
  • the amount is preferably 0.5 to 30 parts by mass, more preferably 1.0 to 20 parts by mass with respect to parts by mass.
  • the photoacid generator that constitutes the radical polymerization type adhesive composition of the present invention generates an acid when irradiated with light such as ultraviolet rays and initiates cationic polymerization of the cationically polymerizable compound. It promotes the decomposition of the radical polymerization initiator.
  • the photoacid generator has the property of promoting the thermal radical polymerization reaction of the radical polymerization type adhesive composition. More specifically, the thermal radical polymerization reaction of the radical polymerization adhesive composition is carried out using a radical polymerization control composition corresponding to the radical polymerization adhesive composition in which the photoacid generator is further removed from the radical polymerization adhesive composition. It is possible to promote the thermal radical polymerization reaction.
  • thermal radical polymerization reaction temperature T 0 of containing no photoacid generator radical polymerization type control composition thermal radical polymerization reaction temperature T 1 of the radical polymerization type adhesive composition containing a photoacid generator, It will be low.
  • the thermal radical polymerization reaction temperature is a reaction temperature necessary for realizing the desired characteristics of the polymer, and is set according to the type of the polymerization system components, the blending ratio thereof, the desired characteristics, etc. Polymerization reaction temperature.
  • the thermal radical polymerization reaction temperature T 0 of the radical polymerization control composition containing no photoacid generator is preferably in the range of 100 to 130 ° C.
  • the thermal radical polymerization reaction temperature T 1 of the radical polymerization type adhesive composition containing the photoacid generator is preferably 10 ° C. or more lower than T 0 .
  • Such a photoacid generator can be appropriately selected from photoacid generators used as a photocationic polymerization initiator, and is an onium salt such as an aromatic diazonium salt; an aromatic sulfonium salt, an aliphatic sulfonium.
  • Sulfonium salts such as salts; pyridinium salts; selenonium salts; iodonium salts such as aromatic iodonium salts; complex compounds including metal arene complexes such as iron arene complexes; tosylate compounds such as benzoin tosylate and o-nitrobenzyl tosylate Etc.
  • sulfonium salts iodonium salts, and iron arene complexes can be preferably mentioned because they can improve the generation efficiency of cationic species.
  • an aromatic sulfonium salt that reacts with high sensitivity to I-line (365 nm) from an LED light source as light specifically, a triarylsulfonium salt can be preferably exemplified.
  • the photoacid generator is a salt
  • hexafluoroborate, hexafluorophosphate, tetrafluoroborate, tetrakis (pentafluorophenyl) borate are used as counter anions constituting the salt from the viewpoint of improving reactivity.
  • Etc. can be preferably employed.
  • tetrakis (pentafluorophenyl) borate can be preferably employed.
  • the blending amount of the photoacid generator in the radical polymerization type adhesive composition is preferably 1.0 to 30 parts by mass, more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the thermal radical polymerization initiator. If it is this range, the effect of promoting decomposition
  • a cyclic ether compound can be preferably mentioned from the viewpoint of low temperature fast curability. Among these, those which are liquid at room temperature are preferable from the viewpoint of compatibility with other components and fluidity. Examples of such cyclic ether compounds include epoxy compounds and oxetane compounds. An epoxy compound can be preferably used from the viewpoints of cost, availability, and the like.
  • Preferred examples of the epoxy compound include polyfunctional glycidyl ether type epoxy compounds and alicyclic epoxy compound compounds. In these, a polyfunctional glycidyl ether type epoxy compound can be used preferably.
  • Polyfunctional glycidyl ether type epoxy compounds include bisphenol A type diglycidyl ether and its prepolymer (condensate), bisphenol F type diglycidyl ether and its prepolymer (condensate), phenol novolac type diglycidyl ether, di ( ⁇ -alkyl glycidyl) resorcinol ether, bisphenol A type di ( ⁇ -alkyl glycidyl) ether, bisphenol F type di ( ⁇ -alkyl glycidyl) ether, and the like.
  • the epoxy equivalent of such an epoxy compound is preferably 100 to 500, more preferably 140 to 300.
  • the blending amount of the cationic polymerizable compound such as an epoxy compound in the radical polymerization type adhesive composition is 1 to 15 parts by mass, preferably 1 to 3 parts by mass with respect to 1 part by mass of the photoacid generator. If it is this range, the effect with which a photo-acid generator accelerates
  • the radical polymerization type adhesive composition of the present invention can further contain a thermoplastic resin such as a phenoxy resin as a film-forming resin.
  • the blending amount of such a thermoplastic resin is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass with respect to 100 parts by mass of the radical polymerizable compound.
  • the radical polymerization type adhesive composition of the present invention can contain a known silane coupling agent.
  • the blending amount of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the radical polymerizable compound. If it is this range, the effect that the adhesiveness with respect to an inorganic and metal type material will improve is acquired.
  • the radical polymerization type adhesive composition of the present invention can contain a known radical photopolymerization initiator, an inorganic filler, an organic filler, a conductive filler, an insulating filler, etc., if necessary.
  • the radical polymerization type adhesive composition of the present invention includes a radical polymerizable compound, a thermal radical polymerization initiator, a photoacid generator, a cationic polymerizable compound, and a thermoplastic resin blended as necessary. Can be prepared by uniformly mixing them with a known mixing means.
  • Part 1 The method for manufacturing an electrical connection body according to the present invention (part 1) includes the following steps (a) to (c). Below, it demonstrates for every process.
  • An adhesive layer is disposed on a terminal of one of the two electrical components to be disposed to face each other according to a known technique.
  • a rigid circuit board, a flexible wiring board, etc. are mentioned as one of the two electric components which should be arrange
  • these terminals include pad electrodes, line electrodes, and bump electrodes formed from electrode materials such as copper, aluminum, silver, gold, and ITO.
  • the adhesive layer is formed from the radical polymerization type adhesive composition of the present invention described above. Such an adhesive layer can be formed by using a known method, for example, various coating methods, printing methods, and photolithographic techniques.
  • the terminal of the other electrical component is placed on the adhesive layer formed in the step (A) according to a known method.
  • the other electrical component include an IC chip, a liquid crystal panel, an organic EL panel, an IC module, and a solar cell module.
  • these terminals include pad electrodes, line electrodes, and bump electrodes formed from electrode materials such as copper, aluminum, silver, gold, and ITO.
  • the adhesive layer is heated while pressing one of the two electric components opposed to each other with a known heating and pressing tool. Simultaneously with this heating or waiting for softening or melting of the composition, after the heating is started, the heating is continued, preferably after 2 or 3 seconds, light such as ultraviolet rays, preferably the I-line of the LED light source, is applied to the adhesive layer. It is irradiated with light to cure the adhesive layer.
  • light irradiation to the adhesive layer is performed from the other side of the transparent substrate of the electrical component. Is preferred.
  • An electrical connector is obtained by curing in this way.
  • an acid is generated from the photoacid generator by light irradiation, thereby cationically polymerizing the cation polymerizable compound, and thermal radical polymerization of the radical polymerization adhesive composition is performed from the radical polymerization adhesive composition.
  • the adhesive layer is cured by accelerating the thermal radical polymerization of the radical polymerization control composition corresponding to the photoacid generator removed.
  • the manufacturing method (part 2) of the electrical connection body of the present invention has the same steps as steps (a) to (c) of the manufacturing method (part 1).
  • the adhesive layer is heated. Clarify the specific heating conditions to be performed at a temperature lower than the thermal radical polymerization reaction temperature of the radical polymerization control composition corresponding to the radical polymerization adhesive composition from which the photoacid generator is further removed. It differs in that it is. Since heat curing is performed at a temperature lower than the thermal radical polymerization reaction temperature T 0, it is possible to suppress the warpage of the electric bonded body, and the heat radical of the radical polymerization type adhesive composition is generated by the acid generated by the photoacid generator.
  • the polymerization reaction temperature T 1 is lower than T 0, it can be sufficiently cured, and the two electric components arranged opposite to each other can be connected with a low conductive resistance value. In addition, good die shear strength can be achieved, and warpage of the electrical connection body can be suppressed.
  • Examples 1 to 5 and Comparative Examples 1 to 4 A mixture (adhesive composition) obtained by mixing the components of the composition shown in Table 1 by a conventional method was applied to a release polyester film and dried at 70 ° C. to obtain an adhesive sheet having a thickness of 20 ⁇ m.
  • the obtained adhesive sheet is provided with an IC (outside dimension: 1.8 mm ⁇ 20 mm, bump height 15 ⁇ m) as an evaluation base, and a 200 ⁇ m wide 500 nm-thick aluminum line electrode (light-shielding portion) on the back surface at a pitch of 200 ⁇ m.
  • UV irradiation was performed for 3 seconds from the back side of the glass substrate (aluminum line electrode forming surface) under the UV irradiation conditions shown in Table 1 (UV light source: UV irradiator ZUV-C30H (OMRON Corporation)). Then, an electrical connection for test evaluation was prepared.
  • the die shear strength of the created electrical connector was measured using a die shear tester (universal bond tester series 4000, manufactured by Daisy Japan Co., Ltd.) under the condition of a tool speed of 100 ⁇ m / second. The obtained results are shown in Table 1. Practically, it is desired to be 130 kgf or more.
  • Comparative Example 4 which contained 8 parts by mass of an organic peroxide which is a radical polymerization initiator without containing a photoacid generator, 4 parts by mass of an organic peroxide, and 4 photoacid generators From the comparison with Comparative Example 1 that contained part by mass, it can be seen that the curing reaction was promoted by replacing half of the organic peroxide, which is a radical polymerization initiator, with a photoacid generator. Therefore, it can be seen that the photoacid generator used in Examples 1 to 5 has the property of promoting the thermal radical polymerization reaction of the radical polymerization type adhesive composition.
  • the radical polymerization type adhesive composition of the present invention includes a radical polymerizable compound, a thermal radical polymerization initiator, a photoacid generator having a property of promoting the thermal radical polymerization reaction of the radical polymerization type adhesive composition, a cation
  • the compounding amount of the cationic polymerizable compound with respect to the photoacid generator is limited to a specific range. For this reason, even if there is a light-shielding part such as metal wiring in the electrical parts to be joined, the electrical connection body does not cause warp that is not negligible in practice, and sufficient die shear strength and low conduction resistance value are realized. can do.
  • the radical polymerization type adhesive composition of the present invention has a low conductive resistance value, a good die shear strength, and an electrical connection body produced by connecting electrical components having a light-shielding portion at the joint portion, This is useful for realizing a small amount of warpage.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

A radically polymerizable adhesive agent composition according to the present invention comprises a radically polymerizable compound, a thermal radical polymerization initiator, a cationically polymerizable compound and a photoacid generator. The photoacid generator has a property of accelerating the thermal radical polymerization reaction of the radically polymerizable adhesive agent composition, and the content of the cationically polymerizable compound in the radically polymerizable adhesive agent 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 radically polymerizable adhesive agent composition is 1.0 to 30 parts by mass relative to 100 parts by mass of the thermal radical polymerization initiator.

Description

ラジカル重合型接着剤組成物、及び電気接続体の製造方法Radical polymerization type adhesive composition and method for producing electrical connector
　本発明は、ラジカル重合性化合物と、熱ラジカル重合開始剤と、光酸発生剤と、カチオン重合性化合物とを含有するラジカル重合型接着剤組成物に関する。 The present invention relates to a radical polymerization type adhesive composition containing a radical polymerizable compound, a thermal radical polymerization initiator, a photoacid generator, and a cationic polymerizable compound.
　液晶パネルや有機ＥＬパネル等の電気部品と、ＩＣチップやフレキシブル基板等の別の電気部品とを、硬化型接着剤組成物から形成された未硬化接着剤層を介して重ね合わせた後、その未硬化接着剤層を硬化させて硬化接着剤層とすることにより電気接続体を製造することが広く行われている。この場合、未硬化接着剤層を硬化させるために過度の加熱を行うと、電気接続体に反りが発生したり、電気部品に損傷が発生したりする場合がある。このため、硬化型接着剤組成物として、エポキシ化合物等のカチオン重合性化合物に、光カチオン重合開始剤として光酸発生剤を配合した光カチオン重合型接着剤組成物を使用することが行われている。 After superposing an electrical component such as a liquid crystal panel or an organic EL panel and another electrical component such as an IC chip or a flexible substrate via an uncured adhesive layer formed from a curable adhesive composition, It is widely performed to manufacture an electrical connection body by curing an uncured adhesive layer to form a cured adhesive layer. In this case, if excessive heating is performed to cure the uncured adhesive layer, the electrical connection body may be warped or the electrical component may be damaged. For this reason, as a curable adhesive composition, a cationic photopolymerizable adhesive composition in which a photoacid generator is mixed as a cationic photopolymerization initiator with a cationically polymerizable compound such as an epoxy compound is used. Yes.
　しかしながら、電気部品に金属配線などの遮光部が存在すると、その遮光部により未硬化の接着剤層に光が十分に照射されなくなり、接合部のダイシェア強度の低下が生ずるという問題があった。このため、光カチオン重合型接着剤組成物に、アクリレート系モノマーやオリゴマー等の熱ラジカル重合性化合物と、有機過酸化物等の熱ラジカル重合開始剤とを配合して熱硬化性を付与することが提案されている（特許文献１）。 However, if there is a light shielding part such as a metal wiring in the electrical component, there is a problem that the uncured adhesive layer is not sufficiently irradiated by the light shielding part and the die shear strength of the joint part is lowered. For this reason, the photocation polymerization type adhesive composition is blended with a thermal radical polymerizable compound such as an acrylate monomer or oligomer and a thermal radical polymerization initiator such as an organic peroxide to impart thermosetting properties. Has been proposed (Patent Document 1).
特許第４４６９０８９号Japanese Patent No. 4469089
　ところで、特許文献１に開示されたような硬化型接着剤組成物を用いて導電接続する際の熱圧着操作時の加熱温度は、当該硬化型接着剤組成物を使用して作成された電気接続体に低い導通抵抗値と良好なダイシェア強度とを実現するために、一般に１３０～１８０℃という温度である。 By the way, the heating temperature at the time of thermocompression bonding when conducting conductive connection using a curable adhesive composition as disclosed in Patent Document 1 is an electrical connection created using the curable adhesive composition. In order to achieve a low conduction resistance value and good die shear strength in the body, the temperature is generally 130 to 180 ° C.
　しかしながら、このような温度で熱圧着処理を行うと、実用上無視できない反りが電気接続体に発生してしまうという問題があった。このため、加熱温度を１００℃程度に低下させることが考えられるが、熱硬化反応が不十分となるため、結果的に遮光部の硬化が不十分となり、導通抵抗値の上昇、あるいはダイシェア強度の低下を生じさせてしまうことが懸念されている。 However, when thermocompression treatment is performed at such a temperature, there is a problem that warpage that cannot be ignored in practice occurs in the electrical connection body. For this reason, it is conceivable to lower the heating temperature to about 100 ° C. However, since the thermosetting reaction becomes insufficient, the light-shielding portion is not sufficiently cured, resulting in an increase in conduction resistance value or die shear strength. There is concern that it will cause a decline.
　本発明の目的は、以上の従来の技術の問題点を解決することであり、液晶パネルや有機ＥＬパネル等の電気部品と、ＩＣチップやフレキシブル基板等の別の電気部品とを、硬化型接着剤組成物から形成された未硬化接着剤層を介して重ね合わせた後、その未硬化接着剤層を硬化させて硬化接着剤層とすることにより電気接続体を製造する際に、接合すべき電気部品に金属配線などの遮光部が存在した場合であっても、電気接続体に実用上無視できない反りを発生させず、しかも十分なダイシェア強度と低い導通抵抗値を実現できるようにすることである。 An object of the present invention is to solve the above-described problems of the conventional technology, and an electrical component such as a liquid crystal panel or an organic EL panel and another electrical component such as an IC chip or a flexible substrate are bonded to each other. When the electrical connection body is manufactured by superposing the uncured adhesive layer formed from the adhesive composition and then curing the uncured adhesive layer to form a cured adhesive layer Even if there is a light-shielding part such as a metal wiring in an electrical component, it will not cause a warp that is not negligible in practical use in the electrical connection body, and it will be possible to realize sufficient die shear strength and low conduction resistance value. is there.
　本発明者は、ラジカル重合性化合物と熱ラジカル重合開始剤とカチオン重合性化合物と光酸発生剤とを含有する重合型組成物を電気接続体の製造に適用した場合に、実用上無視できない反りを発生させず、しかも十分なダイシェア強度と低い導通抵抗値を実現できるようにするためには、光酸発生剤としてラジカル重合反応を促進する作用を有するものを使用し、且つ光酸発生剤に対するカチオン重合性化合物の配合量を特定の範囲に制限することにより達成できることを見出し、本発明を完成させるに至った。 When the present inventors applied a polymerizable composition containing a radical polymerizable compound, a thermal radical polymerization initiator, a cationic polymerizable compound, and a photoacid generator to the production of an electrical connector, the warp cannot be ignored in practice. In order to realize a sufficient die shear strength and a low conduction resistance value, a photoacid generator having a function of promoting a radical polymerization reaction is used, and a photoacid generator is used. The inventors have found that this can be achieved by limiting the blending amount of the cationic polymerizable compound to a specific range, and have completed the present invention.
　即ち、本発明は、ラジカル重合性化合物と、熱ラジカル重合開始剤と、カチオン重合性化合物と、光酸発生剤とを含有するラジカル重合型接着剤組成物であって、
　光酸発生剤は、ラジカル重合型接着剤組成物の熱ラジカル重合反応を促進させる性質を有し、
　カチオン重合性化合物のラジカル重合型接着剤組成物中の含有量が、光酸発生剤１質量部に対し、０．２５～３．７５質量部であるラジカル重合型接着剤組成物
を提供する。 That is, the present invention is a radical polymerization type adhesive composition containing a radical polymerizable compound, a thermal radical polymerization initiator, a cationic polymerizable compound, and a photoacid generator,
The photoacid generator has the property of accelerating the thermal radical polymerization reaction of the radical polymerization type adhesive composition,
Provided is a radical polymerization type adhesive composition in which the content of the cationic polymerizable compound in the radical polymerization type adhesive composition is 0.25 to 3.75 parts by mass with respect to 1 part by mass of the photoacid generator.
　また、本発明は、対向配置されるべき二つの電気部品の一方の電気部品の端子上に、接着剤層を配置する工程と、
　前記接着剤層に、他方の電気部品の端子を配置する工程と、
　対向配置された二つの電気部品の一方を他方に向かって押圧しながら、接着剤層に対し加熱と光照射とを行うことにより接着剤層を硬化させて対向配置された二つの電気部品同士を電気的に接続する工程と
を有する電気接続体の製造方法において、
　当該接着剤層が、上述のラジカル重合型接着剤組成物から形成されたものであって、
　接着剤層の硬化の際、光照射により光酸発生剤から酸を発生させ、それによりラジカル重合型接着剤組成物の熱ラジカル重合反応を促進させて接着剤層の硬化を行う製造方法を提供する。 The present invention also includes a step of disposing an adhesive layer on the terminal of one of the two electrical components to be opposed to each other,
Placing the terminals of the other electrical component on the adhesive layer;
While pressing one of the two electrical components facing each other toward the other, heating and irradiating the adhesive layer, the adhesive layer is cured and the two electrical components disposed facing each other In the manufacturing method of the electrical connection body which has the process of electrically connecting,
The adhesive layer is formed from the above-mentioned radical polymerization type adhesive composition,
Provided a manufacturing method for curing an adhesive layer by generating an acid from a photoacid generator by light irradiation when curing the adhesive layer, thereby promoting a thermal radical polymerization reaction of the radical polymerization type adhesive composition To do.
　更に、本発明は、対向配置されるべき二つの電気部品の一方の電気部品の端子上に、接着剤層を配置する工程と、
　前記接着剤層に、他方の電気部品の端子を配置する工程と、
　対向配置された二つの電気部品の一方を他方に向かって押圧しながら、接着剤層に対し加熱と光照射とを行うことにより接着剤層を硬化させて対向配置された二つの電気部品同士を電気的に接続する工程と
を有する電気接続体の製造方法において、
　当該接着剤層が、上述のラジカル重合型接着剤組成物から形成されたものであって、
　接着剤層に対する加熱を、当該ラジカル重合型接着剤組成物から光酸発生剤が取り除かれているものに相当するラジカル重合型対照組成物の熱ラジカル重合反応温度よりも低い温度で行う製造方法を提供する。 Furthermore, the present invention includes a step of disposing an adhesive layer on a terminal of one of the two electrical components to be opposed to each other,
Placing the terminals of the other electrical component on the adhesive layer;
While pressing one of the two electrical components facing each other toward the other, heating and irradiating the adhesive layer, the adhesive layer is cured and the two electrical components disposed facing each other In the manufacturing method of the electrical connection body which has the process of electrically connecting,
The adhesive layer is formed from the above-mentioned radical polymerization type adhesive composition,
A manufacturing method in which heating to the adhesive layer is performed at a temperature lower than the thermal radical polymerization reaction temperature of the radical polymerization control composition corresponding to the radical polymerization adhesive composition from which the photoacid generator has been removed. provide.
　本発明のラジカル重合型接着剤組成物は、ラジカル重合性化合物と、熱ラジカル重合開始剤と、ラジカル重合型接着剤組成物の熱ラジカル重合反応を促進させる性質を有する光酸発生剤と、カチオン重合性化合物とを含有し、しかも、光酸発生剤に対するカチオン重合性化合物の配合量を特定の範囲に限定している。このため、カチオン重合性化合物のカチオン重合は進行するものの、光照射により光酸発生剤が発生した酸がカチオン重合性化合物のカチオン重合のために消費し尽されず、結果的に、ラジカル重合型接着剤組成物の熱ラジカル重合反応を促進させることが可能となる。よって、接合すべき電気部品に金属配線などの遮光部が存在した場合であっても、電気接続体に実用上無視できない反りを発生させず、しかも十分なダイシェア強度と低い導通抵抗値を実現することができる。 The radical polymerization type adhesive composition of the present invention includes a radical polymerizable compound, a thermal radical polymerization initiator, a photoacid generator having a property of promoting the thermal radical polymerization reaction of the radical polymerization type adhesive composition, a cation In addition, the compounding amount of the cationic polymerizable compound with respect to the photoacid generator is limited to a specific range. Therefore, although the cationic polymerization of the cationic polymerizable compound proceeds, the acid generated by the photoacid generator by light irradiation is not consumed for the cationic polymerization of the cationic polymerizable compound, and as a result, radical polymerization type It becomes possible to accelerate the thermal radical polymerization reaction of the adhesive composition. Therefore, even when a light-shielding part such as a metal wiring exists in the electrical parts to be joined, the electric connection body does not generate a warp that cannot be ignored in practice, and a sufficient die shear strength and a low conduction resistance value are realized. be able to.
＜＜ラジカル重合型接着剤組成物＞＞
　本発明のラジカル重合型接着剤組成物は、ラジカル重合性化合物と、熱ラジカル重合開始剤と、光酸発生剤と、カチオン重合性化合物とを含有するものである。光酸発生剤としては、ラジカル重合型接着剤組成物の熱ラジカル重合反応を促進させる性質を有するものを使用する。また、カチオン重合性化合物のラジカル重合型接着剤組成物中の含有量は、光酸発生剤１質量部に対し、０．２５～３．７５質量部である。 << Radical polymerization type adhesive composition >>
The radical polymerization type adhesive composition of the present invention contains a radical polymerizable compound, a thermal radical polymerization initiator, a photoacid generator, and a cationic polymerizable compound. As the photoacid generator, one having a property of promoting the thermal radical polymerization reaction of the radical polymerization type adhesive composition is used. In addition, the content of the cationic polymerizable compound in the radical polymerization adhesive composition is 0.25 to 3.75 parts by mass with respect to 1 part by mass of the photoacid generator.
＜ラジカル重合性化合物＞
　本発明のラジカル重合型接着剤組成物を構成するラジカル重合性化合物は、熱ラジカル重合開始剤の熱分解により生ずる活性ラジカルによりラジカル重合反応し得る化合物であり、好ましくは分子内に１個以上の炭素不飽和結合を有するものであり、いわゆる単官能ラジカル重合性化合物、多官能ラジカル重合性化合物を包含する。ラジカル重合性化合物が、多官能ラジカル重合性化合物を含有した場合には、ラジカル重合型接着剤組成物の硬化物のダイシェア強度をより向上させることが可能となる。従って、ラジカル重合性化合物は、多官能ラジカル重合性化合物を好ましくは３０質量％以上、より好ましくは５０質量％以上含有する。 <Radically polymerizable compound>
The radical polymerizable compound constituting the radical polymerization type adhesive composition of the present invention is a compound capable of undergoing radical polymerization reaction with active radicals generated by thermal decomposition of a thermal radical polymerization initiator, preferably one or more in the molecule. It has a carbon unsaturated bond, 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 die shear strength of the cured product of the radical polymerization adhesive composition can be further improved. Therefore, the radically polymerizable compound preferably contains a polyfunctional radically polymerizable compound in an amount of 30% by mass or more, more preferably 50% by mass or more.
　単官能ラジカル重合性化合物としては、スチレン、メチルスチレン等の単官能ビニル系化合物、ブチルアクリレート、ブチルメタクリレートなどの単官能（メタ）アクリレート系化合物等が挙げられる。ここで、“（メタ）アクリレート”とは、アクリレートとメタクリレートとを包含する用語である。多官能ラジカル重合性化合物としては、ジビニルベンゼン等の多官能ビニル系化合物、１，６－ヘキサンジオールジアクリレート、トリメチロールプロパントリメタクリレート、ビスフェノールＡ型グリシジルメタクリレート（ＥＡ－１０２０、新中村化学（株））、イソシアヌル酸ＥＯ変性ジアクリレート（Ｍ－２１５，東亞合成（株））等の多官能（メタ）アクリレート系化合物を例示することができる。これらはモノマーでもオリゴマーでもよい。中でも、耐熱性の点から多官能（メタ）アクリレート系化合物、特に、ビスフェノールＡ型グリシジルメタクリレート、イソシアヌル酸ＥＯ変性ジアクリレートが好ましい。 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 acrylate and methacrylate. Polyfunctional radical polymerizable compounds include polyfunctional vinyl compounds such as divinylbenzene, 1,6-hexanediol diacrylate, trimethylolpropane trimethacrylate, bisphenol A glycidyl methacrylate (EA-1020, Shin-Nakamura Chemical Co., Ltd.) And polyfunctional (meth) acrylate compounds such as isocyanuric acid EO-modified diacrylate (M-215, Toagosei Co., Ltd.). These may be monomers or oligomers. Of these, polyfunctional (meth) acrylate compounds, particularly bisphenol A-type glycidyl methacrylate and isocyanuric acid EO-modified diacrylate are preferable from the viewpoint of heat resistance.
　なお、多官能ラジカル重合性化合物は、多官能ビニル系化合物と多官能（メタ）アクリレート系化合物とから構成されていてもよい。このように併用することにより、熱応答性のコントロールが可能となり、また、反応性官能基の導入も可能となる。 In addition, the polyfunctional radically polymerizable compound may be composed of a polyfunctional vinyl compound and a polyfunctional (meth) acrylate compound. By using in combination in this way, it becomes possible to control thermal responsiveness and to introduce reactive functional groups.
＜熱ラジカル重合開始剤＞
　本発明のラジカル重合型接着剤組成物を構成する熱ラジカル重合開始剤は、熱分解により、ラジカル重合性化合物をラジカル重合するための活性ラジカルを発生するものであり、公知の熱ラジカル重合開始剤、例えば、有機過酸化物やアゾ系化合物等を好ましく使用することができる。中でも、優れた保存安定性と低温速硬化性とを実現可能である点から、有機過酸化物を好ましく使用することができる。 <Thermal radical polymerization initiator>
The thermal radical polymerization initiator constituting the radical polymerization type adhesive composition of the present invention generates an active radical for radical polymerization of a radical polymerizable compound by thermal decomposition, and is a known thermal radical polymerization initiator. For example, an organic peroxide or an azo compound can be preferably used. Among these, an organic peroxide can be preferably used from the viewpoint that excellent storage stability and low-temperature rapid curability can be realized.
　有機過酸化物としては、熱ラジカル重合開始剤として公知の有機過酸化物、例えば、化学構造的分類の観点からは、ジアシルパーオキサイド、パーオキシジカーボネート、パーオキシエステル、パーオキシケタール、ジアルキルパーオキサイド、ハイドロパーオキサイド、シリルパーオキサイド等を例示することができる。中でも、加熱分解後に発生する有機酸が少ないという点からパーオキシエステル、ジアシルパーオキサイドを好ましく使用することができる。また、１分間半減期温度の観点からは、反応性の点から８０～１７０℃のものが好ましく、また、分子量の観点からは、１８０～１０００のものが好ましい。 As the organic peroxide, an organic peroxide known as a thermal radical polymerization initiator, for example, from the viewpoint of chemical structural classification, diacyl peroxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide. Examples thereof include oxides, hydroperoxides, and silyl peroxides. Among these, peroxyesters and diacyl peroxides can be preferably used from the viewpoint that less organic acid is generated after thermal decomposition. From the viewpoint of half-life temperature for 1 minute, a temperature of 80 to 170 ° C. is preferable from the viewpoint of reactivity, and from the viewpoint of molecular weight, a temperature of 180 to 1000 is preferable.
　なお、アゾ系化合物としては、熱ラジカル重合開始剤として公知のアゾ系化合物を使用することができる。 As the azo compound, a known azo compound can be used as a thermal radical polymerization initiator.
　ラジカル重合型接着剤組成物における熱ラジカル重合開始剤の配合量は、ラジカル重合型接着剤組成物の硬化を十分なものとし、且つ発泡の原因とならないようにするために、ラジカル重合性化合物１００質量部に対し、好ましくは０．５～３０質量部、より好ましくは１．０～２０質量部である。 The amount of the thermal radical polymerization initiator in the radical polymerization adhesive composition is such that the radical polymerization compound 100 is sufficiently cured to prevent the radical polymerization adhesive composition from curing and cause foaming. The amount is preferably 0.5 to 30 parts by mass, more preferably 1.0 to 20 parts by mass with respect to parts by mass.
＜光酸発生剤＞
　本発明のラジカル重合型接着剤組成物を構成する光酸発生剤は、紫外線などの光の照射を受けると酸を発生し、カチオン重合性化合物のカチオン重合を開始させるものであるが、同時に熱ラジカル重合開始剤の分解を促進するものである。換言すれば、光酸発生剤は、ラジカル重合型接着剤組成物の熱ラジカル重合反応を促進させる性質を有するものである。より具体的には、ラジカル重合型接着剤組成物の熱ラジカル重合反応を、当該ラジカル重合型接着剤組成物から更に光酸発生剤が取り除かれているものに相当するラジカル重合型対照組成物の熱ラジカル重合反応よりも促進させることが可能となる。 <Photo acid generator>
The photoacid generator that constitutes the radical polymerization type adhesive composition of the present invention generates an acid when irradiated with light such as ultraviolet rays and initiates cationic polymerization of the cationically polymerizable compound. It promotes the decomposition of the radical polymerization initiator. In other words, the photoacid generator has the property of promoting the thermal radical polymerization reaction of the radical polymerization type adhesive composition. More specifically, the thermal radical polymerization reaction of the radical polymerization adhesive composition is carried out using a radical polymerization control composition corresponding to the radical polymerization adhesive composition in which the photoacid generator is further removed from the radical polymerization adhesive composition. It is possible to promote the thermal radical polymerization reaction.
　従って、光酸発生剤を含有しないラジカル重合型対照組成物の熱ラジカル重合反応温度Ｔ０よりも、光酸発生剤を含有するラジカル重合型接着剤組成物の熱ラジカル重合反応温度Ｔ１は、低いものとなる。ここで、熱ラジカル重合反応温度は、重合物に所期の特性を実現するために必要な反応温度であり、重合系の成分の種類やその配合割合、所期の特性等に応じて設定される重合反応温度である。 Therefore, than the thermal radical polymerization reaction temperature T 0 of containing no photoacid generator radical polymerization type control composition, thermal radical polymerization reaction temperature T 1 of the radical polymerization type adhesive composition containing a photoacid generator, It will be low. Here, the thermal radical polymerization reaction temperature is a reaction temperature necessary for realizing the desired characteristics of the polymer, and is set according to the type of the polymerization system components, the blending ratio thereof, the desired characteristics, etc. Polymerization reaction temperature.
　本発明において、光酸発生剤を含有しないラジカル重合型対照組成物の熱ラジカル重合反応温度Ｔ０は好ましくは１００～１３０℃の範囲である。他方、光酸発生剤を含有するラジカル重合型接着剤組成物の熱ラジカル重合反応温度Ｔ１は、Ｔ０より好ましくは１０℃以上低温である。 In the present invention, the thermal radical polymerization reaction temperature T 0 of the radical polymerization control composition containing no photoacid generator is preferably in the range of 100 to 130 ° C. On the other hand, the thermal radical polymerization reaction temperature T 1 of the radical polymerization type adhesive composition containing the photoacid generator is preferably 10 ° C. or more lower than T 0 .
　このような光酸発生剤としては、光カチオン重合開始剤として使用されている光酸発生剤から適宜選択することができ、オニウム塩、例えば、芳香族ジアゾニウム塩；芳香族スルホニウム塩、脂肪族スルホニウム塩等のスルホニウム塩；ピリジニウム塩；セレノニウム塩；芳香族ヨードニウム塩等のヨードニウム塩；鉄アレーン錯体等の金属アレーン錯体をはじめとする錯体化合物；ベンゾイントシレート、ｏ－ニトロベンジルトシレート等のトシレート化合物等を挙げることができる。中でも、カチオン種の発生効率を向上させることのできる点から、スルホニウム塩、ヨードニウム塩、鉄アレーン錯体を好ましく挙げることができる。特に、光としてＬＥＤ光源からのＩ線（３６５ｎｍ）に対し高感度で反応する芳香族スルホニウム塩、具体的にはトリアリールスルホニウム塩を好ましく挙げることができる。 Such a photoacid generator can be appropriately selected from photoacid generators used as a photocationic polymerization initiator, and is an onium salt such as an aromatic diazonium salt; an aromatic sulfonium salt, an aliphatic sulfonium. Sulfonium salts such as salts; pyridinium salts; selenonium salts; iodonium salts such as aromatic iodonium salts; complex compounds including metal arene complexes such as iron arene complexes; tosylate compounds such as benzoin tosylate and o-nitrobenzyl tosylate Etc. Of these, sulfonium salts, iodonium salts, and iron arene complexes can be preferably mentioned because they can improve the generation efficiency of cationic species. In particular, an aromatic sulfonium salt that reacts with high sensitivity to I-line (365 nm) from an LED light source as light, specifically, a triarylsulfonium salt can be preferably exemplified.
　なお、光酸発生剤が塩である場合には、反応性を向上させる観点から、塩を構成する対アニオンとして、ヘキサフルオロボレート、ヘキサフルオロフォスフェート、テトラフルオロボレート、テトラキス（ペンタフルオロフェニル）ボレート等を好ましく採用することができる。中でも、テトラキス（ペンタフルオロフェニル）ボレートを好ましく採用することができる。 When the photoacid generator is a salt, hexafluoroborate, hexafluorophosphate, tetrafluoroborate, tetrakis (pentafluorophenyl) borate are used as counter anions constituting the salt from the viewpoint of improving reactivity. Etc. can be preferably employed. Of these, tetrakis (pentafluorophenyl) borate can be preferably employed.
　ラジカル重合型接着剤組成物における光酸発生剤の配合量は、熱ラジカル重合開始剤１００質量部に対し、好ましくは１．０～３０質量部、より好ましくは２～２０質量部である。この範囲であれば、熱ラジカル重合開始剤の分解を促進させるという効果が得られる。 The blending amount of the photoacid generator in the radical polymerization type adhesive composition is preferably 1.0 to 30 parts by mass, more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the thermal radical polymerization initiator. If it is this range, the effect of promoting decomposition | disassembly of a thermal radical polymerization initiator will be acquired.
＜カチオン重合性化合物＞
　本発明のラジカル重合型接着剤組成物を構成するカチオン重合性化合物としては、低温速硬化性の点から、環状エーテル系化合物を好ましく挙げることができる。中でも、他の成分との相溶性及び流動性の点から室温で液状のものが好ましい。このような環状エーテル系化合物としては、エポキシ化合物やオキセタン化合物を挙げることができる。コスト、入手容易性等の点からエポキシ化合物を好ましく使用することができる。 <Cationically polymerizable compound>
As the cationically polymerizable compound constituting the radical polymerization type adhesive composition of the present invention, a cyclic ether compound can be preferably mentioned from the viewpoint of low temperature fast curability. Among these, those which are liquid at room temperature are preferable from the viewpoint of compatibility with other components and fluidity. Examples of such cyclic ether compounds include epoxy compounds and oxetane compounds. An epoxy compound can be preferably used from the viewpoints of cost, availability, and the like.
　エポキシ化合物としては、多官能のグリシジルエーテル型エポキシ化合物、脂環式エポキシ化合物合物を好ましく挙げることができる。これらの中では、多官能のグリシジルエーテル型エポキシ化合物を好ましく使用することができる。 Preferred examples of the epoxy compound include polyfunctional glycidyl ether type epoxy compounds and alicyclic epoxy compound compounds. In these, a polyfunctional glycidyl ether type epoxy compound can be used preferably.
　多官能のグリシジルエーテル型エポキシ化合物としては、ビスフェノールＡ型ジグリシジルエーテル及びそのプレポリマー（縮合物）、ビスフェノールＦ型ジグリシジルエーテル及びそのプレポリマー（縮合物）、フェノールノボラック型ジグリシジルエーテル、ジ（β－アルキルグリシジル）レゾルシノールエーテル、ビスフェノールＡ型ジ（β－アルキルグリシジル）エーテル、ビスフェノールＦ型ジ（β－アルキルグリシジル）エーテル等が挙げられる。 Polyfunctional glycidyl ether type epoxy compounds include bisphenol A type diglycidyl ether and its prepolymer (condensate), bisphenol F type diglycidyl ether and its prepolymer (condensate), phenol novolac type diglycidyl ether, di ( β-alkyl glycidyl) resorcinol ether, bisphenol A type di (β-alkyl glycidyl) ether, bisphenol F type di (β-alkyl glycidyl) ether, and the like.
　このようなエポキシ化合物のエポキシ当量は、好ましくは１００～５００、より好ましくは１４０～３００である。 The epoxy equivalent of such an epoxy compound is preferably 100 to 500, more preferably 140 to 300.
　ラジカル重合型接着剤組成物におけるエポキシ化合物等のカチオン重合性化合物の配合量は、光酸発生剤１質量部に対し、１～１５質量部、好ましくは１～３質量部である。この範囲であれば、光酸発生剤がラジカル重合反応を促進させる効果と、カチオン重合性化合物との反応が可能となる。 The blending amount of the cationic polymerizable compound such as an epoxy compound in the radical polymerization type adhesive composition is 1 to 15 parts by mass, preferably 1 to 3 parts by mass with respect to 1 part by mass of the photoacid generator. If it is this range, the effect with which a photo-acid generator accelerates | stimulates a radical polymerization reaction and reaction with a cationically polymerizable compound will be attained.
＜その他の成分＞
　本発明のラジカル重合型接着剤組成物は、更に、フェノキシ樹脂等の熱可塑性樹脂を成膜用樹脂として含有することができる。このような熱可塑性樹脂の配合量は、ラジカル重合性化合物１００質量部に対し、好ましくは１０～７０質量部、より好ましくは２０～６０質量部である。 <Other ingredients>
The radical polymerization type adhesive composition of the present invention can further contain a thermoplastic resin such as a phenoxy resin as a film-forming resin. The blending amount of such a thermoplastic resin is preferably 10 to 70 parts by mass, more preferably 20 to 60 parts by mass with respect to 100 parts by mass of the radical polymerizable compound.
　また、本発明のラジカル重合型接着剤組成物は、公知のシランカップリング剤を含有することができる。シランカップリング剤の配合量は、ラジカル重合性化合物１００質量部に対し、好ましくは０．１～２０質量部、より好ましくは０．５～１０質量部である。この範囲であれば、無機・金属系材料に対する接着性が向上するという効果が得られる。 Moreover, the radical polymerization type adhesive composition of the present invention can contain a known silane coupling agent. The blending amount of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the radical polymerizable compound. If it is this range, the effect that the adhesiveness with respect to an inorganic and metal type material will improve is acquired.
　本発明のラジカル重合型接着剤組成物は、必要に応じ、公知の光ラジカル重合開始剤、無機フィラ、有機フィラ、導電フィラ、絶縁フィラ等を含有することができる。 The radical polymerization type adhesive composition of the present invention can contain a known radical photopolymerization initiator, an inorganic filler, an organic filler, a conductive filler, an insulating filler, etc., if necessary.
＜ラジカル重合型接着剤組成物の調製＞
　本発明のラジカル重合型接着剤組成物は、ラジカル重合性化合物と、熱ラジカル重合開始剤と、光酸発生剤と、カチオン重合性化合物と、必要に応じて配合される熱可塑性樹脂等の他の成分とを、公知の混合手段により均一に混合することにより調製することができる。 <Preparation of radical polymerization type adhesive composition>
The radical polymerization type adhesive composition of the present invention includes a radical polymerizable compound, a thermal radical polymerization initiator, a photoacid generator, a cationic polymerizable compound, and a thermoplastic resin blended as necessary. Can be prepared by uniformly mixing them with a known mixing means.
＜＜電気接続体の製造方法：その１＞＞
　本発明の電気接続体の製造方法（その１）は、以下の工程（イ）～（ハ）を有する。以下に工程毎に説明する。 << Method for manufacturing electrical connector: Part 1 >>
The method for manufacturing an electrical connection body according to the present invention (part 1) includes the following steps (a) to (c). Below, it demonstrates for every process.
＜工程（イ）＞
　対向配置されるべき二つの電気部品の一方の電気部品の端子上に、公知の手法に従って接着剤層を配置する。ここで、対向配置されるべき二つの電気部品の一方としては、リジッド回路基板、フレキシブル配線基板等が挙げられる。それらの端子としては、銅、アルミニウム、銀、金、ＩＴＯ等の電極材料から形成されたパッド電極、ライン電極、バンプ電極等が挙げられる。また、接着層は、前述した本発明のラジカル重合型接着剤組成物から形成されたものである。かかる接着層の形成は、公知の手法、例えば、各種塗布法や印刷法、更にはフォトリソグラフ技術などを利用して行うことができる。 <Process (I)>
An adhesive layer is disposed on a terminal of one of the two electrical components to be disposed to face each other according to a known technique. Here, a rigid circuit board, a flexible wiring board, etc. are mentioned as one of the two electric components which should be arrange | positioned facing each other. Examples of these terminals include pad electrodes, line electrodes, and bump electrodes formed from electrode materials such as copper, aluminum, silver, gold, and ITO. Further, the adhesive layer is formed from the radical polymerization type adhesive composition of the present invention described above. Such an adhesive layer can be formed by using a known method, for example, various coating methods, printing methods, and photolithographic techniques.
＜工程（ロ）＞
　次に、工程（イ）で形成された接着剤層に、他方の電気部品の端子を公知の手法に従って配置する。他方の電気部品としては、ＩＣチップ、液晶パネル、有機ＥＬパネル、ＩＣモジュール、太陽電池モジュール等が挙げられる。それらの端子としては、銅、アルミニウム、銀、金、ＩＴＯ等の電極材料から形成されたパッド電極、ライン電極、バンプ電極等が挙げられる。 <Process (b)>
Next, the terminal of the other electrical component is placed on the adhesive layer formed in the step (A) according to a known method. Examples of the other electrical component include an IC chip, a liquid crystal panel, an organic EL panel, an IC module, and a solar cell module. Examples of these terminals include pad electrodes, line electrodes, and bump electrodes formed from electrode materials such as copper, aluminum, silver, gold, and ITO.
＜工程（ハ）＞
　工程（ロ）において対向配置された二つの電気部品の一方を他方に向かって、公知の加熱加圧ツールを用いて押圧しながら、接着剤層に対し加熱を行う。この加熱と同時に若しくは組成物の軟化若しくは溶融を待って、加熱開始後、加熱を継続しながら好ましくは２、３秒後から接着剤層に対し紫外線等の光、好ましくはＬＥＤ光源のＩ線を用いて光照射を行い、接着剤層を硬化させる。ここで、少なくとも一方の電気部品が透明基板の片面に遮光部となり得る金属端子が形成されたものである場合、接着剤層への光照射を、電気部品の透明基板の他面側から行うことが好ましい。このように硬化させることにより電気接続体が得られる。この際、光照射により光酸発生剤から酸を発生させ、それによりカチオン重合性化合物をカチオン重合させると共に、ラジカル重合型接着剤組成物の熱ラジカル重合を、当該ラジカル重合型接着剤組成物から光酸発生剤を取り除いたものに相当するラジカル重合型対照組成物の熱ラジカル重合よりも促進させて接着剤層の硬化を行う。これにより、遮光部が存在したとしても接着剤層を十分に硬化させることができ、対向配置された二つの電気部品同士を低い導電抵抗値で接続することができる。しかも、良好なダイシェア強度を実現することができ、また、電気接続体に反りが発生することを抑制することができる。 <Process (C)>
In the step (b), the adhesive layer is heated while pressing one of the two electric components opposed to each other with a known heating and pressing tool. Simultaneously with this heating or waiting for softening or melting of the composition, after the heating is started, the heating is continued, preferably after 2 or 3 seconds, light such as ultraviolet rays, preferably the I-line of the LED light source, is applied to the adhesive layer. It is irradiated with light to cure the adhesive layer. Here, when at least one of the electrical components has a metal terminal that can serve as a light-shielding part on one side of the transparent substrate, light irradiation to the adhesive layer is performed from the other side of the transparent substrate of the electrical component. Is preferred. An electrical connector is obtained by curing in this way. At this time, an acid is generated from the photoacid generator by light irradiation, thereby cationically polymerizing the cation polymerizable compound, and thermal radical polymerization of the radical polymerization adhesive composition is performed from the radical polymerization adhesive composition. The adhesive layer is cured by accelerating the thermal radical polymerization of the radical polymerization control composition corresponding to the photoacid generator removed. Thereby, even if there exists a light-shielding part, an adhesive bond layer can fully be hardened and two electric components arranged facing each other can be connected by a low conductive resistance value. In addition, good die shear strength can be achieved, and warpage of the electrical connection body can be suppressed.
＜＜電気接続体の製造方法：その２＞＞
　本発明の電気接続体の製造方法（その２）は、製造方法（その１）の工程（イ）～（ハ）と同様の工程を有するが、工程（ハ）において、接着剤層に対する加熱を、当該ラジカル重合型接着剤組成物から更に光酸発生剤が取り除かれているものに相当するラジカル重合型対照組成物の熱ラジカル重合反応温度よりも低い温度で行うという具体的な加熱条件を明示している点で異なる。熱ラジカル重合反応温度Ｔ０よりも低い温度で加熱硬化を行うので、電気接合体の反りの発生を抑制でき、しかも光酸発生剤が発生する酸により、ラジカル重合型接着剤組成物の熱ラジカル重合反応温度Ｔ１がＴ０よりも低くなっているので、十分に硬化させることが可能となり、対向配置された二つの電気部品同士を低い導電抵抗値で接続することができる。しかも、良好なダイシェア強度を実現することができ、また、電気接続体に反りが発生することを抑制することができる。 << Method for manufacturing electrical connector: Part 2 >>
The manufacturing method (part 2) of the electrical connection body of the present invention has the same steps as steps (a) to (c) of the manufacturing method (part 1). In the step (c), the adhesive layer is heated. Clarify the specific heating conditions to be performed at a temperature lower than the thermal radical polymerization reaction temperature of the radical polymerization control composition corresponding to the radical polymerization adhesive composition from which the photoacid generator is further removed. It differs in that it is. Since heat curing is performed at a temperature lower than the thermal radical polymerization reaction temperature T 0, it is possible to suppress the warpage of the electric bonded body, and the heat radical of the radical polymerization type adhesive composition is generated by the acid generated by the photoacid generator. Since the polymerization reaction temperature T 1 is lower than T 0, it can be sufficiently cured, and the two electric components arranged opposite to each other can be connected with a low conductive resistance value. In addition, good die shear strength can be achieved, and warpage of the electrical connection body can be suppressed.
　以下、本発明を実施例により具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to examples.
　　実施例１～５、比較例１～４
　表１に示す配合組成の成分を常法にて混合して得た混合物（接着剤組成物）を剥離ポリエステルフィルムに塗布し、７０℃で乾燥することにより、２０μｍ厚の接着シートを得た。 Examples 1 to 5 and Comparative Examples 1 to 4
A mixture (adhesive composition) obtained by mixing the components of the composition shown in Table 1 by a conventional method was applied to a release polyester film and dried at 70 ° C. to obtain an adhesive sheet having a thickness of 20 μm.
＜導通抵抗測定、ダイシェア強度測定、反り量測定用の電気接続体の作成＞
　得られた接着シートを、評価基材としてのＩＣ（外寸：１．８ｍｍ×２０ｍｍ、バンプ高さ１５μｍ）と、裏面に２００μｍ巾の５００ｎｍ厚のアルミニウムライン電極（遮光部）を２００μｍピッチで設けたベースガラス基板としてのＩＴＯコーティングガラス（ガラス厚０．５ｍｍ、ＩＴＯ厚２００ｎｍ）との間に挟み、圧着温度１００℃、圧着圧力８０ＭＰａ、圧着時間５秒間という条件でＩＣを加熱加圧し、加熱開始後２秒後に表１のＵＶ照射条件（ＵＶ光源：ＵＶ照射器ＺＵＶ－Ｃ３０Ｈ（オムロン（株））でＵＶ照射を、ガラス基板の裏面側（アルミニウムライン電極形成面側）から３秒間行うことにより、試験評価用の電気接続体を作成した。 <Conduction resistance measurement, die shear strength measurement, creation of electrical connection body for warpage measurement>
The obtained adhesive sheet is provided with an IC (outside dimension: 1.8 mm × 20 mm, bump height 15 μm) as an evaluation base, and a 200 μm wide 500 nm-thick aluminum line electrode (light-shielding portion) on the back surface at a pitch of 200 μm. Sandwiched between ITO coated glass (glass thickness 0.5mm, ITO thickness 200nm) as the base glass substrate, heat-pressed the IC under the conditions of pressure bonding temperature 100 ° C, pressure bonding pressure 80MPa, pressure bonding time 5 seconds, and start heating 2 seconds later, UV irradiation was performed for 3 seconds from the back side of the glass substrate (aluminum line electrode forming surface) under the UV irradiation conditions shown in Table 1 (UV light source: UV irradiator ZUV-C30H (OMRON Corporation)). Then, an electrical connection for test evaluation was prepared.
＜電気接続体の導通抵抗値の測定＞
　作成した電気接続体に対し、８５℃、８５％ＲＨの高温高湿槽に５００時間放置というエージングテストを行った。そのエージングテストの前後において、電気接続体に２ｍＡの電流を流した際の当該電気接続体の導通抵抗値を、抵抗測定機（デジタルマルチメータ７５５５、横河電機（株）製）を用いて４端子法にて測定した。得られた結果を表１に示す。実用上、エージングテスト前においては１．０Ω以下であることが望まれ、エージングテスト後においては１０Ω以下であることが望まれる。 <Measurement of conduction resistance value of electrical connection body>
An aging test was performed on the prepared electrical connection body by leaving it in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 500 hours. Before and after the aging test, the conduction resistance value of the electrical connection body when a current of 2 mA was passed through the electrical connection body was 4 using a resistance measuring machine (Digital Multimeter 7555, manufactured by Yokogawa Electric Corporation). Measured by the terminal method. The obtained results are shown in Table 1. Practically, it is desirable that it is 1.0Ω or less before the aging test, and it is desirable that it is 10Ω or less after the aging test.
＜電気接続体のダイシェア強度の測定＞
　作成した電気接続体のダイシェア強度を、ダイシェアテスター（万能型ボンドテスターシリーズ４０００、デイジ・ジャパン（株）製）を用いて、ツール速度１００μｍ／秒という条件で測定した。得られた結果を表１に示す。実用上、１３０ｋｇｆ以上であることが望まれる。 <Measurement of die shear strength of electrical connector>
The die shear strength of the created electrical connector was measured using a die shear tester (universal bond tester series 4000, manufactured by Daisy Japan Co., Ltd.) under the condition of a tool speed of 100 μm / second. The obtained results are shown in Table 1. Practically, it is desired to be 130 kgf or more.
＜電気接続体の反り量の測定＞
　作成した電気接続体のガラス基板のアルミニウムライン電極形成面を、触針式表面粗度計（ＳＥ－３Ｈ、（株）小坂研究所）のプローブで走査し、反り量（μｍ）を測定した。得られた結果を表１に示す。実用上、１０μｍ以下であることが望まれる。 <Measurement of warpage of electrical connection body>
The aluminum line electrode formation surface of the glass substrate of the prepared electrical connector was scanned with a probe of a stylus type surface roughness meter (SE-3H, Kosaka Laboratory Ltd.), and the amount of warpage (μm) was measured. The obtained results are shown in Table 1. Practically, it is desired to be 10 μm or less.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
＜表１の結果の考察＞
（１）光酸発生剤を含有せずにラジカル重合開始剤である有機過酸化物を８質量部含有していた比較例４と、有機過酸化物を４質量部と光酸発生剤を４質量部とを含有していた比較例１との対比から、ラジカル重合開始剤である有機過酸化物の半量を光酸発生剤に代えると、硬化反応が促進されていることがわかる。従って、実施例１～５で使用された光酸発生剤が、ラジカル重合型接着剤組成物の熱ラジカル重合反応を促進させる性質を有していることがわかる。 <Discussion of results in Table 1>
(1) Comparative Example 4 which contained 8 parts by mass of an organic peroxide which is a radical polymerization initiator without containing a photoacid generator, 4 parts by mass of an organic peroxide, and 4 photoacid generators From the comparison with Comparative Example 1 that contained part by mass, it can be seen that the curing reaction was promoted by replacing half of the organic peroxide, which is a radical polymerization initiator, with a photoacid generator. Therefore, it can be seen that the photoacid generator used in Examples 1 to 5 has the property of promoting the thermal radical polymerization reaction of the radical polymerization type adhesive composition.
（２）ラジカル重合性化合物、ラジカル重合開始剤（有機過酸化物）、ラジカル重合型接着剤組成物の熱ラジカル重合反応を促進させる性質を有している光酸発生剤、及びカチオン重合性化合物を含有する実施例１～５のラジカル重合性接着剤組成物は、エージングテスト前後で実用上問題のない「導通抵抗値」を示していることがわかる。また、「ダイシェア強度」や「反り量」についても実用上問題のない結果を示した。 (2) a radically polymerizable compound, a radical polymerization initiator (organic peroxide), a photoacid generator having a property of accelerating a thermal radical polymerization reaction of a radical polymerization type adhesive composition, and a cationically polymerizable compound It can be seen that the radically polymerizable adhesive compositions of Examples 1 to 5 containing the above show “conducting resistance values” having no practical problem before and after the aging test. In addition, “die shear strength” and “warp amount” showed no problem in practical use.
（３）また、実施例１～５と、カチオン重合性化合物が配合されていない比較例１並びにカチオン重合性化合物が２０質量部配合されている比較例２とを対比すると、光酸発生剤１質量部に対するカチオン重合性化合物の好ましい配合量が１～１５質量部であることがわかる。 (3) Further, comparing Examples 1 to 5 with Comparative Example 1 in which no cationically polymerizable compound was blended and Comparative Example 2 in which 20 parts by mass of the cationically polymerizable compound was blended, photoacid generator 1 It can be seen that the preferred blending amount of the cationically polymerizable compound with respect to parts by mass is 1 to 15 parts by mass.
（４）なお、比較例３の場合、ラジカル重合開始剤（有機過酸化物）とカチオン重合性化合物が含まれていないので、硬化反応が進行しないことがわかる。 (4) In the case of Comparative Example 3, since the radical polymerization initiator (organic peroxide) and the cationic polymerizable compound are not included, it can be seen that the curing reaction does not proceed.
　本発明のラジカル重合型接着剤組成物は、ラジカル重合性化合物と、熱ラジカル重合開始剤と、ラジカル重合型接着剤組成物の熱ラジカル重合反応を促進させる性質を有する光酸発生剤と、カチオン重合性化合物とを含有し、しかも、光酸発生剤に対するカチオン重合性化合物の配合量を特定の範囲に限定している。このため、接合すべき電気部品に金属配線などの遮光部が存在した場合であっても、電気接続体に実用上無視できない反りを発生させず、しかも十分なダイシェア強度と低い導通抵抗値を実現することができる。従って、本発明のラジカル重合型接着剤組成物は、接合部分に遮光部が存在する電気部品同士を接続して電気接続体を製造する際に、低い導電抵抗値と、良好なダイシェア強度と、小さな反り量とを実現するために有用である。
  The radical polymerization type adhesive composition of the present invention includes a radical polymerizable compound, a thermal radical polymerization initiator, a photoacid generator having a property of promoting the thermal radical polymerization reaction of the radical polymerization type adhesive composition, a cation In addition, the compounding amount of the cationic polymerizable compound with respect to the photoacid generator is limited to a specific range. For this reason, even if there is a light-shielding part such as metal wiring in the electrical parts to be joined, the electrical connection body does not cause warp that is not negligible in practice, and sufficient die shear strength and low conduction resistance value are realized. can do. Therefore, the radical polymerization type adhesive composition of the present invention has a low conductive resistance value, a good die shear strength, and an electrical connection body produced by connecting electrical components having a light-shielding portion at the joint portion, This is useful for realizing a small amount of warpage.

Claims (12)

  1. 　ラジカル重合性化合物と、熱ラジカル重合開始剤と、カチオン重合性化合物と、光酸発生剤とを含有するラジカル重合型接着剤組成物であって、
    　光酸発生剤は、ラジカル重合型接着剤組成物の熱ラジカル重合反応を促進させる性質を有し、
    　カチオン重合性化合物のラジカル重合型接着剤組成物中の含有量が、光酸発生剤１質量部に対し、０．２５～３．７５質量部であるラジカル重合型接着剤組成物。     A radical polymerizable adhesive composition containing a radical polymerizable compound, a thermal radical polymerization initiator, a cationic polymerizable compound, and a photoacid generator,
    The photoacid generator has the property of accelerating the thermal radical polymerization reaction of the radical polymerization type adhesive composition,
    A radical polymerization type adhesive composition in which the content of the cationic polymerizable compound in the radical polymerization type adhesive composition is 0.25 to 3.75 parts by mass with respect to 1 part by mass of the photoacid generator.
  2. 　光酸発生剤のラジカル重合型接着剤組成物中の含有量が、熱ラジカル重合開始剤１００質量部に対し、１．０～３０質量部である請求項１記載のラジカル重合型接着剤組成物。 The radical polymerization adhesive composition according to claim 1, wherein the content of the photoacid generator in the radical polymerization adhesive composition is 1.0 to 30 parts by mass with respect to 100 parts by mass of the thermal radical polymerization initiator. .
  3. 　カチオン重合性化合物が、エポキシ化合物である請求項１又は２記載のラジカル重合型接着剤組成物。 The radical polymerizable adhesive composition according to claim 1 or 2, wherein the cationic polymerizable compound is an epoxy compound.
  4. 　エポキシ化合物のエポキシ当量が、１００～５００である請求項３記載のラジカル重合型接着剤組成物。 The radical polymerization adhesive composition according to claim 3, wherein the epoxy equivalent of the epoxy compound is 100 to 500.
  5. 　熱ラジカル重合開始剤が有機過酸化物であり、光酸発生剤がスルホニウム塩、ヨードニウム塩又は鉄アレーン錯体である請求項１～４のいずれかに記載のラジカル重合型接着剤組成物。 The radical polymerization adhesive composition according to any one of claims 1 to 4, wherein the thermal radical polymerization initiator is an organic peroxide and the photoacid generator is a sulfonium salt, an iodonium salt or an iron arene complex.
  6. 　熱ラジカル重合開始剤である有機過酸化物が１分間半減期温度８０～１７０℃且つ分子量１８０～１０００のパーオキシエステル又はジアシルパーオキサイドであり、光酸発生剤がトリアリールスルホニウム塩である請求項５記載のラジカル重合型接着剤組成物。 The organic peroxide as a thermal radical polymerization initiator is a peroxyester or diacyl peroxide having a half-life temperature of 80 to 170 ° C and a molecular weight of 180 to 1000 for 1 minute, and the photoacid generator is a triarylsulfonium salt. 5. The radical polymerization type adhesive composition according to 5.
  7. 　対向配置されるべき二つの電気部品の一方の電気部品の端子上に、接着剤層を配置する工程と、
    　前記接着剤層に、他方の電気部品の端子を配置する工程と、
    　対向配置された二つの電気部品の一方を他方に向かって押圧しながら、接着剤層に対し加熱と光照射とを行うことにより接着剤層を硬化させて対向配置された二つの電気部品同士を電気的に接続する工程と
    を有する電気接続体の製造方法において、
    　当該接着剤層が、請求項１～６のいずれかに記載のラジカル重合型接着剤組成物から形成されたものであって、
    　接着剤層の硬化の際、光照射により光酸発生剤から酸を発生させ、それによりラジカル重合型接着剤組成物の熱ラジカル重合反応を促進させて接着剤層の硬化を行う製造方法。     Placing an adhesive layer on the terminals of one of the two electrical components to be placed opposite each other;
    Placing the terminals of the other electrical component on the adhesive layer;
    While pressing one of the two electrical components facing each other toward the other, heating and irradiating the adhesive layer, the adhesive layer is cured and the two electrical components disposed facing each other In the manufacturing method of the electrical connection body which has the process of electrically connecting,
    The adhesive layer is formed from the radical polymerization adhesive composition according to any one of claims 1 to 6,
    A production method for curing an adhesive layer by generating an acid from a photoacid generator by light irradiation during curing of the adhesive layer, thereby promoting a thermal radical polymerization reaction of the radical polymerization type adhesive composition.
  8. 　対向配置されるべき二つの電気部品の一方の電気部品の端子上に、接着剤層を配置する工程と、
    　前記接着剤層に、他方の電気部品の端子を配置する工程と、
    　対向配置された二つの電気部品の一方を他方に向かって押圧しながら、接着剤層に対し加熱と光照射とを行うことにより接着剤層を硬化させて対向配置された二つの電気部品同士を電気的に接続する工程と
    を有する電気接続体の製造方法において、
    　当該接着剤層が、請求項１～６のいずれかに記載のラジカル重合型接着剤組成物から形成されたものであって、
    　接着剤層に対する加熱を、当該ラジカル重合型接着剤組成物から光酸発生剤が取り除かれているものに相当するラジカル重合型対照組成物の熱ラジカル重合反応温度よりも低い温度で行う製造方法。     Placing an adhesive layer on the terminals of one of the two electrical components to be placed opposite each other;
    Placing the terminals of the other electrical component on the adhesive layer;
    While pressing one of the two electrical components facing each other toward the other, heating and irradiating the adhesive layer, the adhesive layer is cured and the two electrical components disposed facing each other In the manufacturing method of the electrical connection body which has the process of electrically connecting,
    The adhesive layer is formed from the radical polymerization adhesive composition according to any one of claims 1 to 6,
    A production method in which the adhesive layer is heated at a temperature lower than the thermal radical polymerization reaction temperature of the radical polymerization control composition corresponding to the radical polymerization adhesive composition from which the photoacid generator has been removed.
  9. 　少なくとも一方の電気部品が透明基板の片面に金属端子が形成されたものであり、接着剤層への光照射を、該電気部品の透明基板の他面側から行う請求項７又は８記載の製造方法。 The manufacturing method according to claim 7 or 8, wherein at least one of the electrical components has a metal terminal formed on one side of the transparent substrate, and the adhesive layer is irradiated with light from the other side of the transparent substrate. Method.
  10. 　接着剤層に対する加熱を行った後に、光照射を行う請求項７～９のいずれかに記載の製造方法。 The production method according to any one of claims 7 to 9, wherein the adhesive layer is heated after being heated.
  11. 　熱ラジカル重合開始剤が有機過酸化物であり、光酸発生剤がスルホニウム塩、ヨードニウム塩又は鉄アレーン錯体である請求項７～１０のいずれかに記載の製造方法。 The production method according to any one of claims 7 to 10, wherein the thermal radical polymerization initiator is an organic peroxide, and the photoacid generator is a sulfonium salt, an iodonium salt or an iron arene complex.
  12. 　熱ラジカル重合開始剤である有機過酸化物が１分間半減期温度８０～１７０℃且つ分子量１８０～１０００のパーオキシエステル又はジアシルパーオキサイドであり、光酸発生剤がトリアリールスルホニウム塩である請求項１１記載の製造方法。
     
          The organic peroxide as a thermal radical polymerization initiator is a peroxyester or diacyl peroxide having a half-life temperature of 80 to 170 ° C and a molecular weight of 180 to 1000 for 1 minute, and the photoacid generator is a triarylsulfonium salt. 11. The production method according to 11.

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