JP2015025074A - Circuit connection material, circuit connection structure, method for manufacturing circuit connection structure, adhesive composition, and adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a circuit connection material capable of yielding a circuit connection structure exhibiting, even in a case where circuit members are connected to each other at a low temperature of approximately 120°C, a sufficient adhesive strength and having an excellent connection reliability of maintaining a sufficiently low connection resistance between opposing electrodes even within a high-temperature, high-humidity environment.SOLUTION: The circuit connection material of the present invention is a circuit connection material including radical-polymerizable substances and a radical polymerization initiator and used for connecting circuit members possessing mutually opposing circuit electrodes. In the circuit connection material, a first radical-polymerizable substance expressed by the following general formula (1) and a second radical-polymerizable substance other than the first radical-polymerizable substance and possessing two or more (meth)acryloyl groups are included as the radical-polymerizable substances and dilauroyl peroxide is included as the radical polymerization initiator: [in the formula (1), Xand Xmay be identical or different and express an acryloyl group, a methacryloyl group, or a hydrogen atom, although at least either of them expresses an acryloyl group or a methacryloyl group; n expresses an integer of 8 to 15].

Description

  The present invention relates to a circuit connection material, a circuit connection structure, a method for manufacturing a circuit connection structure, an adhesive composition, and an adhesive sheet.

  As a circuit connection material for a semiconductor element or a liquid crystal display element, a thermosetting resin composition using an epoxy resin having high adhesion and high reliability is known (for example, see Patent Document 1). As a component of the thermosetting resin composition, a curing agent such as an epoxy resin, a phenol resin having reactivity with the epoxy resin, and a latent curing agent that accelerates the reaction between the epoxy resin and the curing agent are generally used. . A latent curing agent may be used for the purpose of ensuring storage stability at room temperature. The latent curing agent is an important factor for determining the curing temperature and the curing rate, and various compounds are used from the viewpoint of storage stability at room temperature and curing rate during heating.

  Recently, radically curable adhesives using radically polymerizable substances such as acrylate derivatives and methacrylate derivatives in combination with peroxides as radical polymerization initiators have attracted attention. The radical curable adhesive can be cured at a low temperature and in a short time because radicals that are reactive species are rich in reactivity (see, for example, Patent Documents 2 and 3).

  By the way, input devices typified by touch panels are widely used as display devices become more multifunctional. Also in the manufacture of this touch panel, a circuit connection material is used for connection between the touch panel sensor and peripheral circuit members.

  Depending on the display device, the configuration of the mounted touch panel is different and diversified. In the case of multifunctional mobile phones (smartphones) and tablet PCs, polyethylene terephthalate (PET), polycarbonate (PC), polyethylene naphthalate (PEN), etc. are considered as base films for touch panel sensors from the viewpoint of low cost and light weight. Or it is being applied. On the other hand, in the case of a liquid crystal display, since the circuit formation technology cultivated by manufacturing the liquid crystal display can be diverted, there are not a few examples of liquid crystal display manufacturers producing touch panels with touch panel sensors on glass. In a liquid crystal display equipped with this touch panel, the glass on which the touch panel sensor is provided and the glass of the liquid crystal display are commonly used for thinning, so a polarizing film having low heat resistance is located in the vicinity of the connection part of the circuit member. Will do.

Japanese Patent Laid-Open No. 1-113480 JP 2002-203427 A International Publication No. WO98 / 044067

  As described above, when the base of the touch panel sensor is a resin film or when there is a member with low heat resistance, a further lower temperature is required for the connection between the sensor of the touch panel and the circuit member even if it is a radical curable adhesive. It is done.

  In order to improve the low temperature activity of the radical curable adhesive, it is conceivable to increase the amount of the radical polymerization initiator. However, it has been clarified by the present inventors that the connection resistance value between opposing electrodes may increase in a high-temperature and high-humidity environment in a circuit connection structure that secures adhesive strength by such a method. did.

  In the present invention, even when the circuit members are connected to each other at a low temperature of about 120 ° C., they have sufficient adhesive strength and the connection resistance between the opposing electrodes is maintained sufficiently low even in a high temperature and high humidity environment. An object of the present invention is to provide a circuit connection material, an adhesive composition, and an adhesive sheet capable of obtaining a circuit connection structure excellent in connection reliability. In addition, the present invention provides a circuit connection structure having sufficient connection strength and excellent connection reliability in which connection resistance between opposing electrodes is maintained sufficiently low even in a high temperature and high humidity environment, and a method for manufacturing the circuit connection structure. The purpose is to do.

  The present invention is a circuit connection material for connecting circuit members having circuit electrodes facing each other, which contains a radical polymerizable substance and a radical polymerization initiator, and includes the following general formula (1) as a radical polymerizable substance: And a second radical polymerizable substance having two or more (meth) acryloyl groups other than the first radical polymerizable substance, and having a divalent radical polymerization initiator as a radical polymerization initiator. A circuit connection material containing lauroyl peroxide is provided.

式（１）中、Ｘ_１及びＸ_２は同一でも異なってもよく、アクリロイル基［ＣＨ_２＝ＣＨ−Ｃ（＝Ｏ）−］、メタクリロイル基［ＣＨ_２＝Ｃ（ＣＨ_３）−Ｃ（＝Ｏ）−］又は水素原子［Ｈ−］を表し、少なくとも一方はアクリロイル基又はメタクリロイル基であり、ｎは８〜１５の整数を表す。

In the formula (1), X ₁ and X ₂ may be the same or different, and an acryloyl group [CH ₂ ═CH—C (═O) —], a methacryloyl group [CH ₂ ═C (CH ₃ ) —C (= O)-] or a hydrogen atom [H-], at least one of which is an acryloyl group or a methacryloyl group, and n represents an integer of 8-15.

  According to the circuit connecting material according to the present invention, even when circuit members are connected at a low temperature of around 120 ° C., the connection between the electrodes having sufficient adhesive strength and facing each other even in a high temperature and high humidity environment. A circuit connection structure excellent in connection reliability in which the resistance is maintained sufficiently low can be obtained.

  The content of dilauroyl peroxide in the circuit connecting material according to the present invention is preferably 10 to 40 parts by mass with respect to 100 parts by mass of the total amount of radical polymerizable substances contained in the circuit connecting material. By setting the content of dilauroyl peroxide within such a numerical range, circuit members can be connected to each other with sufficient adhesive strength, and an increase in connection resistance value in a high-temperature and high-humidity environment can be sufficiently suppressed.

  Moreover, it is preferable that content of a 1st radically polymerizable substance is 30-100 mass parts with respect to 100 mass parts of dilauroyl peroxide content. By setting the content of the first radical polymerizable substance within such a numerical range, circuit members can be connected with sufficient adhesive strength, and an increase in connection resistance value in a high temperature and high humidity environment can be sufficiently suppressed. it can.

  The circuit connecting material according to the present invention preferably further contains a thermoplastic resin. In this case, it is possible to realize a circuit connection material that improves the handleability of the circuit connection material and is excellent in stress relaxation during curing.

  The thermoplastic resin is preferably a polyester urethane resin.

  The circuit connection material according to the present invention preferably further contains a third radical polymerizable substance having a phosphate structure. In this case, the adhesive strength to the surface of an inorganic substance such as metal can be improved.

  The third radical polymerizable substance is preferably a compound represented by the following general formula (2).

式（２）中、Ｒはメチル基又は水素原子を表し、ｎは１〜２の整数を表す。

In formula (2), R represents a methyl group or a hydrogen atom, and n represents an integer of 1 to 2.

  The present invention also includes a first circuit member having a first substrate and a first circuit electrode formed on the main surface of the substrate, a second substrate and the main surface of the substrate. The second circuit electrode has a second circuit electrode, the second circuit electrode and the first circuit electrode are arranged to face each other, and the second circuit electrode is electrically connected to the first circuit electrode. And a connection part interposed between the first circuit member and the second circuit member, and the connection part provides a circuit connection structure which is a cured product of the circuit connection material according to the present invention. To do.

  In the circuit connection structure of the present invention, the connection portion is a cured product of the circuit connection material according to the present invention, so that the connection resistance between the electrodes facing each other even under a high temperature and high humidity environment has sufficient adhesive strength. It can have excellent connection reliability that is kept low enough. Moreover, since the circuit connection structure of this invention can form a connection part at low temperature, even if it has a member with low heat resistance, the influence by heat can be made small.

  The present invention also includes a first circuit member having a first substrate and a first circuit electrode formed on the main surface of the substrate, a second substrate and the main surface of the substrate. The circuit connection material according to the present invention is interposed between a second circuit electrode having a second circuit electrode and disposed so that the second circuit electrode and the first circuit electrode face each other. And a step of pressurizing the first circuit member and the second circuit member so that the first circuit electrode and the second circuit electrode are electrically connected to each other. .

  According to the manufacturing method of the circuit connection structure of the present invention, by connecting the circuit members with the circuit connection material according to the present invention, it has sufficient adhesive strength even under low temperature and short time connection conditions, It is possible to obtain a circuit connection structure excellent in connection reliability in which the connection resistance between opposing electrodes is maintained sufficiently low even in a high temperature and high humidity environment.

  Further, the present invention is an adhesive composition containing a radical polymerizable substance and a radical polymerization initiator, the first radical polymerizable substance represented by the following general formula (1) as a radical polymerizable substance, Provided is an adhesive composition containing a second radical polymerizable substance other than the first radical polymerizable substance having two or more (meth) acryloyl groups and containing dilauroyl peroxide as a radical polymerization initiator. .

式（１）中、Ｘ_１及びＸ_２は同一でも異なってもよく、アクリロイル基［ＣＨ_２＝ＣＨ−Ｃ（＝Ｏ）−］、メタクリロイル基［ＣＨ_２＝Ｃ（ＣＨ_３）−Ｃ（＝Ｏ）−］又は水素原子［Ｈ−］を表し、少なくとも一方はアクリロイル基又はメタクリロイル基であり、ｎは８〜１５の整数を表す。

In the formula (1), X ₁ and X ₂ may be the same or different, and an acryloyl group [CH ₂ ═CH—C (═O) —], a methacryloyl group [CH ₂ ═C (CH ₃ ) —C (= O)-] or a hydrogen atom [H-], at least one of which is an acryloyl group or a methacryloyl group, and n represents an integer of 8-15.

  According to the adhesive composition according to the present invention, sufficient adhesive strength can be exhibited even at a low temperature for a short time.

  The content of dilauroyl peroxide in the adhesive composition according to the present invention is preferably 10 to 40 parts by mass with respect to 100 parts by mass of the total amount of radical polymerizable substances contained in the adhesive composition. By setting the content of dilauroyl peroxide within the numerical range, sufficient adhesive strength can be expressed even at a low temperature for a short time, and crystallization of dilauroyl peroxide can be sufficiently suppressed. .

  Moreover, it is preferable that content of a 1st radically polymerizable substance is 30-100 mass parts with respect to 100 mass parts of dilauroyl peroxide content. By setting the content of the first radical polymerizable substance within such a numerical range, sufficient adhesive strength can be exhibited even at a low temperature for a short time, and crystallization of dilauroyl peroxide is sufficiently suppressed. be able to.

  The adhesive composition according to the present invention preferably further contains a thermoplastic resin. In this case, it is possible to realize an adhesive composition that improves the handleability of the adhesive composition and is excellent in stress relaxation during curing.

  The thermoplastic resin is preferably a polyester urethane resin.

  The adhesive composition according to the present invention preferably further contains a third radical polymerizable substance having a phosphate structure. In this case, the adhesive strength to the surface of an inorganic substance such as metal can be improved.

  The third radical polymerizable substance is preferably a compound represented by the following general formula (2).

式（２）中、Ｒはメチル基又は水素原子を表し、ｎは１〜２の整数を表す。

In formula (2), R represents a methyl group or a hydrogen atom, and n represents an integer of 1 to 2.

  Moreover, this invention provides an adhesive sheet provided with a support film and the film adhesive which consists of an adhesive composition based on this invention provided on this support film.

  According to the adhesive sheet according to the present invention, sufficient adhesive strength can be exhibited even at a low temperature for a short time by having the film adhesive made of the adhesive composition according to the present invention.

  According to the present invention, even when the circuit members are connected to each other at a low temperature around 120 ° C., they have sufficient adhesive strength and the connection resistance between the opposing electrodes is maintained sufficiently low even in a high temperature and high humidity environment. It is possible to provide a circuit connection material, an adhesive composition, and an adhesive sheet that can provide a circuit connection structure having excellent connection reliability. In addition, according to the present invention, a circuit connection structure having a sufficient connection strength and having excellent connection reliability in which connection resistance between opposing electrodes is maintained sufficiently low even in a high temperature and high humidity environment, and a method for manufacturing the circuit connection structure. Can be provided.

It is a schematic cross section showing one embodiment of an adhesive sheet. It is a schematic cross section showing one embodiment of a circuit connection structure. It is a schematic cross section for explaining one embodiment of a manufacturing method of a circuit connection structure.

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as necessary. However, the present invention is not limited to the following embodiments. In addition, the dimension ratio of drawing is not restricted to the illustrated ratio. In the present specification, “(meth) acrylate” means “acrylate” and its corresponding “methacrylate”, and “(meth) acryloyl group” means “acryloyl group” and its corresponding “methacryloyl group”. "Means.

  The adhesive composition according to the present embodiment includes a radical polymerizable substance and a radical polymerization initiator, and includes a first radical polymerizable substance represented by the following general formula (1) as a radical polymerizable substance, And a second radical polymerizable substance other than the first radical polymerizable substance having two or more acryloyl groups, and a dilauroyl peroxide as a radical polymerization initiator.

式（１）中、Ｘ_１及びＸ_２は同一でも異なってもよく、アクリロイル基［ＣＨ_２＝ＣＨ−Ｃ（＝Ｏ）−］、メタクリロイル基［ＣＨ_２＝Ｃ（ＣＨ_３）−Ｃ（＝Ｏ）−］又は水素原子［Ｈ−］を表し、少なくとも一方はアクリロイル基又はメタクリロイル基であり、ｎは８〜１５の整数を表す。

In the formula (1), X ₁ and X ₂ may be the same or different, and an acryloyl group [CH ₂ ═CH—C (═O) —], a methacryloyl group [CH ₂ ═C (CH ₃ ) —C (= O)-] or a hydrogen atom [H-], at least one of which is an acryloyl group or a methacryloyl group, and n represents an integer of 8-15.

  Hereinafter, the case where the adhesive composition according to the present embodiment is applied as a circuit connection material for connecting circuit members having circuit electrodes facing each other will be described.

  The first radical polymerizable substance is a compound having a hydrocarbon skeleton (methylene chain) having a specific length and having one or more (meth) acryloyl groups, as represented by the general formula (1). is there. Specifically, 1,10-decanediol diacrylate, 1,10-decanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-decanediol dimethacrylate, 1,8-octanediol diacrylate, 1,8-octanediol dimethacrylate, 1,11-undecanediol diacrylate, 1,11-undecanediol dimethacrylate, 1,12-dodecanediol diacrylate, 1,12-decanediol dimethacrylate, 1,13-tride Candiol diacrylate, 1,13-tridecanediol dimethacrylate, 1,14-tetradecanediol diacrylate, 1,14-tetradecanediol dimethacrylate, 1,15-pentadecanediol diacrylate, 1,15 Pentadecane diol dimethacrylate and the like.

  The compounds represented by the general formula (1) can be used singly or in combination of two or more.

  Examples of the second radical polymerizable substance include urethane (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and tetramethylolmethane tetra (meth) acrylate. 2-hydroxy-1,3-di (meth) acryloxypropane, 2,2-bis [4-((meth) acryloxymethoxy) phenyl] propane, 2,2-bis [4-((meth) acrylic) Roxypolyethoxy) phenyl] propane, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate and the like. These can be used individually by 1 type or in combination of 2 or more types.

  Moreover, it is preferable that a 2nd radically polymerizable substance has 1 or more types of a dicyclopentenyl group, a tricyclodecanyl group, and a triazine ring from a viewpoint of improving the heat resistance of a circuit connection material.

  The second radical polymerizable substance is not limited to a monomer and may be an oligomer or a polymer. Examples of such radically polymerizable substances include urethane (meth) acrylate oligomers.

  The second radical polymerizable substance described above can be used alone or in combination of two or more.

  The circuit connection material according to the present embodiment can further contain a third radical polymerizable substance having a phosphate structure. In this case, the adhesive strength to the surface of an inorganic substance such as metal can be improved.

  As the third radically polymerizable substance, a compound represented by the following general formula (2) is preferable. Examples of the compound represented by the following general formula (2) include mono (2- (meth) acryloyloxyethyl) acid phosphate, di (2- (meth) allyloyloxyethyl) acid phosphate, and the like. These compounds can be obtained, for example, as a reaction product of phosphoric anhydride and 2-hydroxyethyl (meth) acrylate.

式（２）中、Ｒはメチル基又は水素原子を表し、ｎは１〜２の整数を表す。

In formula (2), R represents a methyl group or a hydrogen atom, and n represents an integer of 1 to 2.

  The third radical polymerizable substance can be used alone or in combination of two or more.

  The circuit connection material of the present embodiment may contain a radical polymerizable substance other than the first, second and third radical polymerizable substances described above. Such a radically polymerizable substance is not particularly limited, and monofunctional (meth) acrylate and the like can be used. Examples of the monofunctional (meth) acrylate include a monofunctional (meth) acrylate having a ring structure and a (meth) acrylate having a urethane group.

  Monofunctional (meth) acrylates having a ring structure include acroyl morpholine, methacryloyl morpholine, isobornyl acrylate, isobornyl methacrylate, tetrahydro-2H-pyran-2-yl-acrylate, tetrahydro-2H-pyran-2 -Yl-methacrylate, 1- (cyclohexyloxy) ethyl acrylate, 1- (cyclohexyloxy) ethyl metallate, 1- (cyclohexyloxy) propyl acrylate, 1- (cyclohexyloxy) propyl metallate, 1- (cyclohexyloxy) ethyl Metallate, 1- (cyclohexyloxy) butyl acrylate, 1- (cyclohexyloxy) butyl metallate, 1- (cyclohexyloxy) pentyl acrylate, 1- (cyclohexyloxy) pentyl methacrylate Lilate, cyclohexyl acrylate, cyclohexyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, phenoxymethyl acrylate, phenoxymethyl methacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, phenoxypropyl acrylate, phenoxypropyl methacrylate, phenoxybutyl acrylate, γ-butyrolactone acrylate , Δ-valerolactone acrylate, and the like can be used.

  Examples of the (meth) acrylate having a urethane group include those obtained as a reaction product of a polyol such as polytetramethylene glycol, a polyisocyanate, and a hydroxyl group-containing acrylic compound. Such a compound is preferable because of its excellent adhesiveness.

  The total content of the radical polymerizable substance in the circuit connecting material according to the present embodiment is preferably 20 to 70 parts by mass, more preferably 30 to 65 parts by mass when the total amount of the circuit connecting material is 100 parts by mass.

  The circuit connecting material according to the present embodiment contains dilauroyl peroxide as a radical polymerization initiator, but a radical polymerization initiator other than dilauroyl peroxide can be used in combination as appropriate depending on the conditions for connecting the circuits. .

  As a radical polymerization initiator other than dilauroyl peroxide, a radical polymerization initiator generally used in radical polymerization can be used. For example, a peroxide compound or an azo compound that generates a free radical by heating is used. Can do. Specifically, it can be selected from diacyl peroxides, peroxydicarbonates, peroxyesters, peroxyketals, dialkyl peroxides, hydroperoxides, and the like.

  Diacyl peroxides include 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, stearoyl peroxide, succinic peroxide, benzoyl peroxide, benzoyl peroxide Etc.

  Peroxydicarbonates include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxymethoxyperoxydicarbonate, di- (2-Ethylhexylperoxy) dicarbonate, dimethoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutylperoxy) dicarbonate and the like.

  Peroxyesters include 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy Isobutyrate, 1,1-bis (t-butylperoxy) cyclohexane, t-hexylperoxyisopropyl Monocarbonate, t-butylperoxy-3,5,5-trimethylhexanonate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toluoylperoxy) hexane, t -Butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, t-butyl peroxyacetate and the like.

  Peroxyketals include 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t -Butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) decane and the like.

  Dialkyl peroxides include α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t- Examples thereof include butyl cumyl peroxide.

  Examples of hydroperoxides include diisopropylbenzene hydroperoxide and cumene hydroperoxide.

  One of the above radical polymerization initiators may be used in combination with dilauroyl peroxide, or two or more thereof may be used in combination with dilauroyl peroxide.

  In the circuit connection material according to the present embodiment, it is preferable to contain a material obtained by coating a radical polymerization initiator with a polyurethane-based or polyester-based polymer substance or the like and microencapsulating from the viewpoint of improving storage stability.

  Moreover, in the circuit connection material which concerns on this embodiment, you may mix and use a radical polymerization initiator and a decomposition accelerator or a decomposition inhibitor.

  The content of dilauroyl peroxide in the circuit connection material according to the present embodiment is preferably 10 to 40 parts by mass, and preferably 15 to 35 parts by mass with respect to 100 parts by mass of the total amount of radical polymerizable substances contained in the circuit connection material. More preferably, 20-30 mass parts is further more preferable. By setting the content of dilauroyl peroxide within the above numerical range, it is possible to sufficiently suppress an increase in connection resistance value in a high-temperature and high-humidity environment while connecting circuit members with sufficient adhesive strength.

  30-100 mass parts is preferable with respect to 100 mass parts of dilauroyl peroxide content, and, as for content of the 1st radically polymerizable substance in the circuit connection material which concerns on this embodiment, 50-80 mass parts is more preferable. . By controlling the content of the first radical polymerizable substance within the above numerical range, circuit members are connected with sufficient adhesive strength, while sufficiently suppressing an increase in connection resistance value in a high-temperature and high-humidity environment. Can do.

  The circuit connecting material according to the present embodiment preferably further contains a thermoplastic resin in terms of excellent handleability and excellent stress relaxation during curing.

  Thermoplastic resins include phenoxy resin, polyurethane resin, polyester urethane resin, acrylic resin, polyvinyl butyral resin, polyvinyl formal resin, polyimide resin, polyamide resin, polyester resin, phenol resin, polystyrene resin, polyethylene resin, polyvinyl chloride resin, Polyphenylene oxide resin, xylene resin, polyisocyanate resin and the like can be used.

  The phenoxy resin can be obtained by reacting a bifunctional phenol and epihalohydrin to a high molecular weight or by polyaddition reaction of a bifunctional epoxy resin and a bifunctional phenol.

  A copolymer such as an ethylene-vinyl acetate copolymer can be used as the thermoplastic resin.

  A thermoplastic resin can be used individually by 1 type or in combination of 2 or more types.

  Among the above thermoplastic resins, phenoxy resin, polyurethane resin, polyester urethane resin, and acrylic resin are preferable.

  The thermoplastic resin may be modified with a radical polymerizable functional group (for example, a (meth) acryloyl group), and in this case, the thermoplastic resin can be incorporated into a curing system.

  In addition, it is preferable that the thermoplastic resin has a polar group such as a hydroxyl group because adhesion is improved. As the thermoplastic resin having a hydroxyl group, a phenoxy resin, a polyvinyl butyral resin, a polyvinyl formal resin, a phenol resin, or the like can be preferably used. By using these hydroxyl group-containing resins, it is possible to obtain the effect of stress relaxation during curing and the effect of further improving the adhesiveness. The hydroxyl group-containing resin may be modified with an epoxy group-containing elastomer, a radical polymerizable functional group, or the like. In particular, those modified with a radically polymerizable functional group are preferable because the heat resistance is improved.

  The weight average molecular weight of the thermoplastic resin is preferably 10,000 or more, and more preferably 10,000 to 1,000,000. If the weight average molecular weight of the thermoplastic resin is 10,000 or more, the film-forming property at the time of forming into a film tends to be improved. On the other hand, if it is 1,000,000 or less, the solubility in a solvent and other components There is a tendency that it is easy to adjust the coating liquid for forming into a film shape. In addition, the weight average molecular weight prescribed | regulated by this specification means the value measured using the calibration curve by a standard polystyrene by the gel permeation chromatography method (GPC) according to the following conditions.

[GPC measurement conditions]
Equipment used: Hitachi L-6000 type [Hitachi, Ltd.]
Column: Gel pack GL-R420 + Gel pack GL-R430 + Gel pack GL-R440 (3 in total) [manufactured by Hitachi Chemical Co., Ltd.]
Eluent: Tetrahydrofuran Measurement temperature: 40 ° C
Flow rate: 1.75 mL / min
Detector: L-3300RI [Hitachi, Ltd.]

  The glass transition temperature (Tg) of the thermoplastic resin is preferably 40 ° C. or higher.

  In the present embodiment, it is preferable to use a polyester urethane resin as the thermoplastic resin.

  The polyester urethane resin can be obtained, for example, by a reaction between a polyester polyol and diisocyanate. The polyester urethane resin preferably has a urethane group and an ester group in its main chain.

  The polyester polyol is a polymer having a plurality of ester groups and a plurality of hydroxyl groups. The polyester polyol is obtained, for example, by a reaction between a dicarboxylic acid and a diol. As the dicarboxylic acid, aromatic or aliphatic dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, and sebacic acid are preferable. As the diol, glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, hexanediol, neopentyl glycol, diethylene glycol, and triethylene glycol are preferable.

  Diisocyanates include 2,4-tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and aromatic and alicyclic rings. An aliphatic or aliphatic diisocyanate is preferably used.

  The polyester urethane resin preferably has an anionic property. Thereby, adhesive strength further improves. The polyester urethane resin having an anionic property can be obtained by copolymerizing a diol or diamine having a sulfonic acid group or a carboxyl group in the side chain in the reaction of the polyester polyol and the diisocyanate. That is, the polyester urethane resin preferably has a sulfonic acid group or a carboxyl group.

  The polyester urethane resin preferably has an aromatic group containing a benzene ring or the like, a cyclic aliphatic group containing a cyclohexane ring or the like.

  Two or more polyester urethane resins can be mixed and used. For example, what is obtained by reaction of an aromatic polyester polyol and aliphatic diisocyanate and what is obtained by reaction of an aliphatic polyester polyol and aromatic diisocyanate can be combined.

  The Tg of the polyester urethane resin is preferably 50 ° C. or higher. The polyester urethane resin can have a glass transition temperature of 50 ° C. or higher by appropriately adjusting the type of polyester polyol or diisocyanate, the weight average molecular weight, and the like.

  The polyester urethane resin preferably has a weight average molecular weight of 5,000 to 100,000. When the weight average molecular weight is 5000 or more, the film-forming property tends to be improved when it is formed into a film, and when the weight average molecular weight is 100,000 or less, the solubility in the solvent and the compatibility are improved. There is a tendency that it becomes easy to adjust the coating liquid for forming into a shape.

  The polyester urethane resin preferably has at least one of an unsaturated double bond having a radical polymerizable group and an epoxy group. Thereby, when hardening a circuit connection material, the epoxy resin or radically polymerizable substance in an adhesive composition reacts, and the elasticity modulus and heat resistance of the hardened | cured material of a circuit connection material can be improved. Therefore, when using the polyester urethane resin which has an epoxy group, it is preferable that a circuit connection material contains an epoxy resin as a thermosetting resin mentioned later.

  The content of the thermoplastic resin in the circuit connection material according to the present embodiment is preferably 30 to 80 parts by mass, and more preferably 35 to 70 parts by mass when the total amount of the circuit connection material is 100 parts by mass.

  The circuit connection material according to the present embodiment can contain a thermosetting resin.

  As the thermosetting resin, urea resin, melamine resin, epoxy resin and the like can be used. In this case, a curing agent and / or a curing accelerator for the thermosetting resin can be further blended. The curing agent is preferably a latent curing agent.

  Any epoxy resin can be used as long as it is an epoxy compound. Typical epoxy resins are bisphenol type epoxy resins which are glycidyl ethers of bisphenols such as bisphenol A, F and D, and epoxy novolac resins derived from phenol novolac or cresol novolac. Other examples include glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins. These can be used individually by 1 type or in mixture of 2 or more types.

It is preferable to use an epoxy resin having an impurity ion (Na ⁺ , Cl ⁻ etc.) concentration or hydrolyzable chlorine of 300 ppm or less to prevent electron migration.

  The circuit connection material according to the present embodiment can further contain a compound having an aminoxyl structure. In this case, the storage stability of the circuit connection material can be further improved.

  The circuit connection material according to the present embodiment may contain a polymerization inhibitor such as hydroquinone or methyl ether hydroquinone.

  The circuit connection material according to the present embodiment may contain conductive particles. Examples of the conductive particles include metal particles such as Au, Ag, Ni, Cu, and solder, and carbon. Further, the surface of a transition metal such as Ni may be coated with a noble metal such as Au. In order to obtain a sufficient pot life, the surface layer is preferably made of Au, Ag, or a platinum group noble metal, and more preferably Au, rather than transition metals such as Ni and Cu. In addition, a conductive layer was formed on the surface of the non-conductive particles by a method such as coating the surface of the non-conductive particles such as glass, ceramic, plastic, etc. with the above-mentioned conductive material, and the outermost layer was composed of noble metals. In the case of particles or hot-melt metal particles, since they are deformable by heating and pressing, the contact area with the electrode is increased at the time of connection, and the reliability is improved.

  The circuit connection material according to the present embodiment can obtain a connection by direct contact of circuit electrodes facing each other at the time of connection without containing conductive particles, but is more stable when further containing conductive particles. Connection can be obtained.

  Although content of the electroconductive particle in the circuit connection material which concerns on this embodiment is set suitably by the use of a circuit connection material, for example, 0.1-30 with respect to 100 volume parts of circuit connection materials containing electroconductive particle. It can be set as the range of a volume part. In order to prevent an adjacent circuit from being short-circuited by excessive conductive particles, the content of the conductive particles is preferably 0.1 to 10 parts by volume.

  The circuit connection material according to the present embodiment can contain a filler, a softener, an accelerator, an anti-aging agent, a colorant, a flame retardant, a thixotropic agent, a coupling agent, and the like.

  Inclusion of a filler in the circuit connection material according to the present embodiment can improve connection reliability and the like. In addition, when a circuit connection material contains electroconductive particle, it is preferable that the maximum diameter of a filler is less than the particle size of electroconductive particle. The content of the filler in the circuit connection material according to the present embodiment can be set in the range of 5 to 60 parts by volume with respect to 100 parts by volume of the circuit connection material from the viewpoint of sufficiently obtaining the effect of the blending.

  As the coupling agent, a compound having at least one functional group selected from the group consisting of a vinyl group, an acryloyl group, an amino group, an epoxy group, and an isocyanate group is preferable from the viewpoint of improving adhesiveness.

  According to the circuit connection material according to the present embodiment, even when the circuit members are connected at a low temperature of around 120 ° C., the connection between the electrodes having sufficient adhesive strength and facing each other even in a high temperature and high humidity environment. A circuit connection structure excellent in connection reliability in which the resistance is maintained sufficiently low can be obtained.

  The present inventors infer the reason why the circuit connection material according to the present embodiment can achieve the above-described effects. First, a circuit connection structure connected using a circuit connection material containing a large amount of dilauroyl peroxide has many bubbles at the connection part after a reliability test at high temperature and high humidity, and connection reliability at a narrow pitch is particularly high. It has been confirmed by the present inventors that it gets worse. Therefore, it is considered that dilauroyl peroxide contained in a large amount in the circuit connection material is crystallized or localized on the material surface as a factor that increases the connection resistance value between the electrodes connected in a high temperature and high humidity environment. . In the circuit connection material according to the present embodiment, dilauroyl peroxide and the radical polymerizable substance (first radical polymerizable substance) represented by the general formula (1) are used in combination, so that the low temperature connection can be achieved. Even when dilauroyl peroxide is added to ensure adhesive strength, crystallization or localization of dilauroyl peroxide is effectively suppressed by the first radical polymerizable substance having a specific structure. Therefore, the present inventors believe that both the adhesive strength and the stability of the connection resistance can be achieved.

  Next, the adhesive sheet according to the present invention will be described with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of an adhesive sheet according to the present invention. The adhesive sheet 4 shown in FIG. 1 includes a support film 1, a film adhesive 2 provided on the support film, and a protection provided on the surface of the film adhesive 2 opposite to the support film 1. Film 3 is provided.

  The film adhesive 2 is composed of the adhesive composition according to the present invention including the same components as those of the circuit connection material according to the above-described embodiment, and the conductive component dispersed in the adhesive component 5 and the adhesive component 5. Active particles 7. Here, the adhesive component refers to a component obtained by removing conductive particles from the adhesive composition.

  Examples of the support film 1 include polyethylene terephthalate film, polyethylene naphthalate film, polyethylene isophthalate film, polybutylene terephthalate film, polyolefin film, polyacetate film, polycarbonate film, polyphenylene sulfide film, polyamide film, and ethylene-vinyl acetate. Various films such as a polymer film, a polyvinyl chloride film, a polyvinylidene chloride film, a synthetic rubber film, and a liquid crystal polymer film can be used. The above film may have a surface subjected to corona discharge treatment, anchor coating treatment, antistatic treatment, or the like as necessary.

  Further, the surface of the support film 1 may be coated with a release treatment agent so that the film adhesive 2 is easily peeled from the support film 1. Various release treatment agents such as silicone resins, copolymers of silicone and organic resins, alkyd resins, amino alkyd resins, resins having long-chain alkyl groups, resins having fluoroalkyl groups, shellac resins, etc. Can be used.

  The thickness of the support film 1 is preferably 4 to 200 μm in consideration of storage of the produced adhesive sheet 4, convenience during use, etc., and 15 in consideration of material cost, productivity, and the like. It is more preferable to set it to -75 micrometers.

  The film adhesive 2 can be prepared by applying a coating solution containing the adhesive composition according to the present invention on the support film 1 using a coating apparatus, and drying it with hot air for a predetermined time. . In this embodiment, it is preferable that the adhesive composition according to the present invention contains the above-described thermoplastic resin as a film forming material.

  The film adhesive 2 may be composed of two or more layers. For example, in the case of a two-layer structure including a layer containing conductive particles and a layer not containing conductive particles, pot life can be improved.

  Examples of the protective film 3 include the same film as the support film 1. The thickness of the protective film is preferably 4 to 200 μm in consideration of storage of the produced adhesive sheet 4, convenience during use, etc., and 15 to 15 in consideration of material cost, productivity, and the like. More preferably, the thickness is 75 μm.

  The adhesive sheet 4 can be produced by forming the film adhesive 2 on the support film 1 and then bonding the protective film 3 thereon using a conventionally known laminator or the like.

  Next, a circuit connection structure and a manufacturing method thereof according to the present invention will be described.

  FIG. 2 is a schematic cross-sectional view showing an embodiment of a circuit connection structure. The connection structure 100 shown in FIG. 2 includes a first circuit member 20 having a first circuit board 21 and a first circuit electrode (first connection terminal) 22 formed on the main surface 21a of the board. A second circuit member 30 having a second circuit board 31 and a second circuit electrode (second connection terminal) 32 formed on the main surface 31a of the board; The connection part 10 which interposes between the two circuit members 30 and adhere | attaches these is provided. The second circuit member 30 is disposed to face the first circuit member 20 so that the second circuit electrode 32 faces the first circuit electrode 22.

  The connection part 10 interposes the circuit connection material which concerns on this embodiment between the 1st circuit member 20 and the 2nd circuit member 30, and the 1st circuit member 20 and the 2nd circuit member 30 in that state Is a cured product of the circuit connection material according to the present embodiment. In addition, in this embodiment, an example at the time of forming the connection part 10 using the circuit connection material containing electroconductive particle is shown, and the connection part 10 and the insulating layer 11 originating in components other than electroconductive particle are shown. , And conductive particles 7 dispersed in the insulating layer 11.

  The first circuit electrode 22 and the second circuit electrode 32 facing each other are electrically connected via the conductive particles 7. On the other hand, the first circuit electrodes 22 and the second circuit electrodes 32 formed on the same circuit board are insulated from each other.

  Examples of the first circuit board 31 and the second circuit board 21 include chip parts such as semiconductor chips, resistor chips, and capacitor chips, and boards such as printed boards. Usually, the circuit member is provided with a large number of connection terminals, but the number of connection terminals may be one in some cases.

  More specifically, examples of the circuit board include a board made of an inorganic material such as a semiconductor, glass and ceramic, a plastic board, a glass / epoxy board, and the like. The circuit board may be a combination of these materials.

  Examples of the plastic substrate include a polyimide film, a polycarbonate (PC) film, and a polyester film. From the viewpoint of low cost and light weight, a polycarbonate (PC) film, polyethylene terephthalate (PET), or polyethylene naphthalate (PEN) is preferable.

  The first circuit electrode and the second circuit electrode are formed from a metal such as copper. In order to obtain better electrical connection, it is preferable that at least one surface of the first circuit electrode and the second circuit electrode be one or more metals selected from the group consisting of gold, silver, tin, and platinum. . For example, a plurality of metals such as copper / nickel / gold may be combined to form a multilayer structure. In this case, the gold layer can be the outermost surface layer.

  Further, one of the first circuit member 20 and the second circuit member 30 may be a liquid crystal display panel having a glass substrate or a plastic substrate as a circuit substrate and having connection terminals formed from ITO or the like. . Further, one of the first circuit member 20 and the second circuit member 30 is a flexible printed wiring board (FPC), a tape carrier package (TCP) or a chip-on-film (COF) having a polyimide film as a circuit board, or It may be a semiconductor silicon chip having a semiconductor substrate as a circuit board. These various circuit members are appropriately combined as necessary to form a connection structure.

  In addition, it is preferable to heat-process the board | substrate provided with the circuit electrode previously before the connection process by a circuit connection material. Thereby, it can prevent that the volatile component generated with the heating at the time of a connection influences a connection.

  The circuit connection structure 100 includes, for example, the first circuit member 20, the circuit connection material according to the present embodiment, and the second circuit member 30, in this order, the first connection terminal 22 and the second connection terminal 32. Are formed so as to be opposed to each other and pressed or further heated in this state.

  The pressure is not particularly limited as long as it does not damage the adherend, but is generally preferably 0.1 to 10 MPa. The heating temperature is not particularly limited but is preferably 100 to 200 ° C. These pressurization and heating are preferably performed in the range of 0.5 to 100 seconds, and can be bonded by heating at 130 to 180 ° C., 3 MPa, and 10 seconds.

  Furthermore, the manufacturing method of the circuit connection structure according to the present embodiment will be described with reference to FIG. In the present embodiment, first, the first circuit member 20 described above and a film adhesive 40 formed by forming the circuit connection material according to the present embodiment into a film shape are prepared (see FIG. 3A). ). In the present embodiment, the circuit connecting material includes conductive particles 7. The adhesive component 5 is a component obtained by removing conductive particles from the circuit connecting material. Even when the circuit connecting material does not contain the conductive particles 7, the circuit connecting material can be used for anisotropic conductive bonding as an insulating adhesive.

  Next, the film adhesive 40 is placed on the surface of the first circuit member 20 on which the circuit electrode 22 is formed. Next, the film adhesive 40 is pressurized in the directions of arrows A and B in FIG. 3A to temporarily connect the film adhesive 40 to the first circuit member 20 (see FIG. 3B). At this time, you may pressurize, heating. However, the heating temperature is lower than the curing temperature of the adhesive composition in the film adhesive 40. The heating temperature at the time of temporary connection is preferably 50 to 120 ° C, more preferably 60 to 110 ° C. Moreover, it is preferable that the pressure at the time of temporary connection is 0.1-3 MPa.

  In this embodiment, a film adhesive can be disposed on the first circuit member using the adhesive sheet 4 according to this embodiment described above. Specifically, the film adhesive 2 exposed by peeling the protective film 3 from the adhesive sheet 4 is bonded to the first circuit member 20 using a laminator. After sticking, the support film 1 is peeled off.

  Subsequently, as shown in FIG. 3C, the second circuit member 30 is placed on the film adhesive 40 so that the second circuit electrode faces the first circuit member 20. At this time, the second circuit member can be temporarily fixed by positioning so that the first and second circuit electrodes face each other and then heating and pressurizing from above the second circuit member. By doing so, it is possible to suppress the positional deviation of the electrodes during the subsequent main connection. The heating temperature at the time of temporary fixing is set to a temperature lower than the curing temperature of the adhesive composition in the film adhesive 40, and the time from alignment to completion of temporary fixing is preferably 5 seconds or less for shortening the throughput. In addition, the heating temperature at the time of temporary fixing becomes like this. Preferably it is 50-120 degreeC, More preferably, it is 60-110 degreeC. Moreover, it is preferable that the pressure at the time of temporary fixing is 0.1-3 MPa.

  And it heats through the 1st and 2nd circuit members 20 and 30 to the arrow A and B direction of FIG.3 (c), heating the film adhesive 40. FIG. The heating temperature at this time is set to a temperature at which the polymerization reaction can be started. In the present embodiment, as described above, the connection conditions can be a pressure of 0.1 to 10 MPa and a connection time of 0.5 seconds to 120 seconds. Moreover, you may postcure as needed.

  Thus, the film adhesive 40 is cured, and a circuit connection structure as shown in FIG. 2 is obtained.

  According to the method for manufacturing a circuit connection structure according to the present embodiment, even when the circuit connection material according to the present embodiment is used and the film-like adhesive 40 made of the circuit connection material is used, the circuit connection structure is used. The members 20 and 30 can be bonded to each other with sufficient adhesive strength, the connection resistance between the electrically connected circuit electrodes can be sufficiently reduced, and further, when placed in a high temperature and high humidity environment for a long time. Even if it exists, the circuit connection structure by which increase in connection resistance was fully suppressed can be obtained.

  The adhesive composition and the adhesive sheet according to the present embodiment can provide sufficient adhesive strength at low temperatures and sufficiently reduce defects caused by the radical polymerization initiator. Therefore, the adhesive composition and the adhesive sheet can adhere to a member including a material having low heat resistance. Is preferred.

[Preparation of adhesive sheet]
Example 1
Polyester urethane resin (UR-8200, manufactured by Toyobo, 30% solution) as a thermoplastic resin is 40 parts by mass in terms of nonvolatile content, and ethylene vinyl acetate copolymer (EV40W, manufactured by Mitsui Dupont Polychemical, 20% solution) is nonvolatile content. 10 parts by mass in terms of conversion, 5 parts by mass of 1,10-decanediol diacrylate (A-DOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) as the first radical polymerizable substance, urethane as the second radical polymerizable substance A 70 mass% solution of an acrylate oligomer (UA5500, manufactured by Shin-Nakamura Chemical Co., Ltd.) dissolved in toluene in 33 mass parts in terms of non-volatile content, and 2-methacryloxyethyl acid phosphate (P-2M, Kyoeisha Chemical) as the third radical polymerizable substance 2 parts by weight, dilauroyl peroxide (Perroyl L, NOF) as radical polymerization initiator 10 parts by mass) and a nickel layer having a thickness of 0.2 μm was provided on the surface of particles having polystyrene as a core, and a gold layer (gold plating) having a thickness of 0.04 μm was provided outside the nickel layer. 5 parts by mass of conductive particles having an average particle diameter of 10 μm were mixed. This mixed solution was applied onto a PET film as a supporting film with an applicator, and a film-like adhesive having a thickness of 20 μm was formed by hot air drying at 70 ° C. for 10 minutes to obtain an adhesive sheet.

(Example 2)
Example except that 5 parts by mass of 1,10-decanediol dimethacrylate (DOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) was blended in place of 1,10-decanediol diacrylate (A-DOD-N) In the same manner as in No. 1, an adhesive sheet was obtained.

Example 3
In place of 1,10-decanediol diacrylate (A-DOD-N), except that 5 parts by mass of 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) was blended, An adhesive sheet was obtained in the same manner as in Example 1.

Example 4
Example except that 5 parts by mass of 1,9-nonanediol dimethacrylate (NOD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) was blended in place of 1,10-decanediol diacrylate (A-DOD-N) In the same manner as in No. 1, an adhesive sheet was obtained.

(Example 5)
Example 1 except that the amount of 1,10-decanediol diacrylate (A-DOD-N) was changed to 8 parts by mass and the amount of urethane acrylate oligomer (UA5500) was changed to 30 parts by mass. Similarly, an adhesive sheet was obtained.

(Example 6)
The compounding amount of urethane acrylate oligomer (UA5500) was changed to 27 parts by mass, and further 3 parts by mass of isocyanuric acid EO-modified diacrylate (M-215, manufactured by Toagosei Co., Ltd.) was added as a second radical polymerizable substance, and dilauroyl An adhesive sheet was obtained in the same manner as in Example 1 except that the amount of the peroxide was changed to 13 parts by mass.

(Example 7)
The blending amount of the urethane acrylate oligomer (UA5500) was changed to 30 parts by mass, and further 3 parts by mass of isocyanuric acid EO-modified diacrylate (M-215, manufactured by Toagosei Co., Ltd.) was added as a second radical polymerizable substance, and dilauroyl The compounding amount of peroxide was changed to 7 parts by mass, and further 3 mass of di-t-butylperoxyhexahydroterephthalate (HTP-65W, manufactured by Kayaku Akzo, 20% solution) as a radical polymerization initiator in terms of nonvolatile content. An adhesive sheet was obtained in the same manner as in Example 1 except that parts were mixed.

(Comparative Example 1)
The same as Example 1 except that 1,10-decanediol diacrylate (A-DOD-N) was not blended and 5 parts by mass of isocyanuric acid EO-modified diacrylate (M-215, manufactured by Toagosei Co., Ltd.) was blended. Thus, an adhesive sheet was obtained.

(Comparative Example 2)
The same as Example 1 except that 1,10-decanediol diacrylate (A-DOD-N) was not blended and 5 parts by mass of isocyanuric acid EO-modified triacrylate (M-315, manufactured by Toagosei Co., Ltd.) was blended. Thus, an adhesive sheet was obtained.

(Comparative Example 3)
The same as Example 1 except that 1,10-decanediol diacrylate (A-DOD-N) was not blended and 5 parts by mass of dicyclopentadiene type diacrylate (DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.) was blended. Thus, an adhesive sheet was obtained.

  Table 1 shows the compositions of the film adhesives in Examples and Comparative Examples. The unit in the table is part by mass. Moreover, about content of the dilauroyl peroxide and 1st radically polymerizable substance (compound represented by the said General formula (1)) in a film adhesive, dilauroyl par with respect to 100 mass parts of total amounts of a radically polymerizable substance. Table 2 shows the ratio of the oxide (parts by mass) and the ratio of the first radical polymerizable substance (parts by mass) to 100 parts by mass of dilauroyl peroxide.

[Production of circuit connection structure]
A copper circuit having a line width of 50 μm, a pitch of 100 μm and a thickness of 18 μm formed directly on a polyimide having a thickness of 75 μm using the adhesive sheets of Examples 1 to 7 and Comparative Examples 1 to 3, respectively. .1 μm tin-plated flexible circuit board (FPC) and PET film whose surface is covered with silicon dioxide or PET film whose surface is covered with silver paste, 130 ° C.−2 MPa−10 seconds, width Connected at 2.0 mm. At this time, after pasting the adhesive surface of the film-like adhesive of the adhesive sheet on the above PET film in advance, it is temporarily connected by heating and pressing at 70 ° C., 1 MPa, 2 seconds, and then supported from the adhesive sheet. The PET film, which is a film, was peeled off and connected to the FPC.

A circuit connection structure (FPC-SiO ₂ PET film) between the PET film on the silicon dioxide surface and the FPC is used for the evaluation of the adhesive strength, and a circuit connection structure between the PET film on the silver paste surface and the FPC is used for the evaluation of the connection resistance. (FPC-Ag paste PET film) was used.

[Measurement of adhesive strength]
The adhesive strength of the produced circuit connection structure (FPC-SiO ₂ PET film) was measured by a 90-degree peeling method according to JIS-Z0237. As a measuring device for adhesion strength, “Tensilon UTM-4” (trade name) (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used. The obtained results are shown in Table 3.

[Measurement of connection resistance]
Measure the resistance value between the opposing electrodes of the fabricated circuit connection structure (FPC-Ag paste PET film) with a multimeter immediately after connection and after a reliability test of holding for 250 hours in an environment of 85 ° C./85% RH. did. For the resistance value, an average value and a maximum value of 37 resistance values between circuit electrodes facing each other were measured. The obtained results are shown in Table 3.

  As shown in Table 3, according to the adhesive sheets of Examples 1 to 7, the adhesive strength is 5 N / cm or more, and the maximum resistance value after the reliability test is within twice the average value. A circuit connection structure was obtained. On the other hand, although the adhesive sheets of Comparative Examples 1 to 3 had good adhesive strength, variation in connection resistance after the reliability test of the circuit connection structure was large, and connection reliability was insufficient. Further, in the adhesive sheet of the example, crystallization of dilauroyl peroxide on the surface of the film adhesive was reduced as compared with the comparative example.

  DESCRIPTION OF SYMBOLS 1 ... Support film, 2 ... Film adhesive, 3 ... Protective film, 4 ... Adhesive sheet, 5 ... Adhesive component, 7 ... Conductive particle, 10 ... Connection part, 11 ... Insulating layer, 20 ... First Circuit member, 21 ... first circuit board, 22 ... first circuit electrode (first connection terminal), 30 ... second circuit member, 31 ... second circuit board, 32 ... second circuit electrode ( 2nd connection terminal), 40 ... film adhesive, 100 ... circuit connection structure.

Claims (17)

A circuit connection material for connecting circuit members having circuit electrodes facing each other, containing a radical polymerizable substance and a radical polymerization initiator,
As the radical polymerizable substance, a first radical polymerizable substance represented by the following general formula (1) and a second radical other than the first radical polymerizable substance having two or more (meth) acryloyl groups A polymerizable substance,
A circuit connection material containing dilauroyl peroxide as the radical polymerization initiator.

[In Formula (1), X ₁ and X ₂ may be the same or different and each represents an acryloyl group, a methacryloyl group or a hydrogen atom, at least one of which is an acryloyl group or a methacryloyl group, and n is an integer of 8 to 15. Represent. ]   2. The circuit connection material according to claim 1, wherein the content of the dilauroyl peroxide is 10 to 40 parts by mass with respect to 100 parts by mass of the total amount of radical polymerizable substances contained in the circuit connection material.   The circuit connection material according to claim 1 or 2, wherein the content of the first radical polymerizable substance is 30 to 100 parts by mass with respect to 100 parts by mass of the dilauroyl peroxide.   The circuit connection material according to claim 1, further comprising a thermoplastic resin.   The circuit connection material according to claim 4, wherein the thermoplastic resin is a polyester urethane resin.   The circuit connection material according to any one of claims 1 to 5, further comprising a third radical polymerizable substance having a phosphate structure. The circuit connection material according to claim 6, wherein the third radical polymerizable substance is a compound represented by the following general formula (2).

[In Formula (2), R represents a methyl group or a hydrogen atom, and n represents the integer of 1-2. ] A first circuit member having a first substrate and a first circuit electrode formed on the main surface of the substrate;
A second substrate and a second circuit electrode formed on a main surface of the substrate, the second circuit electrode and the first circuit electrode being arranged to face each other, the second circuit electrode A second circuit member having a circuit electrode electrically connected to the first circuit electrode;
A connecting portion interposed between the first circuit member and the second circuit member;
With
The said connection part is a circuit connection structure which is the hardened | cured material of the circuit connection material as described in any one of Claims 1-7.   A first circuit member having a first substrate and a first circuit electrode formed on the main surface of the substrate; a second circuit electrode formed on the main surface of the second substrate and the substrate; The circuit connecting material according to claim 1, wherein the second circuit electrode and the second circuit member arranged so that the first circuit electrode is opposed to each other. And pressurizing the first circuit member and the second circuit member so that the first circuit electrode and the second circuit electrode are electrically connected to each other. Manufacturing method of structure. An adhesive composition containing a radical polymerizable substance and a radical polymerization initiator,
Second radical polymerization other than the first radical polymerizable substance represented by the following general formula (1) and the first radical polymerizable substance having two or more (meth) acryloyl groups as the radical polymerizable substance A substance,
An adhesive composition containing dilauroyl peroxide as the radical polymerization initiator.

[In Formula (1), X ₁ and X ₂ may be the same or different and each represents an acryloyl group, a methacryloyl group or a hydrogen atom, at least one of which is an acryloyl group or a methacryloyl group, and n is an integer of 8 to 15. Represent. ]   11. The adhesive composition according to claim 10, wherein the content of the dilauroyl peroxide is 10 to 40 parts by mass with respect to 100 parts by mass of the total amount of radical polymerizable substances contained in the adhesive composition.   12. The adhesive composition according to claim 10, wherein the content of the first radical polymerizable substance is 30 to 100 parts by mass with respect to 100 parts by mass of the dilauroyl peroxide.   The adhesive composition according to any one of claims 10 to 12, further comprising a thermoplastic resin.   The adhesive composition according to claim 13, wherein the thermoplastic resin is a polyester urethane resin.   The adhesive composition according to any one of claims 10 to 14, further comprising a third radical polymerizable substance having a phosphate ester structure. The adhesive composition according to claim 15, wherein the third radical polymerizable substance is a compound represented by the following general formula (2).

[In Formula (2), R represents a methyl group or a hydrogen atom, and n represents the integer of 1-2. ]   An adhesive sheet provided with a support film and the film adhesive which consists of an adhesive composition as described in any one of Claims 10-16 provided on this support film.

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