JP6024261B2 - Adhesive for circuit connection, connection structure for circuit member and solar cell module - Google Patents

Description

  The present invention relates to an adhesive for circuit connection, a circuit member connection structure using the adhesive, and a solar cell module.

  In the semiconductor element and the liquid crystal display element, various adhesives are conventionally used for the purpose of bonding various members in the element. The demand for adhesives is diverse, including adhesiveness, heat resistance, and reliability in high temperature and high humidity conditions. The adhesive includes a connection between a liquid crystal display element and a tape carrier package (Tape Carrier Package, TCP) (Chip On Film (COF)), a flexible printed circuit board (Flexible Printed Circuit, FPC) and TCP. It is used for connection (COF), connection between TCP and printed wiring board (COF), connection between FPC and printed wiring board (COF), and the like. It is also used when a semiconductor element is mounted on a substrate.

The adherend used for bonding includes organic substrates such as printed wiring boards, polyimide, polyethylene terephthalate (PET), polycarbonate (PC) and polyethylene naphthalate (PEN), metals such as copper and aluminum, ITO ( Various surface states such as indium and tin composite oxide), IZO (composite of indium oxide and zinc oxide), AZO (zinc / aluminum oxide), SiN (silicon nitride) and SiO ₂ (silicon dioxide). It is necessary to design a molecule according to each adherend.

  Conventionally, as an adhesive for the semiconductor element and the liquid crystal display element, a thermosetting resin using an epoxy resin having high adhesiveness and high reliability has been used (for example, see Patent Document 1). As a component of the thermosetting resin, a curing agent such as an epoxy resin, a phenol resin having reactivity with the epoxy resin, and a thermal latent catalyst that accelerates the reaction between the epoxy resin and the curing agent are generally used. A thermal latent catalyst is a substance that does not react at a storage temperature such as room temperature and exhibits high reactivity upon heating, and is an important factor that determines the curing temperature and the curing rate. Various compounds have been used from the viewpoints of storage stability at room temperature and curing rate during heating. In the actual process, the desired adhesion was obtained under the curing conditions of curing at a temperature of 170 to 250 ° C. for 1 to 3 hours.

  Recently, along with the high integration of semiconductor devices and the high definition of liquid crystal display devices, the pitch between devices and between wires has been reduced. In addition, a semiconductor element, a liquid crystal display element, a touch panel, and the like using an organic base material having low heat resistance such as PET, PC, and PEN are used. The adhesive composition applied to such a semiconductor element has a high heating temperature when cured. Further, when the adhesive composition cures slowly, not only the desired connection part but also the peripheral member is excessively heated, which tends to cause damage to the peripheral member. Furthermore, there is a need to improve throughput in order to reduce costs. Therefore, there is a demand for curing at a lower temperature and in a shorter time, that is, adhesion at a lower temperature and faster curing.

  Recently, radically curable adhesives using radically polymerizable compounds 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 for a short time because radicals which are reactive species are rich in reactivity, and can be cured at a lower temperature than those using a thermosetting resin (for example, Patent Document 2). However, since the radical curable adhesive has a large curing shrinkage at the time of curing, it is generally inferior in adhesive strength as compared with the case of using an epoxy resin. Therefore, as a method for improving the adhesive strength, a method of imparting flexibility to the cured product by ether bond and improving the adhesive strength (refer to Patent Documents 3 and 4), containing a rubber-based stress relaxation agent in the adhesive A method for improving the adhesive strength has been proposed (see Patent Document 5). On the other hand, radically curable adhesives may have reduced heat resistance when imparted with flexibility to improve adhesive strength, and stable connection characteristics even after long-term reliability tests (high temperature and high humidity tests) May be difficult to hold. Therefore, as a method for improving heat resistance, a method of dispersing an inorganic filler such as silica particles in an adhesive has been proposed (see Patent Document 6).

Japanese Patent Laid-Open No. 1-113480 JP 2002-203427 A Japanese Patent No. 3522634 JP 2002-285128 A JP 2010-106244 A JP 2001-164232 A

Radical curable adhesives can be cured at low temperature in a short time, but have sufficient wettability to organic substrates such as polyimide, PET, PC, PEN, and inorganic substrates such as ITO, IZO, SiN, and SiO ₂ There is a tendency not to be obtained. Therefore, in the methods described in Patent Documents 3, 4, and 5 described above, sufficient wettability with respect to an adherend (ITO, IZO, SiN, SiO ₂ , polyimide, PET, PC, PEN, etc.) cannot be obtained. There is a tendency for strength to decrease. Further, when the base material (polyimide, PET, PC, PEN, etc.) becomes flexible, the flexibility and elongation of the adhesive are required more. However, in the methods described in Patent Documents 3, 4, and 5 described above, sufficient flexibility and elongation cannot be obtained for an adhesive, and sufficient adhesive strength can be obtained for a flexible substrate. There is no tendency. Further, in the method described in Patent Document 6, if the adhesive strength is to be improved, the dispersibility of the inorganic filler tends to deteriorate, and the fluidity and connection reliability of the adhesive tend to be reduced.

  Therefore, the present invention provides a circuit connection capable of obtaining excellent adhesive strength and maintaining stable performance (adhesive strength and connection resistance) even after a long-term reliability test (high temperature and high humidity test). It is an object of the present invention to provide a connecting structure for circuit members manufactured using the same adhesive.

  The present invention is interposed between a first circuit member having a first connection terminal and a second circuit member having a second connection terminal, the first connection terminal and the second connection terminal, An adhesive for circuit connection, wherein the adhesive for circuit connection is (a) a thermoplastic resin, (b) a radical polymerizable compound, (c) a radical polymerization initiator, and (d) an inorganic filler. And (d) an adhesive for circuit connection in which the shape of the inorganic filler is piece-like.

  According to such an adhesive for circuit connection, stable performance (adhesion strength and connection resistance) can be maintained even after a long-term reliability test (high temperature and high humidity test).

  (D) It is preferable that the inorganic filler contains at least one selected from alumina and boron nitride. Thereby, the more stable performance (adhesion strength and connection resistance) can be maintained after a long-term reliability test (high temperature and high humidity test) without impairing the fluidity at the time of pressure bonding.

  (D) It is preferable that content of an inorganic filler is 0.5-20 mass% with respect to the whole adhesive for circuit connection. Thereby, the heat resistance of the adhesive for circuit connection is further improved, and further stable performance (adhesion strength and connection resistance) can be maintained after a long-term reliability test (high temperature and high humidity test).

  (B) The radically polymerizable compound may contain at least one vinyl compound having a phosphate group and one or more radically polymerizable compounds other than the vinyl compound. In this case, adhesion by low-temperature curing is further facilitated, and adhesion strength with the substrate having the connection terminals can be further improved.

  Further, (a) the thermoplastic resin is selected from the group consisting of phenoxy resin, polyurethane resin, polyester urethane resin, butyral resin, acrylic resin, polyimide resin and polyamide resin, and a copolymer having vinyl acetate as a structural unit. At least one kind may be included. In this case, heat resistance and adhesiveness are further improved, and these excellent characteristics can be more easily maintained even after a long-term reliability test (high temperature and high humidity test).

  Further, the adhesive for circuit connection according to the present invention may further contain (e) conductive particles. In this case, since good electrical conductivity or anisotropic conductivity can be imparted to the adhesive for circuit connection, the adhesive is more suitably used for adhesion between circuit members having connection terminals and for connection of solar cells. It becomes possible. Further, the connection resistance of the connection structure obtained by electrical connection via the circuit connection adhesive can be further sufficiently reduced.

  Further, the adhesive for circuit connection according to the present invention includes a first connection terminal disposed on the main surface of the first substrate, and a second connection terminal disposed on the main surface of the second substrate. May be used to electrically connect the connection terminal of the solar battery cell having the connection terminal disposed on the main surface of the substrate and the wiring member. Also good.

  A circuit member connection structure according to one aspect of the present invention includes a first circuit member having a first connection terminal, a second circuit member having a second connection terminal, a first circuit member, and a first circuit member. A connection member that is disposed between the two circuit members and electrically connects the first connection terminal and the second connection terminal, and the connection member includes a cured product of the adhesive for circuit connection. . In the connection structure according to one aspect of the present invention, when the connection member contains the cured product of the circuit connection adhesive, the reliability (connection resistance and adhesive strength) of the connection structure can be improved.

  In the circuit member connection structure according to one aspect of the present invention, at least one of the first circuit member and the second circuit member is made of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or lower. May be. In this case, the adhesion strength of the connection structure manufactured using the circuit connection adhesive is further improved, and more stable performance (adhesion strength and connection resistance) after a long-term reliability test (high temperature and high humidity test). Can be maintained.

  In the circuit member connection structure according to one aspect of the present invention, at least one of the first circuit member and the second circuit member includes at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. You may be comprised from the base material. In this case, even when the first circuit member or the second circuit member having the substrate made of the specific material is used, by using the circuit connecting adhesive according to the present invention, Since it can sufficiently cope with the deformation that occurs during the time reliability test (high temperature and high humidity test), excellent connection reliability can be obtained.

  In the circuit member connection structure according to one aspect of the present invention, one of the first circuit member and the second circuit member includes at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. The aspect comprised from the base material and the other is comprised from the base material containing at least 1 sort (s) chosen from the group which consists of a polyimide resin and a polyethylene terephthalate may be sufficient. In this case, even when the first circuit member and the second circuit member having the substrate made of the specific material are used, by using the circuit connecting adhesive according to the present invention, Since it can sufficiently cope with the deformation that occurs during the time reliability test (high temperature and high humidity test), excellent connection reliability can be obtained.

  A solar cell module according to another aspect of the present invention is disposed between a solar cell having a substrate and a connection terminal disposed on the main surface of the substrate, a wiring member, and the solar cell and the wiring member. A connecting member that electrically connects the solar battery cell and the wiring member, and the connecting member includes a cured product of the adhesive for circuit connection. In the solar cell module according to another aspect of the present invention, the reliability (connection resistance and adhesive strength) of the solar cell module can be improved when the connection member contains the cured product of the circuit connection adhesive. it can.

  The present invention further comprises (a) a thermoplastic resin, (b) a radical polymerizable compound, (c) a radical polymerization initiator, and (d) an inorganic filler, and (d) the shape of the inorganic filler is flaky. It may be related to the application of the composition as an adhesive for circuit connection and the application of the composition for the production of an adhesive for circuit connection.

  According to the present invention, it is possible to obtain excellent adhesive strength, and for circuit connection that can maintain stable performance (adhesive strength and connection resistance) even after a long-term reliability test (high temperature and high humidity test). An adhesive and a connection structure for a circuit member manufactured using the adhesive can be provided.

It is a schematic cross section which shows the connection structure which concerns on 1st Embodiment of this invention. It is a schematic cross section which shows the manufacturing method of the connection structure shown in FIG. It is a schematic cross section which shows the connection structure which concerns on 2nd Embodiment of this invention. It is a schematic cross section which shows the manufacturing method of the connection structure shown in FIG. It is a schematic cross section which shows the connection structure which concerns on 3rd Embodiment of this invention. It is a SEM image which shows an example of an inorganic filler.

  Hereinafter, preferred embodiments of the present invention will be described in detail. In the present specification, “(meth) acrylic acid” means acrylic acid and methacrylic acid corresponding thereto, “(meth) acrylate” means acrylate and methacrylate corresponding thereto, and “(( The “meth) acryloyl group” means an acryloyl group and a methacryloyl group, and the “(meth) acryloyloxy group” means an acryloyloxy group and a methacryloyloxy group corresponding thereto.

Moreover, in this specification, a weight average molecular weight and a number average molecular weight say the value measured using the analytical curve by a standard polystyrene from a gel permeation chromatograph (GPC) according to the following conditions.
(Measurement condition)
Device: GPC-8020 manufactured by Tosoh Corporation
Detector: RI-8020 manufactured by Tosoh Corporation
Column: Gelpack GL-A-160-S + GL-A150 manufactured by Hitachi Chemical Co., Ltd.
Sample concentration: 120mg / 3ml
Solvent: Tetrahydrofuran Injection volume: 60 μl
Pressure: 2.94 × 10 ⁶ Pa (30 kgf / cm ² )
Flow rate: 1.00 ml / min

  The adhesive for circuit connection according to this embodiment contains (a) a thermoplastic resin, (b) a radical polymerizable compound, (c) a radical polymerization initiator, and (d) an inorganic filler.

((A): thermoplastic resin)
(A) When the thermoplastic resin is heated at a temperature equal to or higher than the melting point or the glass transition temperature, it becomes a liquid state having a high viscosity and is freely deformed by an external force, and is cooled and hardened while maintaining its shape when the external force is removed. A resin (polymer) having the property of repeating this process. Further, (a) the thermoplastic resin may be a resin (polymer) having a reactive functional group having the above properties. (A) The glass transition temperature (Tg) of the thermoplastic resin is preferably −30 ° C. or higher and 190 ° C. or lower, more preferably −25 ° C. or higher and 170 ° C. or lower, and further preferably −20 ° C. or higher and 150 ° C. or lower.

  (A) Thermoplastic resins include, for example, phenoxy resins, polyurethane resins, polyester urethane resins, butyral resins (for example, polyvinyl butyral resins), acrylic resins, polyimide resins and polyamide resins, and copolymers having vinyl acetate as structural units It can contain at least one selected from the group consisting of (vinyl acetate copolymer, for example, ethylene-vinyl acetate copolymer). Among these, it is more preferable to include at least one selected from the group consisting of phenoxy resin, polyurethane resin, polyester urethane resin, butyral resin, acrylic resin, and polyimide resin. These can be used individually by 1 type or in mixture of 2 or more types. Furthermore, these (a) thermoplastic resins may contain a siloxane bond and a fluorine substituent. These are preferably in a state in which the resins to be mixed are completely compatible with each other, or in a state in which microphase separation occurs and white turbidity occurs.

  When the adhesive for circuit connection is used in the form of a film, (a) the higher the weight average molecular weight of the thermoplastic resin, the easier the film-forming property is obtained, and the adhesive for the film-like circuit connection A wide range of melt viscosities affecting fluidity can be set. (A) The weight average molecular weight of the thermoplastic resin is preferably 5000 or more, more preferably 7000 or more, and still more preferably 10,000 or more. (A) When the weight average molecular weight of the thermoplastic resin is 5000 or more, the film formability tends to be further improved while maintaining the fluidity of the adhesive composition. (A) The weight average molecular weight of the thermoplastic resin is preferably 150,000 or less, more preferably 100,000 or less, and still more preferably 80000 or less. (A) When the weight average molecular weight of the thermoplastic resin is 150,000 or less, the film formability tends to be further improved while maintaining compatibility with other components.

  The content of the thermoplastic resin (a) in the circuit connecting adhesive is preferably 5% by mass or more based on the total mass of the adhesive components (components excluding conductive particles in the circuit connecting adhesive), and 15% by mass. % Or more is more preferable. (A) When the content of the thermoplastic resin is 5% by mass or more, the film formability tends to be further improved particularly when the circuit connecting adhesive is used in the form of a film. (A) 80 mass% or less is preferable on the basis of the total mass of an adhesive component, and, as for content of a thermoplastic resin, 70 mass% or less is more preferable. (A) When the content of the thermoplastic resin is 80% by mass or less, the film formability tends to be further improved while maintaining the fluidity of the circuit connecting adhesive.

((B) Radical polymerizable compound)
The (b) radical polymerizable compound refers to a compound that generates radical polymerization by the action of a radical polymerization initiator, but may be a compound that itself generates radicals by applying activation energy such as light and heat. (B) As the radically polymerizable compound, for example, a compound having a functional group that is polymerized by an active radical such as a vinyl group, a (meth) acryloyl group, an allyl group, or a maleimide group can be preferably used.

  (B) Specific examples of radically polymerizable compounds include epoxy (meth) acrylate oligomers, urethane (meth) acrylate oligomers, polyether (meth) acrylate oligomers, oligomers such as polyester (meth) acrylate oligomers, and trimethylolpropane. Tri (meth) acrylate, polyethylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, neopentyl glycol di (meth) acrylate , Dipentaerythritol hexa (meth) acrylate, isocyanuric acid modified bifunctional (meth) acrylate, isocyanuric acid modified trifunctional (meth) acrylate, bisphenoxye Add (meth) acrylic acid to the glycidyl group of epoxy (meth) acrylate, bisphenoxyethanol fluorene acrylate, or bisphenol fluorenediglycidyl ether obtained by adding (meth) acrylic acid to the glycidyl group of norfluorene acrylate or bisphenol fluorenediglycidyl ether. Epoxy (meth) acrylate, a compound in which ethylene glycol and propylene glycol are added to a glycidyl group of bisphenol fluorenediglycidyl ether, a compound in which a (meth) acryloyloxy group is introduced, the following general formula (A) or general formula (B) And the like.

[In Formula (A), R ¹ and R ² each independently represent a hydrogen atom or a methyl group, and a and b each independently represent an integer of 1 to 8. ]

[In Formula (B), R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and c and d each independently represents an integer of 0 to 8. ]

  The radically polymerizable compound (b) is a solid state having no fluidity such as waxy, waxy, crystalline, glassy or powdery when left alone at 30 ° C. However, it can be used without any particular limitation. Specific examples of such (b) radical polymerizable compounds include N, N′-methylenebisacrylamide, diacetone acrylamide, N-methylol acrylamide, N-phenyl methacrylamide, and 2-acrylamido-2-methylpropane. Sulfonic acid, tris (2-acryloyloxyethyl) isocyanurate, N-phenylmaleimide, N- (o-methylphenyl) maleimide, N- (m-methylphenyl) maleimide, N- (p-methylphenyl) maleimide, N -(O-methoxyphenyl) maleimide, N- (m-methoxyphenyl) maleimide, N- (p-methoxyphenyl) maleimide, N-methylmaleimide, N-ethylmaleimide, N-octylmaleimide, 4,4'-diphenylmethane Bismaleimide, m-fe Renbismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, N-methacryloxymaleimide, N-acryloxymaleimide 1,6-bismaleimide- (2,2,4-trimethyl) hexane, N-methacryloyloxysuccinimide, N-acryloyloxysuccinimide, 2-naphthyl methacrylate, 2-naphthyl acrylate, pentaerythritol tetraacrylate, Divinylethyleneurea, divinylpropyleneurea, 2-polystyrylethyl methacrylate, N-phenyl-N ′-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, N-phenyl-N ′-(3-acryloyl) Oxy 2-hydroxypropyl) -p-phenylenediamine, tetramethylpiperidyl methacrylate, tetramethylpiperidyl acrylate, pentamethylpiperidyl methacrylate, pentamethylpiperidyl acrylate, octadecyl acrylate, Nt-butylacrylamide, diacetone acrylamide, N- (hydroxy) And methyl) acrylamide and compounds represented by the following general formulas (C) to (L).

[In formula (C), e shows the integer of 1-10. ]

[In Formula (E), R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, and f represents an integer of 15 to 30. ]

[In Formula (F), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and g represents an integer of 15 to 30. ]

[In formula (G), R ⁹ represents a hydrogen atom or a methyl group. ]

[In Formula (H), R ¹⁰ represents a hydrogen atom or a methyl group, and h represents an integer of 1 to 10. ]

[In formula (I), R ¹¹ represents a hydrogen atom or an organic group represented by the following general formula (i) or (ii), and i represents an integer of 1 to 10. However, at least one of the plurality of R ¹¹ is an organic group represented by the following general formula (i) or (ii). ]

[In formula (J), R ¹² represents a hydrogen atom or an organic group represented by the following general formula (iii) or (iv), and j represents an integer of 1 to 10. However, at least one of a plurality of R ¹² is an organic group represented by the following general formula (iii) or (iv). ]

[In the formula (K), R ¹³ represents a hydrogen atom or a methyl group. ]

[In the formula (L), R ¹⁴ represents a hydrogen atom or a methyl group. ]

  Moreover, urethane acrylate can be used as the radically polymerizable compound (b). Urethane acrylate may be used alone or in combination with (b) a radical polymerizable compound other than urethane acrylate. By using urethane acrylate alone or in combination with (b) a radical polymerizable compound other than urethane acrylate, flexibility is improved and adhesive strength can be further improved.

  Although there is no restriction | limiting in particular as urethane acrylate, The urethane acrylate represented with the following general formula (M) is preferable. Here, the urethane acrylate represented by the following general formula (M) includes an aliphatic diisocyanate or an alicyclic diisocyanate, an aliphatic ester diol, an alicyclic ester diol, an aliphatic carbonate diol, and an alicyclic ring. It can be obtained by a condensation reaction with at least one selected from the group consisting of a carbonate-based diol.

[In Formula (M), R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a methyl group, R ¹⁷ represents an ethylene group or a propylene group, and R ¹⁸ represents a saturated aliphatic group or a saturated alicyclic group. , R ¹⁹ represents a saturated aliphatic group or saturated alicyclic group containing an ester group, or a saturated aliphatic group or saturated alicyclic group containing a carbonate group, and k represents an integer of 1 to 40. . In the formula (M), a plurality of R ¹⁷ and R ¹⁸ may be the same or different. ]

  The aliphatic diisocyanate constituting the urethane acrylate is tetramethylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, 2,2,4. Trimethylhexamethylene-1,6-diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, isophorone diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated trimethylxylylene diisocyanate Selected from etc.

The aliphatic ester-based diol constituting the urethane acrylate is a low molecular diol, a dibasic acid or a polyester diol obtained by dehydration condensation of a corresponding acid anhydride, cyclic ester compounds such as ε-caprolactone Is selected from polyester diols obtained by dehydration condensation.
Examples of the low molecular diols include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,2 -Pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2 , 2,4-trimethyl-1,3-pentanediol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2-ethyl-1,3- Hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-octanediol, 1,8-octanediol 1,7-heptanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,12-decanediol, dodecanediol, pinacol, 1,4-butynediol, triethylene Examples include glycol, diethylene glycol, dipropylene glycol, cyclohexane dimethanol and 1,4-cyclohexane dimethanol.
Examples of the dibasic acid include adipic acid, 3-methyladipic acid, 2,2,5,5-tetramethyladipic acid, maleic acid, fumaric acid, succinic acid, 2,2-dimethylsuccinic acid, and 2-ethyl. 2-methylsuccinic acid, 2,3-dimethylsuccinic acid, oxalic acid, malonic acid, methylmalonic acid, ethylmalonic acid, butylmalonic acid, dimethylmalonic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 2,4-dimethylglutaric acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.
The aliphatic ester diols can be used alone or in combination of two or more.

  The aliphatic polycarbonate diol and alicyclic carbonate diol constituting the urethane acrylate may be selected from polycarbonate diols obtained by reaction of at least one kind of the diols with phosgene. The polycarbonate-type diol obtained by reaction of the said glycols and phosgene can be used individually by 1 type or in mixture of 2 or more types.

  Moreover, the said urethane acrylate can adjust a weight average molecular weight freely within the range of 5000 or more and less than 30000 from a viewpoint of further improving adhesive strength, and can be used conveniently. If the weight average molecular weight of the urethane acrylate is within the above range, both flexibility and cohesion can be sufficiently obtained, and the adhesive strength with organic base materials such as PET, PC, PEN and the like can be further improved. Excellent connection reliability can be obtained. Further, from the viewpoint of obtaining such an effect more sufficiently, the weight average molecular weight of the urethane acrylate is more preferably 8000 or more and less than 25,000, and further preferably 10,000 or more and less than 20,000. In addition, when this weight average molecular weight is 5000 or more, flexibility tends to be further improved while maintaining the fluidity of the adhesive composition, and when the weight average molecular weight is less than 30000, adhesion for circuit connection The flexibility tends to be further improved while maintaining the fluidity of the agent.

  The urethane acrylate content is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more, based on the total mass of the adhesive component. There exists a tendency for the heat resistance after hardening to further improve that the said content is 5 mass% or more. The urethane acrylate content is preferably 95% by mass or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less, based on the total mass of the adhesive component. When the content is 95% by mass or less, when the circuit connecting adhesive is used as a film adhesive, the flexibility of the circuit connecting adhesive tends to be further improved while maintaining the fluidity of the circuit connecting adhesive. is there.

  (B) The radical polymerizable compound may contain at least one kind of a phosphate group-containing vinyl compound (a vinyl compound having a phosphate group) and a radical polymerizable compound other than the phosphate group-containing vinyl compound. Good. (B) The radical polymerizable compound includes an N-vinyl compound selected from the group consisting of an N-vinyl compound and an N, N-dialkylvinyl compound, and a radical polymerizable compound other than the N-vinyl compound, respectively. One or more kinds may be included. When the phosphate group-containing vinyl compound is used in combination with another radical polymerizable compound, the adhesiveness of the circuit connection adhesive to the substrate having the connection terminals can be further improved. Moreover, the cross-linking rate of the adhesive for circuit connection can be improved by using the N-vinyl compound together.

  The phosphate group-containing vinyl compound is not particularly limited as long as it is a compound having a phosphate group and a vinyl group, but compounds represented by the following general formulas (N) to (P) are preferable.

[In the formula (N), R ²⁰ represents a (meth) acryloyloxy group, R ²¹ represents a hydrogen atom or a methyl group, and l and m each independently represent an integer of 1 to 8. In the formula (N), a plurality of R ^{20 s} , R ^{21 s} , l s and m may be the same or different. ]

[In the formula (O), R ²² represents a (meth) acryloyloxy group, and n, o and p each independently represent an integer of 1 to 8. In the formula (O), a plurality of R ²² , n, o and p may be the same or different. ]

[In Formula (P), R ²³ represents a (meth) acryloyloxy group, R ²⁴ represents a hydrogen atom or a methyl group, and q and r each independently represents an integer of 1 to 8. ]

  Specific examples of the phosphoric acid group-containing vinyl compound include acid phosphooxyethyl methacrylate, acid phosphooxyethyl acrylate, acid phosphooxypropyl methacrylate, acid phosphooxypolyoxyethylene glycol monomethacrylate, and acid phosphooxypolyoxypropylene glycol monoester. Examples include methacrylate, 2,2′-di (meth) acryloyloxydiethyl phosphate, ethylene oxide (EO) -modified phosphate dimethacrylate, phosphate-modified epoxy acrylate, 2- (meth) acryloyloxyethyl phosphate, vinyl phosphate, and the like.

  Specific examples of the N-vinyl compound include N-vinylimidazole, N-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, 4,4′-vinylidenebis (N, N— Dimethylaniline), N-vinylacetamide, N, N-dimethylacrylamide, N, N-diethylacrylamide and the like.

  Each of the contents of the above-mentioned phosphate group-containing vinyl compound and N-vinyl compound is independent of the contents of radical polymerizable compounds other than the phosphate group-containing vinyl compound and N-vinyl compound. Is preferably 0.2% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.5% by mass or more. There exists a tendency for adhesive strength to further improve that the said content is 0.2 mass% or more. Each of the contents of the above-mentioned phosphate group-containing vinyl compound and N-vinyl compound is preferably 15% by mass or less, more preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the adhesive component. Is more preferable. When the content is 15% by mass or less, there is a tendency that it is easier to ensure reliability while suppressing deterioration in physical properties after curing of the adhesive for circuit connection.

  In addition, the content of the radical polymerizable compound (b) excluding the compound corresponding to the above-described phosphate group-containing vinyl compound or N-vinyl compound is 5% by mass or more based on the total mass of the adhesive component. Preferably, 10 mass% or more is more preferable, and 15 mass% or more is still more preferable. There exists a tendency for the heat resistance after hardening to further improve that the said content is 5 mass% or more. The content of the radically polymerizable compound (b) excluding the compound corresponding to the vinyl compound described above is preferably 95% by mass or less, more preferably 80% by mass or less, based on the total mass of the adhesive component, 70 A mass% or less is more preferable. When the content is 95% by mass or less, when the circuit connection adhesive is used as a film adhesive, the flexibility tends to be further improved while maintaining the fluidity of the adhesive composition. .

((C) radical polymerization initiator)
(C) As the radical polymerization initiator, conventionally known compounds such as organic peroxides and azo compounds that generate radicals by external energy application can be used. (C) The radical polymerization initiator is preferably an organic peroxide having a one-minute half-life temperature of 90 to 175 ° C. and a weight average molecular weight of 180 to 1000 from the viewpoints of stability, reactivity, and compatibility. . When the 1-minute half-life temperature is in this range, the storage stability is further improved, the radical polymerizability is sufficiently high, and the composition can be cured in a short time.

Specific examples of the organic peroxide include 1,1,3,3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, and di (2-ethylhexyl). Peroxydicarbonate, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, dilauroyl peroxide, 1-cyclohexyl-1-methylethylperoxynoedecanoate T-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylper Xyl-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyneoheptanoate, t-amylperoxy-2-ethylhexanoate, di-t-butyl Peroxyhexahydroterephthalate, t-amylperoxy-3,5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxyneodecanoate, 1,1,3,3-tetramethyl Butyl peroxy-2-ethylhexanoate, t-amylperoxyneodecanoate, t-amylperoxy-2-ethylhexanoate, di (3-methylbenzoyl) peroxide, dibenzoyl peroxide, di (4-Methylbenzoyl) peroxide, t-hexylperoxyisopropyl monocarbonate , T-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (3-methylbenzoyl) Peroxy) hexane, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxybenzoate, dibutyl Examples include peroxytrimethyl adipate, t-amyl peroxy normal octoate, t-amyl peroxy isononanoate, and t-amyl peroxybenzoate.
Specific examples of the azo compound include 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis (1-acetoxy-1-phenylethane), and 2,2′-azobisiso. Butyronitrile, 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyronitrile, 4,4′-azobis (4-cyanovaleric acid), 1,1 ′ -Azobis (1-cyclohexanecarbonitrile) etc. are mentioned.
These radical polymerization initiators can be used singly or in combination of two or more.

  Moreover, as (c) radical polymerization initiator, the compound which generate | occur | produces a radical by 150-750 nm light irradiation can be used. Such compounds include, for example, Photoinitiation, Photopolymerization, and Photocuring, J. Mol. -P. Examples thereof include compounds having high sensitivity to light irradiation, such as α-aminoacetophenone derivatives and phosphine oxide derivatives described in Fouassier, Hanser Publishers (1995, p17 to p35). These compounds may be used alone or in combination with the above organic peroxides and azo compounds.

  The content of the (c) radical polymerization initiator is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 2% by mass or more, based on the total mass of the adhesive component. When the content is 0.5% by mass or more, the circuit connecting adhesive tends to be more easily cured. The content of the (c) radical polymerization initiator is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 20% by mass or less, based on the total mass of the adhesive component. When the content is 40% by mass or less, the adhesive for circuit connection tends to be more easily cured while maintaining storage stability.

((D) inorganic filler)
(D) The inorganic filler is flaky. The piece shape means a flat shape or an indefinite shape of a thin piece, and includes a shape having a flat surface and a thickness in a direction perpendicular to the flat surface. Examples of the flake shape include shapes called plate shape, dish shape, scale shape, and flake shape, and the shape of the plane includes a circle, an ellipse, a polygon, an indefinite shape, and the like. An example of the SEM image of the inorganic filler is shown in FIG. FIG. 6A is an SEM image of a piece of inorganic filler made of boron nitride, and FIG. 6B is an enlarged view of FIG.

  (D) The average particle diameter of the inorganic filler is preferably 0.5 to 20 μm, more preferably 1 to 15 μm, and even more preferably 1 to 10 μm with respect to the planar average width. The ratio of the plane average major axis to the plane average width (plane average major axis / plane average width) is preferably 1 to 200, more preferably 1.2 to 150, and still more preferably 1.3 to 120. Here, the width of the plane of the inorganic filler is the shortest interval among the combinations of two parallel lines in contact with the end of the plane of the inorganic filler so as to sandwich the inorganic filler in the plane direction. The plane average width is defined by the median diameter (D50) of the plane width according to the number distribution. On the other hand, the major axis of the plane is the distance between the two parallel lines having the longest distance among the combinations of the two parallel lines selected as described above, and the average major axis of the plane is the median of the major axis of the plane according to the number distribution. It is defined by the diameter (D50). The number distribution can be evaluated, for example, by extracting about 500 to 1000 fine particles from an SEM image and using image analysis type particle size distribution measurement software. When the plane average width is 0.5 μm or more, the surface area of the particles becomes small, and the fluidity during connection tends to be further improved. On the other hand, when it is 20 μm or less, the physical properties of the circuit connecting adhesive tend to be further improved while maintaining the fluidity of the circuit connecting adhesive. When the ratio of the plane average major axis to the plane average width is 1 or more, the area of the plane portion increases, and the physical properties of the circuit connection adhesive tend to be further improved. On the other hand, when it is 200 or less, the area of the plane portion is reduced, and the fluidity of the adhesive for circuit connection tends to be improved.

  (D) The average thickness of the inorganic filler is preferably 0.01 to 1 μm, more preferably 0.02 to 0.8 μm, and still more preferably 0.04 to 0.6 μm. The average thickness here is defined as an average value obtained for five randomly selected inorganic fillers. There exists a tendency for adhesiveness and connection reliability to improve further that average thickness is 0.01 micrometer or more. On the other hand, when it is 1 μm or less, the physical properties of the adhesive for circuit connection tend to be further improved while maintaining the electrical connection between the connecting terminals facing each other.

  (D) The aspect ratio (plane average width / average thickness) of the inorganic filler is preferably 2 to 500, more preferably 2 to 400, and still more preferably 2 to 300. When the aspect ratio is 2 or more, the adhesive composition tends to be more elastic. On the other hand, when it is 500 or less, the electrical connection between the connecting terminals facing each other becomes more reliable.

  The inorganic filler used in the present embodiment is, for example, alumina, boron nitride, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, Crystalline silica, titania, glass, iron oxide, and ceramic can be used, and boron nitride is preferably used from the viewpoint of dispersibility. When the inorganic filler is spherical, the fluidity of the adhesive for circuit connection may not be sufficient due to the increase in surface area, and sufficient connection reliability may not be obtained. Further, when the inorganic filler is fibrous, it is filled randomly in the adhesive for circuit connection, so that sufficient connection reliability may not be obtained.

  As a kind of flake boron nitride, there is hexagonal boron nitride (h-BN), which has high lubricity and heat resistance.

  (D) As for content of an inorganic filler, 0.5-20 mass% is preferable with respect to the whole adhesive agent for circuit connection, 0.5-15 mass% is more preferable, 1-10 mass% is especially preferable. The effect of the heat resistance improvement by an inorganic filler can fully be exhibited as it is 0.5 mass% or more. On the other hand, when it is 20% by mass or less, the connection reliability tends to be further improved while maintaining the fluidity of the circuit connecting adhesive.

  It is preferable to treat the surface of the inorganic filler contained in the circuit connection adhesive of this embodiment with a silane coupling agent or the like. By treating the surface of the inorganic filler with a silane coupling agent, wettability and adhesion with other components of the circuit connecting adhesive can be improved, and fluidity and adhesive strength can be further improved. The presence or absence of the surface treatment of the inorganic filler can be confirmed using EDX (Energy Dispersive X-ray spectroscopy).

((E) conductive particles)
(E) The conductive particles may be particles having conductivity on the whole or on the surface, but when used for connecting members having connection terminals, the average particle diameter is smaller than the distance between the connection terminals. Is preferred.

  (E) Examples of the conductive particles include metal particles composed of metals such as Au, Ag, Ni, Cu, Pd, solder, and particles composed of carbon. Further, (e) the conductive particles may be particles in which non-conductive glass, ceramic, plastic, or the like is used as a core and the core is coated with the metal, metal particles, or carbon. (E) Conductive particles, plastic cores coated with the above metals, metal particles or carbon, and hot-melt metal particles are deformable by heating and pressurization, so that the contact area with the electrode increases during connection. This is preferable because reliability is improved. (E) The electroconductive particle may be a particle obtained by coating silver on a metal particle made of copper, for example. Further, as the conductive particles (e), a metal powder having a shape in which a large number of fine metal particles are connected in a chain shape as described in JP-A-2005-116291 can be used.

  Further, (e) fine particles obtained by further covering the surface of the conductive particles with a polymer resin or the like, and (e) an insulating layer made of an insulating material is provided on the surface of the conductive particles by a method such as hybridization. By using one, short-circuiting due to contact between particles when the content of conductive particles increases is suppressed, and insulation between electrode circuits is improved. You may mix and use with particle | grains.

  (E) As for the average particle diameter of electroconductive particle, 1-18 micrometers is preferable from a dispersibility and an electroconductive point. When (e) such conductive particles are contained, an adhesive for circuit connection can be suitably used as the anisotropic conductive adhesive.

  (E) The content of the conductive particles is not particularly limited, but is preferably 0.1% by volume or more, more preferably 0.2% by volume or more based on the total volume of the adhesive component. There exists a tendency for the insulation between adjacent connection terminals to improve further, ensuring the electroconductivity between the opposing connection terminals as the said content is 0.1 volume% or more. (E) The content of the conductive particles is preferably 30% by volume or less, more preferably 10% by volume or less, based on the total volume of the adhesive component. When the content is 30% by volume or less, a short circuit tends to be less likely to occur. “Volume%” is determined based on the volume of each component before curing at 23 ° C., but the volume of each component can be converted from mass to volume using specific gravity. In addition, do not dissolve or swell the component in a graduated cylinder, etc., and put in a suitable solvent (water, alcohol, etc.) that wets the component well. It can also be determined as a volume.

(Other ingredients)
A stabilizer can be added to the adhesive for circuit connection according to the present embodiment in order to further improve the control of the curing rate and the storage stability. As such a stabilizer, known compounds can be used without particular limitation, but quinone derivatives such as benzoquinone and hydroquinone; phenol derivatives such as 4-methoxyphenol and 4-t-butylcatechol; Preferred are aminoxyl derivatives such as 1,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl; hindered amine derivatives such as tetramethylpiperidyl methacrylate. A stabilizer can be used individually by 1 type or in mixture of 2 or more types.

  The content of the stabilizer is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.02% by mass or more, based on the total mass of the adhesive component. When the content is 0.005% by mass or more, the curing rate tends to be more easily controlled and the storage stability tends to be further improved. The content of the stabilizer is preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less, based on the total mass of the adhesive component adhesive component. When the content is 10% by mass or less, the storage stability tends to be further improved without impairing the curability.

  In addition, an adhesive aid such as a coupling agent represented by an alkoxysilane derivative and a silazane derivative, an adhesion improver, and a leveling agent may be appropriately added to the adhesive for circuit connection according to the present embodiment. As the coupling agent, specifically, a compound represented by the following general formula (Q) is preferable. A coupling agent can be used individually by 1 type or in mixture of 2 or more types.

[In formula (Q), R ²⁵ , R ²⁶ and R ²⁷ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or an alkoxycarbonyl group having 1 to 5 carbon atoms. Or R ²⁸ is a (meth) acryloyl group, vinyl group, isocyanate group, imidazole group, mercapto group, amino group, methylamino group, dimethylamino group, benzylamino group, phenylamino group, cyclohexylamino group , Morpholino group, piperazino group, ureido group or glycidyl group, and s represents an integer of 1 to 10. ]

  The adhesive for circuit connection according to the present embodiment may contain a rubber component for the purpose of stress relaxation and adhesion improvement. The rubber component refers to a component that exhibits rubber elasticity (JIS K6200) as it is or a component that exhibits rubber elasticity by reaction. The rubber component may be solid or liquid at room temperature (25 ° C.), but is preferably liquid from the viewpoint of improving fluidity. As the rubber component, a compound having a polybutadiene skeleton is preferable. The rubber component may have a cyano group, a carboxyl group, a hydroxyl group, a (meth) acryloyl group, or a morpholine group. From the viewpoint of improving adhesiveness, a rubber component containing at least one of a cyano group and a carboxyl group, which are highly polar groups, in the side chain or terminal is preferable. In addition, even if it has a polybutadiene skeleton, if it exhibits thermoplasticity, it is classified as (a) a thermoplastic resin, and if it exhibits radical polymerizability, it is classified as (b) a radically polymerizable compound.

  Specific examples of the rubber component include polyisoprene, polybutadiene, carboxyl-terminated polybutadiene, hydroxyl-terminated polybutadiene, 1,2-polybutadiene, carboxyl-terminated 1,2-polybutadiene, hydroxyl-terminated 1,2-polybutadiene, acrylic rubber, Styrene-butadiene rubber, hydroxyl-terminated styrene-butadiene rubber, acrylonitrile-butadiene rubber, carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group-containing acrylonitrile-butadiene rubber, carboxylated nitrile rubber, hydroxyl-terminated poly ( Oxypropylene), alkoxysilyl group-terminated poly (oxypropylene), poly (oxytetramethylene) glycol, polyolefin glycol and the like. The content of the rubber component is preferably 3 to 60% by mass, more preferably 5 to 30% by mass, based on the total mass of the adhesive component.

  In addition, the rubber component having a high polar group and being liquid at room temperature specifically includes a liquid acrylonitrile-butadiene rubber, a carboxyl group, a hydroxyl group, a (meth) acryloyl group or a morpholine group at the polymer end. Examples thereof include liquid acrylonitrile-butadiene rubber and liquid carboxylated nitrile rubber. The content of the rubber component having a highly polar group and being liquid at room temperature is preferably 3 to 60% by mass, and more preferably 5 to 30% by mass based on the total mass of the adhesive component.

  These rubber components can be used individually by 1 type or in mixture of 2 or more types.

  In addition, organic fine particles may be added to the circuit connection adhesive according to the present embodiment for the purpose of stress relaxation and improvement of adhesion. The average particle size of the organic fine particles is preferably 0.05 to 1.0 μm. In addition, when organic fine particles consist of the above-mentioned rubber component, it classifies into a rubber component instead of organic fine particles, and when organic fine particles consist of the above-mentioned (a) thermoplastic resin, it is not organic fine particle (a) thermoplastic resin Classify into:

  Specific examples of the organic fine particles include polyisoprene, polybutadiene, carboxyl group-terminated polybutadiene, hydroxyl group-terminated polybutadiene, 1,2-polybutadiene, carboxyl group-terminated 1,2-polybutadiene, acrylic rubber, styrene-butadiene rubber, and acrylonitrile-butadiene. Rubber, carboxyl group, hydroxyl group, acrylonitrile-butadiene rubber, carboxylated nitrile rubber, hydroxyl-terminated poly (oxypropylene), alkoxysilyl group-terminated poly (oxypropylene), poly (polypropylene) containing (meth) acryloyl group or morpholine group at the polymer end (Oxytetramethylene) glycol, polyolefin glycol (meth) acrylic acid alkyl-butadiene-styrene copolymer, (meth) acrylic acid alkyl-silicone copolymer or Silicone - (meth) acrylic copolymer, or organic fine particles made of composites thereof.

  In addition, as an adhesive for circuit connection for manufacturing a connection structure in which a substrate described later is composed of a base material containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate and polyethylene naphthalate, silicone is used. It may contain fine particles.

  The adhesive for circuit connection for manufacturing the connection structure comprised from the base material in which a board | substrate contains at least 1 sort (s) chosen from the group which consists of a polyethylene terephthalate, a polycarbonate, and a polyethylene naphthalate contains a silicone microparticle. Since the internal stress can be sufficiently relaxed, the adhesive strength to polyethylene terephthalate, polycarbonate and polyethylene naphthalate can be further improved, and the adhesive strength to a member having a connection terminal can be further improved. In addition, more stable performance can be maintained even after a long-term reliability test.

  As the silicone fine particles, fine particles of polyorganosilsesquioxane resin having rubber elasticity are known, and spherical or amorphous silicone fine particles are used. Moreover, it is preferable that a silicone fine particle has a weight average molecular weight of 1 million or more from a viewpoint of a dispersibility and relaxation of an internal stress. The silicone fine particles preferably have a three-dimensional crosslinked structure. Such silicone fine particles have high dispersibility with respect to the resin, and are further excellent in stress relaxation after curing. Since the silicone fine particles having a weight average molecular weight of 1 million or more and / or having a three-dimensional cross-linked structure are all low in solubility in polymers such as thermoplastic resins, monomers, and solvents, the above-described effects can be obtained more remarkably. be able to. Here, “having a three-dimensional crosslinked structure” indicates that the polymer chain has a three-dimensional network structure. The glass transition temperature of the silicone fine particles is preferably from −130 ° C. to −20 ° C., more preferably from −120 ° C. to −40 ° C. Such silicone fine particles can sufficiently relieve the internal stress of the adhesive for circuit connection as a circuit connection material.

  Specifically, the silicone fine particles having such a structure include an organopolysiloxane containing at least two vinyl groups, an organohydropolyene polysiloxane having at least two hydrogen atoms bonded to silicon atoms, and a platinum series. Silicone fine particles obtained by reaction with a catalyst (for example, JP-A-62-2579939); silicone fine particles obtained by using an organopolysiloxane having an alkenyl group, an organopolysiloxane having a hydrosilyl group, and a platinum-based catalyst (for example, , JP 63-77942 A); silicone fine particles obtained using diorganosiloxane, monoorganosilsesquioxane, triorganosiloxy and a platinum-based catalyst (for example, JP 62-270660 A); methyl Silanetriol and / Or silicone particles (e.g., Patent No. 3,970,453 discloses) obtained water / alcohol solution of the partial condensate made to perform an addition and polycondensation reaction in an aqueous alkaline solution or the like may be used. In addition, in order to improve dispersibility and adhesion to the substrate, silicone fine particles to which an epoxy compound is added or copolymerized (for example, JP-A-3-167228), an acrylate compound is added or copolymerized. Silicone fine particles can also be used.

  In order to further improve dispersibility, it is preferable to use silicone fine particles having a core-shell structure. The core-shell type structure includes a structure in which a surface layer (shell layer) having a glass transition temperature higher than the glass transition temperature of the surface of the core material (core layer) is formed, and a graft layer (shell) outside the core material (core layer). Layer), and silicone fine particles having different compositions in the core layer and the shell layer can be used. Specifically, core-shell type silicone fine particles (for example, Japanese Patent No. 2832143) obtained by adding an alkaline substance or an alkaline aqueous solution and an organotrialkoxysilane to an aqueous dispersion of spherical silicone rubber fine particles, followed by hydrolysis and condensation reaction, International Core-shell type silicone fine particles as described in JP 2009/051067 A can also be used. Silicone fine particles containing a functional group such as a hydroxyl group, an epoxy group, a ketimine, a carboxyl group, or a mercapto group at the molecular terminal or the inner chain can be used. Such silicone fine particles are preferable because dispersibility in a film-forming component and a radical polymerizable substance is improved.

  The average particle size of the silicone fine particles is preferably 0.05 to 25 μm, more preferably 0.1 to 20 μm. When the average particle diameter is 0.05 μm or more, the internal stress tends to be further improved while maintaining the fluidity of the circuit connecting adhesive. Moreover, when the average particle size is 25 μm or less, the effect of relaxing internal stress tends to be sufficiently exhibited.

  The content of the silicone fine particles is preferably 3% by mass or more, more preferably 5% by mass or more, based on the total mass of the adhesive component. When the content of the silicone fine particles is 3% by mass or more, the effect of relieving internal stress tends to be sufficiently exhibited. The content of the silicone fine particles is preferably 40% by mass or less, more preferably 30% by mass or less, based on the total mass of the adhesive component. When the content of the silicone fine particles is 40% by mass or less, the flexibility (elastic modulus, elongation) of the adhesive for circuit connection is further improved, and the adhesive strength tends to be further improved.

  These silicone fine particles can be used singly or in combination of two or more.

  The circuit connecting adhesive according to the present embodiment can be used in a paste form when the circuit connecting adhesive is liquid at room temperature. When the circuit connection adhesive is solid at room temperature, it may be heated and used, or may be made into a paste using a solvent. Solvents that can be used are preferably those that are not reactive with circuit connection adhesives and additives and that exhibit sufficient solubility, and those having a boiling point of 50 to 150 ° C. at normal pressure. When the boiling point is 50 ° C. or higher, volatilization is reduced even when left at room temperature, and use in an open system tends to be facilitated. Further, when the boiling point is 150 ° C. or lower, the solvent does not easily evaporate, so that the paste can be applied while maintaining compatibility, and the reliability after adhesion tends to be further improved.

  Moreover, the adhesive for circuit connection which concerns on this embodiment can also be used in film form. The film-like adhesive is liquefied by dissolving or dispersing the composition containing the above-described components in an organic solvent, and is applied on a peelable substrate or a substrate such as a nonwoven fabric, and the activation temperature of the curing agent. It can be obtained by removing the solvent below. As the peelable substrate, a fluororesin film, a polyethylene terephthalate film, a release paper or the like can be used. If it is used in the form of a film, it is more convenient in terms of handleability.

  The adhesive for circuit connection according to the present embodiment can be bonded by using heating and pressurization together. The heating temperature is preferably 100 to 200 ° C. The pressure is preferably in a range that does not damage the adherend, and generally 0.1 to 10 MPa. These heating and pressurization are preferably performed in the range of 0.5 to 120 seconds, and can be bonded by heating at 120 to 190 ° C., 3 MPa, and 10 seconds.

  The adhesive for circuit connection according to the present embodiment can be used as an adhesive for different types of adherends having different thermal expansion coefficients. Specifically, circuit connection materials represented by anisotropic conductive adhesive, silver paste, silver film, etc., elastomer for chip size package (CSP), underfill material for CSP, lead-on-chip (Lead On Chip) (Chip, LOC) It can be used as a semiconductor element adhesive material represented by a tape.

(Connection structure)
Next, a connection structure manufactured using the above-described adhesive for circuit connection will be described. FIG. 1 is a schematic cross-sectional view showing a connection structure according to the first embodiment. FIG. 2 is a schematic cross-sectional view showing a manufacturing method of the connection structure shown in FIG. The circuit member connection structure 100 shown in FIG. 1 is manufactured using (e) an adhesive for circuit connection that does not contain conductive particles.

  A circuit member connection structure 100 shown in FIG. 1 includes a circuit member (first circuit member) 10, a circuit member (second circuit member) 20, and a connection member 30. The circuit member 10 includes a circuit board (first board) 12 and connection terminals (first connection terminals) 14 arranged on the main surface 12 a of the circuit board 12. The circuit member 20 includes a circuit board (second board) 22 and connection terminals (second connection terminals) 24 disposed on the main surface 22 a of the circuit board 22.

  The connection member 30 is disposed between the circuit member 10 and the circuit member 20. The connecting member 30 connects the circuit member 10 and the circuit member 20 so that the main surface 12a and the main surface 22a face each other substantially in parallel. In the connection structure 100, the connection terminal 14 and the connection terminal 24 are arranged to face each other and are electrically connected by being in contact with each other. The connection member 30 is made of a cured product of a circuit connection adhesive 30a described later.

  The connection structure 100 can be manufactured as follows, for example. First, as shown in FIG. 2, a circuit member 10, a circuit member 20, and a circuit connecting adhesive 30a are prepared. The circuit connecting adhesive 30a is formed, for example, by forming the above-described circuit connecting adhesive into a film shape. Next, the circuit connection adhesive 30a is placed on the main surface 22a of the circuit member 20 on which the connection terminals 24 are formed. Then, the circuit member 10 is placed on the circuit connection adhesive 30 a so that the connection terminal 14 faces the connection terminal 24. Subsequently, the circuit connection adhesive 30a is cured while heating the circuit connection adhesive 30a through the circuit member 10 and the circuit member 20, and the circuit member 10 is pressed in a direction perpendicular to the main surfaces 12a and 22a. The connecting member 30 is formed between the two. Thereby, the connection structure 100 is obtained.

  In the cured product of the circuit connecting adhesive 30a, the plane of the inorganic filler contained in the circuit connecting adhesive 30a and the circuit member are preferably substantially parallel, and the major axis direction of the inorganic filler is substantially the same. More preferably, they match. Since the plane of the inorganic filler and the circuit member are substantially parallel, the stress between the circuit member and the adhesive for circuit connection generated by expansion and contraction due to thermal expansion in the surface direction of the circuit member during the moisture resistance reliability test is further increased. Can be suppressed.

  Moreover, when the cured product is viewed in the thickness direction, it is preferable that the portions where the concentration of the inorganic filler is high and the thin portions are distributed in layers. In particular, when viewed in the thickness direction of the cured product, it is more preferable that the layer structure has a portion where an inorganic filler is present and a portion where no inorganic filler is present.

  When the adhesive for circuit connection contains conductive particles, the anisotropic conductive film produced using such an adhesive for circuit connection is interposed between the connecting terminals facing each other, and heated and pressurized, A circuit member connection structure can be obtained by bonding the circuit members while electrically connecting the connection terminals via the conductive particles. FIG. 3 is a schematic cross-sectional view showing the connection structure according to the second embodiment. FIG. 4 is a schematic cross-sectional view showing a manufacturing method of the connection structure shown in FIG. The circuit member connection structure 200 shown in FIG. 3 is manufactured using (e) an adhesive for circuit connection containing conductive particles.

  The circuit member connection structure 200 shown in FIG. 3 includes the circuit member 10, the circuit member 20, and the connection member 40 in the same manner as the connection structure 100. In the connection structure 200, the connection terminal 14 and the connection terminal 24 are arranged to face each other in a state of being separated from each other.

  The connection member 40 is disposed between the circuit member 10 and the circuit member 20. The connection member 40 is made of a cured product of an adhesive 40a for circuit connection described later, and has an adhesive component 42 and conductive particles 44 dispersed in the adhesive component 42. The adhesive component 42 is made of a cured product of an adhesive component 42a described later. In the connection structure 200, the conductive particles 44 are in contact with the connection terminals 14 and 24 between the connection terminals 14 and 24 that face each other, so that the connection terminals 14 and 24 are electrically connected to each other via the conductive particles 44. It is connected to the.

  The connection structure 200 can be manufactured as follows, for example. First, as shown in FIG. 4, a circuit member 10, a circuit member 20, and a circuit connecting adhesive 40a made of the above circuit connecting adhesive are prepared. The circuit connecting adhesive 40a is formed, for example, by forming the circuit connecting adhesive into a film. The circuit connecting adhesive 40a includes an adhesive component 42a and conductive particles 44 dispersed in the adhesive component 42a. Thereafter, the circuit member 10 and the circuit member 20 are connected through the circuit connecting adhesive 40a by the same method as the method of obtaining the circuit member connection structure 100 described above. Thereby, the connection structure 200 is obtained.

  At least one of the circuit board 12 and the circuit board 22 in the circuit member connection structures 100 and 200 may be formed of a base material containing a thermoplastic resin having a glass transition temperature of 200 ° C. or lower. For example, at least one of the circuit board 12 and the circuit board 22 may be composed of an organic base material including at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate. As a result, when organic base materials such as polyethylene terephthalate, polycarbonate, and polyethylene naphthalate are used, the wettability of the circuit board with the adhesive for circuit connection is improved, resulting in excellent adhesive strength even under low temperature curing conditions. Can be obtained. Therefore, stable performance (adhesion strength and connection resistance) can be maintained even after a long-term reliability test (high temperature and high humidity test), and excellent connection reliability can be obtained.

  When one of the circuit board 12 and the circuit board 22 is composed of a base material containing at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate, the circuit board 12 And the other circuit board of the circuit boards 22 may be composed of a base material containing at least one selected from the group consisting of polyimide and polyethylene terephthalate. Thereby, the wettability with the adhesive for circuit connection in a circuit board and adhesive strength further improve, and the further excellent connection reliability can be acquired.

  In addition, the circuit boards 12 and 22 may be comprised from the base materials containing inorganic materials, such as a semiconductor, glass, a ceramic; Organic substances, such as a polyimide and a polycarbonate; These composite materials, such as glass / epoxy. The circuit boards 12 and 22 may be flexible boards.

  FIG. 5 is a schematic cross-sectional view showing a connection structure according to the third embodiment. A solar cell module 300 shown in FIG. 5 includes solar cells 310a and 310b, a wiring member 320, and a connection member 330.

  The solar cells 310a and 310b include a substrate 312, a surface electrode (connection terminal) 314 disposed on the surface (main surface) 312a of the substrate 312, and a back surface disposed on the back surface (main surface) 312b of the substrate 312. And an electrode (connection terminal) 316. The substrate 312 is made of, for example, a semiconductor, an inorganic material such as glass or ceramic, or a composite material such as glass / epoxy. The substrate 312 may be a flexible substrate. The surface 312a is a light receiving surface.

  The wiring member 320 is a member for electrically connecting the solar battery cell 310a and another member, and for example, electrically connects one solar battery cell to another solar battery cell. In FIG. 5, the surface electrode 314 of the solar battery cell 310 a and the back electrode 316 of the solar battery cell 310 b are electrically connected by the wiring member 320.

  The connection member 330 is disposed between the solar battery cell 310a and the wiring member 320, and between the solar battery cell 310b and the wiring member 320, and connects the solar battery cells 310a and 310b and the wiring member 320. Yes. The connection member 330 contains the hardened | cured material of the said adhesive agent for circuit connections, and contains the insulating substance. The connection member 330 may further contain conductive particles or may not contain conductive particles. When the connection member 330 contains electroconductive particle, the surface electrode 314 and the wiring member 320 of the photovoltaic cell 310a can be electrically connected through electroconductive particle. Further, the back electrode 316 of the solar battery cell 310b and the wiring member 320 can also be electrically connected via conductive particles. When the connection member 330 does not contain conductive particles, for example, the surface electrode 314 of the solar battery cell 310a and the back electrode 316 of the solar battery cell 310b may be in contact with the wiring member 320.

  In the solar cell module 300, the connection member 330 is formed of a cured product of the above-described circuit connection adhesive. Thereby, the adhesive strength of the connection member 330 between the photovoltaic cells 310a and the wiring members 320 and between the photovoltaic cells 310b and the wiring members 320 is sufficiently high, and the connection resistance between the photovoltaic cells 310a and the wiring members 320 is sufficiently small. ing. Moreover, even when it is left for a long time in a high temperature and high humidity environment, it is possible to sufficiently suppress a decrease in adhesive strength and an increase in connection resistance. Further, the connecting member 330 can be formed by a heat treatment at a low temperature for a short time. Therefore, the solar cell module shown in FIG. 5 can be manufactured without deteriorating the solar cells 310a and 310b at the time of connection, and can have higher reliability than conventional ones.

  The solar cell module 300 uses the solar cells 310a and 310b and the wiring member 320 in place of the circuit member 10 and the circuit member 20 in the method for manufacturing the connection structures 100 and 200 described above, and the method for manufacturing the connection structure described above. It can be manufactured by the same method.

  In the connection structures 100 and 200 and the solar cell module 300, the circuit connection adhesive used as a connection member does not need to be completely cured (the highest degree of curing that can be achieved under a predetermined curing condition). A partially cured state may be used as long as the characteristics are produced.

  Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited thereto.

<Thermoplastic resin>
(Preparation of polyester urethane)
Polyester urethane resin (manufactured by Toyobo Co., Ltd., UR-4800 (trade name), weight average molecular weight: 32000, glass transition temperature: 106 ° C.) is dissolved in a mixed solvent of methyl ethyl ketone and toluene in a weight ratio of 1: 1 to obtain a resin content of 30. A mass% solution was prepared.

(Preparation of phenoxy resin)
40 parts by mass of phenoxy resin (trade name: YP-50 (manufactured by Tohto Kasei Co., Ltd.), weight average molecular weight: 60000, glass transition temperature: 80 ° C.) is dissolved in 60 parts by mass of methyl ethyl ketone, and the resin content is 40% by mass Prepared.

<Radically polymerizable compound>
(Synthesis of urethane acrylate (UA1))
Poly (1,6-hexanediol carbonate) having a number average molecular weight of 1000 (trade name: DURANOL) in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser equipped with a calcium chloride drying tube, and a nitrogen gas introduction tube. T5562, Asahi Kasei Chemicals Corporation) 2500 parts by mass (2.50 mol) and dibutyltin dilaurate (Sigma Aldrich) 5.53 parts by mass were added. After sufficiently introducing nitrogen gas, the mixture was heated to 70 to 75 ° C., and 666 parts by mass (3.00 mol) of isophorone diisocyanate (manufactured by Sigma-Aldrich) was uniformly added dropwise over 3 hours to be reacted. After completion of the dropwise addition, the reaction was continued for about 10 hours. 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Sigma-Aldrich) and 0.53 parts by weight of hydroquinone monomethyl ether (manufactured by Sigma-Aldrich) were added to this and reacted at 70 ° C. for 6 hours in an air atmosphere. The urethane acrylate (UA1) was obtained. The weight average molecular weight of the obtained urethane acrylate was 15000.

(Preparation of vinyl compound having phosphoric acid group (P-2M))
As a vinyl compound having a phosphoric acid group, 2- (meth) acryloyloxyethyl phosphate (trade name: Light Ester P-2M, manufactured by Kyoeisha Chemical Co., Ltd.) was prepared.

(Preparation of isocyanuric acid-modified bifunctional acrylate (M-215))
Isocyanuric acid-modified bifunctional acrylate (manufactured by Toagosei Co., Ltd., M-215 (trade name)) was prepared.

<Preparation of inorganic filler>
As an inorganic filler, scaly boron nitride particles (trade name: Denkaboron nitride HGP, manufactured by Denki Kagaku Kogyo Co., Ltd.), scaly alumina particles (trade name: Seraph 02025, manufactured by Kinsei Matec Co., Ltd.), silica particles (trade name) : Aerosil R805, manufactured by Nippon Aerosil Co., Ltd.).
DENKABORON NITRIDE HGP (hereinafter abbreviated as “HGP”) had a planar average width of 5 μm, an average thickness of 0.5 μm, and an aspect ratio of 10. Seraph 02025 (hereinafter abbreviated as “02025”) had a planar average width of 2 μm, an average thickness of 0.08 μm, and an aspect ratio of 25.

<Radical polymerization initiator>
Dibenzoyl peroxide (trade name: Nyper BW, manufactured by NOF Corporation) was prepared as a radical polymerization initiator.

<Conductive particles>
(Preparation of conductive particles)
A nickel layer having a thickness of 0.2 μm is provided on the surface of particles having polystyrene as a core, and then a gold layer having a thickness of 0.02 μm is provided on the outside of the nickel layer. Particles were made.

[Examples 1 to 10 and Comparative Examples 1 to 5]
(Production of adhesive for circuit connection)
As shown in Table 1 in terms of solid mass ratio, a thermoplastic resin, a radical polymerizable compound, a radical polymerization initiator, and an inorganic filler were blended, and further an adhesive component (excluding conductive particles in the adhesive for circuit connection). Based on the total volume of the component), 1.5% by volume of conductive particles were blended and dispersed to obtain an adhesive for circuit connection. The obtained adhesive for circuit connection is applied onto a fluororesin film having a thickness of 80 μm using a coating apparatus, and the adhesive for film-like circuit connection having an adhesive layer thickness of 16 μm is dried by hot air at 70 ° C. for 10 minutes. An agent was obtained.

(Measurement of connection resistance and adhesive strength)
The flexible circuit board (FPC) which has 500 copper circuits of line width 25micrometer, pitch 50micrometer, and thickness 8micrometer on the polyimide film, and the adhesive for circuit connection of Examples 1-10 and Comparative Examples 1-5, and 0.2 micrometer And a glass with a thickness of 1.1 mm (ITO, surface resistance 20Ω / □) on which a thin layer of ITO was formed. Using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.), this was heated and pressurized at 160 ° C. and 3 MPa for 10 seconds to be connected over a width of 2 mm to produce a connection structure A. Using a multimeter, the resistance value between adjacent circuits of this connection structure A immediately after connection and after being kept in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 240 hours (after a high-temperature and high-humidity test) Measured. The resistance value was shown as an average of 37 resistances between adjacent circuits.

  Moreover, the adhesive strength of the connection structure A was measured by a 90-degree peeling method according to JIS-Z0237 immediately after the connection and after the high temperature and high humidity test. Here, Tensilon UTM-4 (peeling speed 50 mm / min, 25 ° C.) manufactured by Toyo Baldwin Co., Ltd. was used as an adhesive strength measuring device.

  A flexible circuit board (FPC) having 80 copper circuits having a line width of 150 μm, a pitch of 300 μm, and a thickness of 8 μm on the polyimide film (Tg 350 ° C.) with the adhesives for circuit connection of Examples 1 to 10 and Comparative Examples 1 to 5; And a 0.1 μm thick PET substrate (Ag) on which a thin layer of 5 μm thick Ag paste was formed. Using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.), this was heated and pressurized at 140 ° C. and 2 MPa for 20 seconds to be connected over a width of 2 mm to produce a connection structure B. The resistance value between the adjacent circuits of the connection structure B composed of the FPC and the PET substrate on which a thin layer of Ag paste is formed is 240 hours in a high-temperature and high-humidity bath at 85 ° C. and 85% RH immediately after the connection. After holding (after the high temperature and high humidity test), the measurement was performed using a multimeter. The resistance value was shown as an average of 37 resistances between adjacent circuits.

  Moreover, the adhesive strength of the connection structure B was measured and evaluated under the same conditions as the connection structure A immediately after connection and after the high temperature and high humidity test.

  The measurement results of the connection resistance and the adhesive strength of the connection structures A and B measured as described above are shown in Table 2 below.

  The FPC / ITO connection structure A manufactured using the circuit connection adhesives of Examples 1 to 10 was 240 immediately after connection at a heating temperature of 160 ° C. and in a high-temperature and high-humidity tank of 85 ° C. and 85% RH. After holding for a long time (after the high temperature and high humidity test), a good connection resistance of about 3.8Ω or less and a good adhesive strength of 610 N / m or more were exhibited. Also in the FPC / PET connection structure B, immediately after connection at a heating temperature of 140 ° C. and after being held in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 240 hours (after a high-temperature and high-humidity test), Good connection resistance of about 1.9Ω or less and good adhesive strength of 600 N / m or more were exhibited. It was confirmed that the adhesive for circuit connection obtained in Examples 1 to 10 was excellent in adhesiveness and connection reliability.

  On the other hand, in the connection structure manufactured using the adhesive for circuit connection of Comparative Examples 1 to 5, the adhesive force is low (Comparative Examples 1 to 3), or after connection, and in a high-temperature and high-humidity tank. It was confirmed that the connection resistance after the holding for 240 hours (after the high temperature and high humidity test) increased (Comparative Examples 4 and 5).

  DESCRIPTION OF SYMBOLS 10 ... Circuit member (1st circuit member), 12 ... Circuit board (1st board | substrate), 12a ... Main surface, 14 ... Connection terminal (1st connection terminal), 20 ... Circuit member (2nd circuit member) ), 22 ... Circuit board (second board), 22a ... Main surface, 24 ... Connection terminal (second connection terminal), 30, 40 ... Connection member, 30a, 40a ... Adhesive for circuit connection, 42 ... Adhesion Agent component, 44 ... conductive particles, 100, 200 ... connection structure of circuit members, 300 ... solar cell module (connection structure), 310a, 310b ... solar cell, 312 ... substrate, 312a ... surface (main surface) , 312b ... back surface (main surface), 314 ... front electrode, 316 ... back electrode, 320 ... wiring member, 330 ... connection member.

Claims (10)

Interposed between a first circuit member having a first connection terminal and a second circuit member having a second connection terminal, and electrically connecting the first connection terminal and the second connection terminal. An adhesive for circuit connection,
The adhesive for circuit connection contains (a) a thermoplastic resin, (b) a radical polymerizable compound, (c) a radical polymerization initiator, and (d) an inorganic filler, and the shape of the (d) inorganic filler is fragmented. Jodea is,
(D) The adhesive for circuit connection whose content of an inorganic filler is 0.5-20 mass% with respect to the whole adhesive for circuit connection.   The adhesive for circuit connection according to claim 1, wherein (d) the inorganic filler contains at least one selected from alumina and boron nitride. The adhesive for circuit connection according to claim 1 or 2 , wherein the radical polymerizable compound (b) contains at least one vinyl compound having a phosphate group and one or more radical polymerizable compounds other than the vinyl compound. Agent. Wherein (a) thermoplastic resin, phenoxy resin, polyurethane resin, polyester urethane resins, butyral resins, containing at least one selected from the group consisting of acrylic resin and polyimide resin, any one of claims 1 to 3 The adhesive for circuit connection as described in 2. (E) The adhesive for circuit connection as described in any one of Claims 1-4 which further contains electroconductive particle. A first circuit member having a first connection terminal; a second circuit member having a second connection terminal; and the first circuit member and the second circuit member disposed between the first circuit member and the first circuit member. A connection member for electrically connecting the connection terminal and the second connection terminal,
The connection structure of a circuit member in which the said connection member contains the hardened | cured material of the adhesive agent for circuit connections as described in any one of Claims 1-5 . The circuit member connection structure according to claim 6 , wherein at least one of the first circuit member and the second circuit member is formed of a base material including a thermoplastic resin having a glass transition temperature of 200 ° C. or lower. body. At least one of the first circuit member and the second circuit member, polyethylene terephthalate, and a substrate comprising at least one selected from the group consisting of polycarbonate and polyethylene naphthalate, claim 6 Circuit member connection structure. One of the first circuit member and the second circuit member is composed of a base material including at least one selected from the group consisting of polyethylene terephthalate, polycarbonate, and polyethylene naphthalate,
The circuit member connection structure according to claim 6 , wherein the other is composed of a base material containing at least one selected from the group consisting of polyimide and polyethylene terephthalate. A solar battery cell having a connection terminal disposed on a main surface of the substrate and the substrate, a wiring member, and disposed between the solar battery cell and the wiring member, and electrically connecting the solar battery cell and the wiring member. A connection member for connecting
The solar cell module in which the said connection member contains the hardened | cured material of the adhesive agent for circuit connections as described in any one of Claims 1-5 .