KR101211813B1 - Adhesive composition and connection structure - Google Patents
Adhesive composition and connection structure Download PDFInfo
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- KR101211813B1 KR101211813B1 KR1020100068812A KR20100068812A KR101211813B1 KR 101211813 B1 KR101211813 B1 KR 101211813B1 KR 1020100068812 A KR1020100068812 A KR 1020100068812A KR 20100068812 A KR20100068812 A KR 20100068812A KR 101211813 B1 KR101211813 B1 KR 101211813B1
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- 0 COc(cc1)c(cccc2)c2c1OC(C(*)=C)=O Chemical compound COc(cc1)c(cccc2)c2c1OC(C(*)=C)=O 0.000 description 2
- LVNDUJYMLJDECN-UHFFFAOYSA-N Cc1cc(N)cc(N)c1 Chemical compound Cc1cc(N)cc(N)c1 LVNDUJYMLJDECN-UHFFFAOYSA-N 0.000 description 1
Abstract
The present invention provides an adhesive composition capable of obtaining excellent adhesive strength under low temperature and short curing conditions and maintaining stable performance (adhesive strength or connection resistance) even after a reliability test (high temperature and high humidity test) and a connection member of a circuit member using the same. To provide.
The present invention relates to a branched polymer obtained by polymerizing (a) a thermoplastic resin, (b) a radical polymerizable compound, (c) a compound represented by the following general formula (1), and the following general formulas (1), (2a) and (3b). Branched polymers obtained by polymerizing at least two compounds of the compounds represented, or branched polymers formed by polymerizing at least two compounds of the compounds represented by the following formulas (1), (2b) and (3a), and
AR 20- (B) X. (One)
R 21- (A) 2 . (2a), R 21- (B) 2 . (2b)
R 22- (A) 3 . (3a), R 22- (B) 3 ... (3b)
[Wherein R 20 is a (1 + x) valent organic group, R 21 is a divalent organic group, R 22 is a trivalent organic group, x is an integer of 2 or more, A is a functional group reactive with B, B is a Each reactive functional group]
(d) relates to an adhesive composition containing a radical polymerization initiator.
Description
The present invention relates to an adhesive composition and a bonded structure.
Various adhesives are used in order to combine the various members which comprise elements, such as a semiconductor element and a liquid crystal display element. The demand for such an adhesive is wide, including adhesiveness, heat resistance, reliability in high temperature and high humidity. Examples of adherends used for bonding include organic substrates such as printed wiring boards and polyimides, as well as substrates having various surface states such as metals such as copper and aluminum, ITO (composite oxide of indium and tin), SiN, and SiO 2 . It is used, and the adhesive requires the molecular design suited to a to-be-adhered body.
As an adhesive agent for semiconductor elements and liquid crystal display elements, thermosetting resin using the epoxy resin which is high adhesiveness and shows high reliability has been used (for example, refer patent document 1). As a constituent 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 for promoting the reaction between the epoxy resin and the curing agent are generally used. The thermal latent catalyst does not react at a storage temperature such as room temperature, and has a high reactivity when heated, and is an important factor for determining the curing temperature and curing rate. In view of the storage stability of the adhesive at room temperature and the curing rate upon heating, various compounds have been used as the thermal latent catalyst. In actual processes, desired adhesion is often obtained by curing at 170 to 250 ° C. for 1 to 3 hours. Due to the recent high integration of semiconductor devices and high definition of liquid crystal devices, the pitch between devices and wirings is narrowed and cured. There is a risk of adversely affecting the peripheral members due to heating. Moreover, in order to reduce cost, hardening (low temperature fast hardening) at low temperature and a short time is calculated | required. In order to achieve this low temperature fast curing with an adhesive using an epoxy resin, it is necessary to use a thermal latent catalyst having a low activation energy. However, it is known that it is very difficult to have storage stability in the vicinity of room temperature.
In recent years, the radical curable adhesive which used together radical polymerizable compounds, such as an acrylate derivative and a methacrylate derivative, and a peroxide which is a radical polymerization initiator, attracts attention. Radical hardening was able to harden for a short time because the radical which is reactive active species is rich in reactivity (for example, refer patent document 2). However, since adhesive shrinkage at the time of heating is large in the adhesive agent of radical curing system, adhesive strength is inferior compared with the case where an epoxy resin is used. As a method of solving such a problem, the method of adding liquid rubber to an adhesive and improving wettability and improving adhesive strength is proposed (for example, patent document 3).
However, since organic substrates, such as polyimide, have a rigid, planar molecular structure and form a strong charge transfer complex between molecules, formation of covalent bonds with the adhesive composition is very difficult. Moreover, since a polyimide surface is smooth normally, the adhesive effect by a physical anchoring effect (anchor effect) is small. Therefore, only by improving wettability, adhesive strength will fall as expected after long time exposure (for example, 85 degreeC / 85% RH) in high temperature, high humidity conditions. When such a material is used for an adhesive of a semiconductor device or a liquid crystal display device which requires stable performance even after a long time exposure under high temperature and high humidity conditions, characteristics such as adhesive force and connection resistance deteriorate after a reliability test.
Therefore, the present invention provides an adhesive composition capable of obtaining excellent adhesive strength under low temperature and short curing conditions and maintaining stable performance (adhesive strength or connection resistance) even after a long time reliability test (high temperature and high humidity test) and a circuit using the same. It is an object to provide a connection structure of a member.
The present invention relates to a branched polymer obtained by polymerizing (a) a thermoplastic resin, (b) a radical polymerizable compound, (c) a compound represented by the following general formula (1), and the following general formulas (1), (2a) and (3b). Branched polymers obtained by polymerizing at least two compounds of the compounds represented, or branched polymers formed by polymerizing at least two compounds of the compounds represented by the following formulas (1), (2b) and (3a), and
AR 20- (B) X. (One)
R 21- (A) 2 . (2a), R 21- (B) 2 . (2b)
R 22- (A) 3 . (3a), R 22- (B) 3 ... (3b)
[Wherein R 20 is a (1 + x) valent organic group, R 21 is a divalent organic group, R 22 is a trivalent organic group, x is an integer of 2 or more, A is a functional group reactive with B, B is a Each reactive functional group]
(d) An adhesive composition containing a radical polymerization initiator is provided. According to such a structure, adhesion | attachment in low temperature fast hardening is attained and the stable adhesive strength can be maintained even after a long time reliability test.
(c) It is preferable that a branched polymer has at least 1 or more of a urethane bond and an imide bond. By having at least one or more such bonds in the branched polymer, heat resistance, adhesive strength with organic substrates such as printed wiring boards and polyimides can be further improved, and excellent connection reliability can be obtained.
(c) It is preferable that a branched polymer has an isocyanurate ring. By using the branched polymer of such a structure, the adhesive strength with organic substrates, such as a printed wiring board and a polyimide, and heat resistance can be improved further, and it becomes possible to obtain the outstanding connection reliability.
(c) The weight average molecular weight of a branched polymer can be 1000 or more and less than 20000. By using the branched polymer of such molecular weight, heat resistance further improves and the outstanding connection reliability can be obtained.
(c) The branched polymer may have a radical polymerizable functional group. When the branched polymer has a radically polymerizable functional group, the branched polymer reacts with other components to obtain a crosslinked structure, further improves heat resistance, and obtains excellent connection reliability.
In the above case, it is preferable that the branched polymer (c) has three or more radically polymerizable functional groups per molecule. When the number of radically polymerizable functional groups is more than the above-mentioned numerical value, a high crosslinking density is obtained, heat resistance further improves and the outstanding connection reliability can be obtained.
(b) It is preferable that a radically polymerizable compound contains the vinyl compound which has a phosphoric acid group, and 1 or more types of radically polymerizable compounds other than the said compound, respectively. When the radically polymerizable compound contains such a compound, excellent adhesion strength to the substrate, especially the metal, can be obtained.
(a) It is preferable that a thermoplastic resin contains at least 1 sort (s) of resin chosen from the group which consists of a phenoxy resin, a polyurethane resin, polyesterurethane resin, butyral resin, an acrylic resin, and a polyimide resin. By using such a resin as a thermoplastic resin, heat resistance and adhesiveness further improve, and these outstanding characteristics can be maintained even after a long time reliability test (high temperature, high humidity test).
It is preferable that an adhesive composition contains (e) electroconductive particle further. By containing electroconductive particle, favorable electroconductivity or anisotropic electroconductivity can be provided to an adhesive composition, and it becomes possible to use an adhesive composition especially preferably for adhesive use etc. of circuit members which have a circuit electrode. Moreover, the connection resistance between the circuits electrically connected through the said adhesive composition can be reduced more fully.
The present invention provides a connection structure between a first circuit member having a first connection terminal on a main surface, a second circuit member having a second connection terminal on a main surface, and a circuit member provided with a connection member. While the 1st and 2nd circuit member are arrange | positioned through a connection member so that a connection terminal may oppose, the 1st and 2nd connection terminal are electrically connected, and a connection member is comprised from the hardened | cured material of the adhesive composition of this invention. Provided is a connection structure of a circuit member. Since the above-mentioned hardened | cured material of the adhesive composition is used for connection of a pair of circuit members, such a bonded structure can make adhesive strength between circuit members high enough, and also long-term reliability test (for example, 85 degreeC) / 85% RH), stable performance can be maintained. In addition, the adhesive composition of this invention used as a connection member does not need to be fully hardened (the highest hardening which can be achieved by predetermined hardening conditions), and may be in the state of partial hardening as long as the said characteristic is produced. .
According to the present invention, excellent adhesive strength can be obtained even at low temperature and short curing conditions, and stable performance can be maintained even after a long time reliability test (for example, standing at 85 ° C / 85% RH) and handling The adhesive composition excellent in the property and the connection structure of the circuit member using the same can be provided.
Hereinafter, preferred embodiments of the present invention will be described in detail. In addition, (meth) acrylic acid represents acrylic acid or methacrylic acid corresponding to it, (meth) acrylate means an acrylate or a methacrylate corresponding to it, and a (meth) acryloyl group corresponds to an acryloyl group or it It means a methacryloyl group.
In addition, in this specification, (a) glass transition temperature (Tg) of a thermoplastic resin means main dispersion peak temperature defined below. That is, using a dynamic viscoelasticity measuring device (for example, viscoelastic analyzer "RSA-3" (trade name) manufactured by TA Instruments, Inc.), the temperature increase rate 5 占 폚 / min, frequency 10 Hz for the film of the thermoplastic resin (a) And dynamic viscoelasticity are measured on condition of -150-300 degreeC, and the peak temperature of tan-delta is made into main dispersion peak temperature.
In addition, in this invention, a weight average molecular weight and a number average molecular weight mean the value measured using the analytical curve by standard polystyrene from a gel permeation chromatograph (GPC) according to the conditions shown in Table 1.
EMBODIMENT OF THE INVENTION Hereinafter, embodiment of the adhesive composition of this invention is described in detail.
The thermoplastic resin (a) used in the present invention is a solid at room temperature, becomes a liquid state by heating, and can be freely deformed by external force, and when cooled to remove the external force, it becomes hard while maintaining its shape. Resin (polymer) which has the property which can be performed repeatedly. Moreover, resin (polymer) which has the reactive functional group which has the said property is also included. (a) 0-190 degreeC is preferable and, as for Tg of a thermoplastic resin, 20-170 degreeC is more preferable. In addition, even if it corresponds to the definition of said thermoplastic resin, the compound which has a structure of (c) branched polymer mentioned later is classified into (c) branched polymer.
It is preferable that a thermoplastic resin has a linear main chain. When a thermoplastic resin has a side chain, it is preferable that the said side chain is not a dendritic shape (it refers to the shape which branches increase as it goes to a front end). As such a thermoplastic resin, a polyimide resin, a polyamide resin, a phenoxy resin, a (meth) acrylic resin, a urethane resin, a polyester urethane resin (urethane modified polyester resin), polyvinyl butyral resin, etc. can be used. These can be used individually or in mixture of 2 or more types. In addition, these thermoplastic resins may contain a siloxane bond and a fluorine substituent. These resins can be suitably used as long as the resins to be mixed are completely compatible or have a microphase separation. When using an adhesive composition as a film form, the larger the molecular weight of the said thermoplastic resin is, the film formability is easily obtained, and the melt viscosity which affects the fluidity | liquidity as a film adhesive composition can be set extensively. As a weight average molecular weight, 5,000-150,000 are preferable and 10,000-80,000 are especially preferable. When this value is 5,000 or more, good film formability is obtained, while when it is 150,000 or less, good compatibility with other components tends to be easily obtained.
In the adhesive composition of the present invention, the content of the (a) thermoplastic resin is preferably 5 to 80% by mass, more preferably 15 to 70% by mass based on the total amount of the adhesive composition. When the adhesive composition is used in the form of a film at 5 mass% or more, particularly good film formability tends to be obtained, and when it is 80 mass% or less, the fluidity of the good adhesive composition tends to be easily obtained.
(b) The radically polymerizable compound refers to a compound which generates radical polymerization by the action of a radical polymerization initiator, and may be a compound which generates its own radical by applying activation energy such as light or heat. As a radically polymerizable compound, the compound which has a functional group superposed | polymerized by active radicals, such as a vinyl group, a (meth) acryloyl group, an allyl group, and a maleimide group, can be used preferably, for example.
Specifically, oligomers, such as an epoxy (meth) acrylate oligomer, a urethane (meth) acrylate oligomer, a polyether (meth) acrylate oligomer, and a polyester (meth) acrylate oligomer, and a trimethylol propane tri (meth) acrylate , Polyethylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, neopentyl glycoldi (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, isocyanuric acid modified bifunctional (meth) acrylate, isocyanuric acid modified trifunctional (meth) acrylate, bisphenoxyethanol fluorene acrylate, Epoxy (meth) acrylate and bisphenoxy ethanol flu which added (meth) acrylic acid to the glycidyl group of bisphenol fluorene diglycidyl ether The compound which introduce | transduced the (meth) acryloyloxy group into the compound which added ethylene glycol or propylene glycol to the glycidyl group of ethylene acrylate and bisphenol fluorene diglycidyl ether, and is represented by following General formula (I) and (II) The compound which becomes.
(Wherein 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)
(Wherein R 3 and R 4 each independently represent a hydrogen atom or a methyl group, and c and d each independently represent an integer of 0 to 8)
In addition, when (b) the radically polymerizable compound is left alone at 30 ° C., it can be used without particular limitation even if it exhibits a solid state without fluidity such as wax, lead, crystal, glass, or powder.
Specifically, N, N'-methylenebisacrylamide, diacetone acrylamide, N-methylol acrylamide, N-phenyl methacrylamide, 2-acrylamide-2-methylpropanesulfonic acid, tris (2-acrylo) Iloxyethyl) 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'-diphenylmethanebismaleimide, m-phenylenebismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl- 1,3-phenylenebismaleimide, N-methacryloxymaleimide, N-acryloxymaleimide, 1,6-bismaleimide- (2,2,4-trimethyl) hexane, N-methacryloyl Oxysuccinimide, N-acryloyloxy succinimide, 2-naphthyl methacrylate, 2-naphthyl acrylate, pentaerythritol tetraacrylate, divinyl ethylene urea, divinyl propylene urea, 2-polytyryl ethyl methacrylate, N-phenyl-N '-(3 -Methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, N-phenyl-N '-(3-acryloyloxy-2-hydroxypropyl) -p-phenylenediamine, tetramethyl Piperidyl methacrylate, tetramethylpiperidyl acrylate, pentamethyl piperidyl methacrylate, pentamethyl piperidyl acrylate, octadecyl acrylate, Nt-butyl acrylamide, diacetone acrylamide, N- (Hydroxymethyl) acrylamide and the compound represented by following General formula (III)-(XII) are mentioned.
(e represents an integer of 1 to 10)
(Wherein R 5 represents a hydrogen atom or a methyl group, R 6 represents a hydrogen atom or a methyl group, and f represents an integer of 15 to 30)
(Wherein R 7 represents a hydrogen atom or a methyl group, R 8 represents a hydrogen atom or a methyl group, and g represents an integer of 15 to 30)
(Wherein R 9 represents a hydrogen atom or a methyl group)
(Wherein R 10 represents a hydrogen atom or a methyl group, h represents an integer from 1 to 10)
(Wherein R 11 represents a hydrogen atom or an organic group represented by the following formula (i) or (ii), i represents an integer of 1 to 10, and * in formulas (i) and (ii) represents a bonding position) )
(Wherein R 12 represents hydrogen or an organic group represented by the following formula (iii) or (iv), j represents an integer of 1 to 10, and * in formulas (iii) and (iv) represents a bonding position)
(Wherein R 13 represents a hydrogen atom or a methyl group)
(Wherein R 14 represents a hydrogen atom or a methyl group)
Using together the vinyl compound which has a phosphoric acid group which is a compound which belongs to (b) component, and the N-vinyl type compound chosen from the group which consists of N-vinyl compound and N, N-dialkylvinyl compound with (b) component other than these can do. By using together with the vinyl compound which has a phosphoric acid group, it becomes possible to improve adhesiveness with respect to the metal base material of an adhesive composition. Moreover, the crosslinking rate of an adhesive composition can be improved by using together with N-vinyl type compound.
Although there will be no restriction | limiting in particular if it is a compound which has a phosphoric acid group and a vinyl group as a vinyl compound which has a phosphoric acid group, The compound represented by following formula (XIII)-(XV) is preferable.
(Wherein R 15 represents a (meth) acryloyl group, R 16 represents a hydrogen atom or a methyl group, k and l each independently represent an integer of 1 to 8, wherein, R 15 and R 16 are k and l may be the same or different)
(Wherein R 17 represents a (meth) acryloyl group, m and n each independently represent an integer of 1 to 8, wherein R 17 , m and n may be the same or different, respectively.
(Wherein R 18 represents a (meth) acryloyl group, R 19 represents a hydrogen atom or a methyl group, and o and p each independently represent an integer of 1 to 8)
Specifically as said compound, an acid phospho oxyethyl methacrylate, an acid phospho oxyethyl acrylate, an acid phospho oxypropyl methacrylate, an acid phospho oxy polyoxyethylene glycol monomethacrylate Acid phosphooxy polyoxypropylene glycol monomethacrylate, 2,2'-di (meth) acryloyloxydiethyl phosphate, EO modified phosphate dimethacrylate, phosphoric acid modified epoxy acrylate, vinyl phosphate, etc. are mentioned. Can be.
It is preferable that the addition amount of the vinyl compound which has a phosphoric acid group shall be 0.2-300 mass parts with respect to 100 mass parts of (a) thermoplastic resins independently of the addition amount of the (b) radically polymerizable compound other than the vinyl compound which has a phosphoric acid group, and also 1 It is more preferable to set it as 200 mass parts. When the addition amount of the vinyl compound having a phosphate group is 0.2 parts by mass or more, high adhesive strength is easily obtained, and when it is 300 parts by mass or less, the physical properties of the adhesive composition after curing are less likely to be reduced, thereby making it easy to secure reliability.
Specific examples of the N-vinyl compound include N-vinylimidazole, N-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, N-vinyl caprolactam, and 4,4'-vinylidene bis. (N, N-dimethylaniline), N-vinylacetamide, N, N-dimethyl acrylamide, N, N-diethyl acrylamide, etc. are mentioned.
It is preferable that the addition amount of the (b) radically polymerizable compound except the compound contained in the vinyl compound which has a phosphoric acid group mentioned above is 50-250 mass parts with respect to 100 mass parts of (a) thermoplastic resin, More preferably, it is 60-150 mass It is wealth. Sufficient heat resistance is easy to be obtained after hardening that addition amount is 50 mass parts or more. Moreover, when it is 250 mass parts or less, favorable film formability will be easy to be obtained, when using as a film.
In addition, the branched polymers used in the present invention include, for example two to one type of substituent group in the self-polymerization, one molecule of AB X type monomer having more than three total substituents of two (x is an integer of 2 or more) in a molecule more Polymerization of an A 2 type monomer having and a B 3 type monomer having three substituents different from A in one molecule, or at least two or more monomers selected from AB X type, A 2 type and B 3 type It can be obtained by polymerization. Branched polymers are also polymerized with a B 2 type monomer having two types of substituents in one molecule and an A 3 type monomer having three types of substituents different from B in one molecule, or AB X type and B 2 It can obtain by superposition | polymerization of the monomer chosen from at least 2 or more from a type | mold and an A <3> type.
In the monomer, the AB X type is represented by AR 20- (B) X , the A 2 type is represented by R 21- (A) 2 , and the B 3 type is represented by R 22- (B) 3 . In addition, B 2 type, R 21 - (B) 2, A 3 R 22 is type - is represented by (A) 3. Here, A and B are selected from hydroxyl group (including phenol hydroxyl group), carboxylic acid group (including anhydride carboxylic acid), amino group, thiol group, isocyanate group, etc., and each of A and B represents a different functional group. It is preferable. In the case of A and B are hydroxyl groups (including phenol hydroxyl groups), carboxylic acid groups (including anhydride carboxylic acids), amino groups, and isocyanate groups, A and B react to react with ester bonds, amide bonds, urethane bonds, and imides. A bond can be formed, and interaction and wettability with respect to organic base materials, such as a printed wiring board and a polyimide, improve by this, and high adhesive strength is obtained. R 20 , R 21 , and R 22 are preferably selected from aromatic hydrocarbon groups, aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, hetero atom-containing groups, groups represented by the formulas (XVI) to (XXVII), and the like. * Indicates a bonding position. In terms of flexibility, aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, groups derived from compounds having aliphatic hydrocarbon backbones and aromatic hydrocarbon backbones, groups derived from compounds having alicyclic hydrocarbon backbones and aromatic hydrocarbon backbones, aliphatic hydrocarbon backbones and alicyclics More preferred are groups derived from compounds having a hydrocarbon backbone and an aromatic hydrocarbon backbone. Here, "the group derived" means the group of the structure from which the hydrogen atom was removed. Moreover, the group mentioned above may have an isocyanurate ring like group represented by Formula (XXVII). By employ | adopting the group mentioned above as R <20> , R <21> and R <22> , moderate flexibility is provided to the hardened | cured material of an adhesive composition, adhesive strength improves and connection reliability improves.
(Wherein q represents an integer of 1 to 10)
(Wherein r represents an integer of 1 to 10)
The branched polymers obtained from these monomers may be used alone or in combination of two or more kinds as the branched polymers.
Moreover, in the adhesive composition of this invention, in terms of the improvement of the adhesive strength with respect to a polyimide base material, it is preferable that a branched polymer contains an isocyanurate ring. When the branched polymer contains an isocyanurate ring, the heat resistance and the adhesive strength with organic substrates, such as a printed wiring board and a polyimide, can be improved and excellent connection reliability can be obtained. Moreover, it is more preferable that the bond produced | generated by reaction of the functional group represented by A and B contains a urethane bond and / or an imide bond. Since the branched polymer contains an imide bond, heat resistance and adhesive strength with organic substrates such as printed wiring boards and polyimides can be improved, and excellent connection reliability can be obtained. Moreover, since a branched polymer contains a urethane bond, adhesive strength with a base material improves and it exists in the tendency to suppress peeling.
Moreover, as long as the weight average molecular weight is 1000 or more and less than 20000, the polymerization degree of the branched polymer used by this invention can be adjusted freely and can be used preferably. When the weight average molecular weight of the branched polymer is 1000 or more, the film formability and physical properties tend to be improved. When the weight average molecular weight of the branched polymer is less than 20000, the solubility when the branched polymer is dissolved in a solvent and used, and the fluidity of the adhesive composition tends to be improved. There is this.
Moreover, it is preferable that (c) branched polymer in this invention has radical polymerizability in the functional group of all or one part terminal, It is more preferable to have 3 or more radically polymerizable functional group from a heat resistant viewpoint, 3 or more and 15 or less It is more preferable to have a radically polymerizable functional group. When the number of radically polymerizable functional groups is three or more, sufficient crosslinking density is easily obtained, and heat resistance tends to be improved.
Moreover, the addition amount of the (c) branched polymer used for this invention is 0.2-100 mass parts with respect to 100 mass parts of (a) thermoplastic resin, Preferably it is 0.5-70 mass parts. When addition amount is 0.2 mass part or more, heat resistance improves, and when it is less than 100 mass parts, when using as a film, there exists a tendency for film formability to improve.
As a (d) radical polymerization initiator used by this invention, the compound which generate | occur | produces a radical by the provision of energy from the exterior, such as a conventionally known organic peroxide and an azo compound, can be used, and it is 1 minute from a stability, reactivity, and a compatibility point, Organic peroxides having a liver half-life temperature of 90 to 175 ° C and a molecular weight of 180 to 1,000 are preferable. When the half-life temperature for 1 minute is in this range, it is excellent in storage stability, the radical polymerizability is also high enough, and it can harden | cure in a short time.
Specific examples of the (d) radical polymerization initiator include 1,1,3,3-tetramethylbutylperoxy neodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, and di (2-ethylhexyl Peroxydicarbonate, cumyl peroxy neodecanoate, dilauroyl peroxide, 1-cyclohexyl-1-methylethylperoxy neodecanoate, t-hexyl peroxy neodecanoate, t-butylper Oxyneodecanoate, t-butylperoxy pivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethyl Hexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy neoheptanoate, t-amylperoxy-2 Ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, t-amylperoxy-3,5,5-trimethylhexanoate, 3-hydroxy-1,1-dimethylbutylperoxyneode Decanoate, t-amylperoxy Odecanoate, t-amylperoxy-2-ethylhexanoate, di (3-methylbenzoyl) peroxide, dibenzoylperoxide, di (4-methylbenzoyl) peroxide, t-hexylperoxyisopropylmono Carbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (3-methyl Benzoylperoxy) hexane, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxy Organic peroxides such as benzoate, dibutyl peroxytrimethyl adipate, t-amylperoxy normal octoate, t-amyl peroxy isononanoate, t-amyl peroxy benzoate, and 2,2'-azobis- 2,4-dimethylvaleronitrile, 1,1'-azobis (1-acetoxy-1-phenylethane), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2- Methylbutyronitrile), dimethyl-2,2'-azobisisobutyro Trill, there may be mentioned azo compounds such as 4,4'-azobis (4-cyanovaleric acid), 1,1'-azobis (1-cyclohexane carbonitrile).
These compounds may be used alone or in combination of two or more compounds.
Moreover, as the (d) radical polymerization initiator of this invention, the compound which generate | occur | produces a radical by light irradiation of 150-750 nm can be used. Such compounds are described, for example, in Photoinitiation, Photopolymerization, and Photocuring, J.-P. [Alpha] -acetoaminophenone derivatives and phosphine oxide derivatives described in Fouassier, Hanser Publishers (1995, p17 to p35) are more preferable because of their high sensitivity to light irradiation.
These compounds may be used alone or in combination with the above organic peroxides and azo compounds.
0.1-500 mass parts is preferable with respect to 100 mass parts of (a) thermoplastic resins, and, as for the addition amount of the (d) radical polymerization initiator of this invention, 1-300 mass parts is more preferable. (d) When the addition amount of the radical polymerization initiator is 0.1 part by mass or more, the adhesive composition tends to be sufficiently cured, and when it is 500 parts by mass or less, the storage stability tends to be good.
(e) Although electroconductive particle should just be a particle | grain which has electroconductivity in the whole or the surface, When using for the connection of the circuit member which has a connection terminal, the thing whose average particle diameter is smaller than the distance between connection terminals is used.
Examples of the (e) conductive particles used in the present invention include metal particles such as Au, Ag, Ni, Cu, and solder, carbon, and the like. It is also possible to use a non-conductive glass, ceramic, plastic, or the like as a nucleus and coating the nucleus with the metal, metal particles, or carbon. (e) The conductive particles are made of plastic as a nucleus, and the nucleus is coated with the metal, metal particles or carbon, or hot molten metal particles, which are deformable by heating and pressurization. It is preferable because it increases and reliability improves.
Moreover, the microparticles | fine-particles which further coat | covered the surface of these (e) electroconductive particle with a polymer resin etc. can suppress the short circuit by the contact of the particles when the compounding quantity of electroconductive particle is increased, and the insulation between electrode circuits can improve. In view of the above, this may be used alone or in combination with (e) conductive particles.
It is preferable that the average particle diameter of this (e) electroconductive particle is 1-18 micrometers from a dispersibility and electroconductivity. When it contains such (e) electroconductive particle, an adhesive composition can be used suitably as an anisotropically conductive adhesive agent.
(e) Although the usage-amount of electroconductive particle is not specifically limited, It is preferable to set it as 0.1-30 volume% with respect to the whole volume of adhesive composition, and it is more preferable to set it as 0.1-10 volume%. If this value is 0.1 volume% or more, electroconductivity will tend to become high, and if it is less than 30 volume%, there exists a tendency for the short circuit of a circuit to become difficult to occur. In addition, although the volume% is determined based on the volume of each component before hardening at 23 degreeC, the volume of each component can be converted from volume to volume using specific gravity. In addition, the increased volume can be obtained as the volume by adding the component to an appropriate solvent (water, alcohol, etc.) that wets the component well without dissolving or swelling the component in a measuring cylinder or the like.
Stabilizers can be added to the adhesive composition of the present invention in order to control the curing rate and impart storage stability. As such a stabilizer, a well-known compound can be used without a restriction | limiting, Quinone derivatives, such as benzoquinone and hydroquinone; Phenol derivatives such as 4-methoxy phenol and 4-t-butyl catechol; Aminoxyl derivatives such as 2,2,6,6-tetramethylpiperidine-1-oxyl and 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl; Hindered amine derivatives, such as tetramethyl piperidyl methacrylate, are preferable.
The addition amount of a stabilizer is 0.01-30 mass parts with respect to 100 mass parts of adhesive compositions, Preferably it is 0.05-10 mass parts. When the amount is 0.01 parts by mass or more, control of the curing rate and storage stability are easily imparted, and when it is less than 30 parts by mass, it is difficult to adversely affect the compatibility with other components.
Into the adhesive composition of this invention, adhesion | attachment adjuvant, such as a coupling agent represented by an alkoxysilane derivative and a silazane derivative, an adhesion promoter and a leveling agent, can also be added suitably. Specifically, the compound represented by the following general formula (XXVIII) is preferable, and in addition to being used alone, two or more kinds of compounds may be mixed and used.
(Herein, R 23 , R 24 , and R 25 independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxycarbonyl group having 1 to 5 carbon atoms, or an aryl group, and R 26 represents (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 S represents an integer of 1 to 10).
The adhesive composition of this invention may use a rubber component together for the purpose of stress relaxation and an adhesive improvement. A rubber component means the component which shows rubber elasticity by the component or reaction which shows rubber elasticity (for example, JIS K6200) in the state as it is. The rubber component may be solid or liquid at room temperature (25 ° C.), but is preferably liquid in terms of fluidity improvement. 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. Moreover, the rubber component which contains the cyano group which is a high polar group, and a carboxyl group in a side chain or a terminal from an adhesive improvement viewpoint is preferable. Moreover, even if it has a polybutadiene frame | skeleton, when it shows thermoplasticity, it classifies as (a) component, and when it shows radically polymerizable, it classifies as (b) component.
Specific examples of the rubber component include polyisoprene, polybutadiene, carboxyl terminal polybutadiene, hydroxyl terminal polybutadiene, 1,2-polybutadiene, carboxyl terminal 1,2-polybutadiene, hydroxyl terminal 1,2-polybutadiene, acrylic rubber, Styrene-butadiene rubber, hydroxyl group terminal Styrene-butadiene rubber, acrylonitrile-butadiene rubber, carboxyl group, hydroxyl group, (meth) acryloyl group or acrylonitrile-butadiene rubber containing a (meth) acryloyl group or morpholine group at the polymer terminal, carboxylated nitrile rubber And hydroxyl group terminated poly (oxypropylene), alkoxysilyl group terminated poly (oxypropylene), poly (oxytetramethylene) glycol, and polyolefin glycol.
Moreover, as a rubber component which has the said high polar group and is liquid at room temperature, Specifically, the liquid acrylonitrile- which contains a liquid acrylonitrile- butadiene rubber, a carboxyl group, a hydroxyl group, a (meth) acryloyl group, or a morpholine group at a polymer terminal- Butadiene rubber and a liquid carboxylated nitrile rubber are mentioned, As for an acrylonitrile content which is a polar group, 10-60 mass% is preferable.
These compounds may be used alone or in combination of two or more compounds.
Moreover, the adhesive composition of this invention can also use organic fine particles together for the purpose of stress relaxation and an adhesive improvement. The average particle diameter of organic microparticles | fine-particles is 0.05-1.0 micrometer. In addition, when organic microparticles | fine-particles consist of the rubber component mentioned above, it classifies as a rubber component instead of organic microparticles | fine-particles, and when organic microparticles | fine-particles consist of the above-mentioned (a) thermoplastic resin, it classifies as a thermoplastic resin instead of organic microparticles | fine-particles.
Specific examples of the organic fine particles include polyisoprene, polybutadiene, carboxyl end polybutadiene, hydroxyl end polybutadiene, 1,2-polybutadiene, carboxyl end 1,2-polybutadiene, acrylic rubber, styrene-butadiene rubber, acrylonitrile- Acrylonitrile-butadiene rubber containing a butadiene rubber, a carboxyl group, a hydroxyl group, a (meth) acryloyl group, or a morpholine group at the polymer terminal, a carboxylated nitrile rubber, a hydroxyl group-terminated poly (oxypropylene), an alkoxysilyl group-terminated poly (oxy Propylene), poly (oxytetramethylene) glycol, polyolefinglycol, alkyl (meth) acrylate-butadiene-styrene copolymer, alkyl (meth) acrylate-silicone copolymer or silicone- (meth) acrylic copolymer or composite Can be mentioned.
These organic fine particles may be used alone or in combination of two or more kinds thereof.
The adhesive composition of the present invention can be used in paste form when it is liquid at room temperature. In the case of a solid at room temperature, in addition to heating, it can also paste into a solvent. As a solvent which can be used, it is preferable that it is not reactive with an adhesive composition and an additive, and shows sufficient solubility, and it is preferable that the boiling point in normal pressure is 50-150 degreeC. When boiling point is 50 degreeC or more, even if it leaves to stand at room temperature, there is little possibility that it will volatilize and use in an open system will become easy. Moreover, when a boiling point is less than 150 degreeC, it will be easy to volatilize a solvent and it will become less likely to adversely affect the reliability after adhesion | attachment.
The adhesive composition of this invention can also be used as a film form. If necessary, a solution obtained by adding a solvent or the like to the adhesive composition is applied onto a peelable base material such as a fluororesin film, a polyethylene terephthalate film, a release paper, or impregnated with the solution to a base such as a nonwoven fabric. It can be used as a film by removing the solvent and the like. When used in the shape of a film, it is more convenient in terms of handling properties.
The adhesive composition of this invention can be bonded together using heating and pressurization. As for heating temperature, the temperature of 100-250 degreeC is preferable. The pressure is preferably in a range that does not damage the adherend, and in general, 0.1 to 10 MPa is preferable. It is preferable to perform these heatings and pressurization in the range for 0.5 second-120 second, and it is possible to make it adhere | attach even by heating of 140-200 degreeC, 3 MPa, and 10 second.
The adhesive composition of the present invention can be used as an adhesive for heterogeneous adherends having different thermal expansion coefficients. Specifically, it can be used as a semiconductor device bonding material represented by a circuit connecting material such as an anisotropic conductive adhesive, a silver paste, or a silver film, an elastomer for CSP, an underfill material for CSP, an LOC tape or the like.
Below, an example of the connection of the adhesive composition of this invention containing electroconductive particle, and the anisotropic conductive film produced using and an electrode is demonstrated. The anisotropic conductive film is present between the opposite electrodes on the substrate, and heated and pressurized to obtain contact between the two electrodes and adhesion between the substrates, and to connect the electrodes. As a board | substrate which forms an electrode, each combination of these composites, such as inorganic substance, such as a semiconductor, glass, and ceramic, organic substance, such as polyimide or polycarbonate, and glass / epoxy, is applicable.
[Example]
EMBODIMENT OF THE INVENTION Although this invention is demonstrated concretely based on an Example below, this invention is not limited to this.
(Production of thermoplastic resin (phenoxy resin))
Phenoxy resin (trade name: YP-50, manufactured by Toto Kasei Co., Ltd.) dissolved 40 parts by mass of the resin in 60 parts by mass of methyl ethyl ketone to obtain a solution having a solid content of 40% by mass.
(Preparation of thermoplastic resin (polyester urethane resin))
As the polyester urethane resin (trade name: UR-1400, manufactured by Toyobo Co., Ltd.), a 1: 1 mixed solvent dissolved product of methyl ethyl ketone and toluene having a resin content of 30% by mass was used.
(Synthesis of urethane resin)
450 parts by mass of polybutylene adipate diol (manufactured by Aldrich) and a mass average molecular weight of 450 parts by mass of polyoxytetramethylene glycol (manufactured by Aldrich), 1,4- 100 parts by mass of butylene glycol (manufactured by Aldrich Co., Ltd.) were dissolved in 4000 parts by mass of methyl ethyl ketone (manufactured by Wako Junyaku Kogyo Co., Ltd.), and 390 parts by mass of diphenylmethane diisocyanate (manufactured by Aldrich Co., Ltd.) was added to 70 ° C. The reaction was carried out for 60 minutes to obtain a urethane resin. It was 100000 when the weight average molecular weight of the obtained urethane resin was measured by GPC method.
(Preparation of rubber ingredient)
Liquid rubber (brand name: Nipol DN601, manufactured by Nihon Xeon Co., Ltd.) was prepared.
(Preparation of Branched Polymer)
A hyperbranched polyimide polymer (trade name: V-8000 (Mw 11500, acid value 40.3 mgKOH / g), manufactured by DIC Corporation) was prepared.
Synthesis of Branched Polymer (HB-1)
100 g of V-8000, 150 ml of methylethylketone as reaction solvent, 0.001 g of hydroquinone as stabilizer, tetrabutylammonium chloride as base catalyst in a reactor equipped with a reflux condenser, stirrer, thermometer, thermostat and water separator g was added and 0.7 g (0.0049 mol) of glycidyl methacrylate (made by Tokyo Kasei Kogyo Co., Ltd.) was dripped under stirring. After refluxing and refluxing for 2 hours, the reaction mixture was dropped into water, reprecipitated, and the obtained solid was dried to obtain 95 g of branched polymer (HB-1). The weight average molecular weight of the obtained branched polymer was 12500, and the acid value was 37.9 mgKOH / g.
Synthesis of Branched Polymer (HB-2)
A branched polymer (HB-2) was prepared in the same manner as in the case of HB-1 except that 1.9 g (0.013 mol) of glycidyl methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 0.14 g of tetrabutylammonium chloride were added. 95 g was obtained. The weight average molecular weight of the obtained branched polymer was 12500, and the acid value was 33.2 mgKOH / g.
(Preparation of Branched Polymer)
Branched polymer type urethane acrylate (trade name: CN9013, manufactured by SARTOMER) was prepared.
(Preparation of a radically polymerizable compound)
Isocyanuric acid EO modified diacrylate (brand name: M-215, Toagosei Co., Ltd. make) was prepared.
(Synthesis of urethane acrylate (UA))
860 parts by mass of poly (hexamethylene carbonate) diol (manufactured by Aldrich Co., Ltd.) having a number average molecular weight of 860 in a reaction vessel equipped with a stirrer, a thermometer, a reflux cooling tube having a calcium chloride drying tube, and a nitrogen gas introduction tube. And 5.53 parts by mass of dibutyltin dilaurate (manufactured by Aldrich Co., Ltd.). After introducing nitrogen gas sufficiently, it heated at 70-75 degreeC, and 666 mass parts (3.00 mol) of isophorone diisocyanate (made by Aldrich Co., Ltd.) were dripped uniformly for 3 hours, and it was made to react. After completion of the dropping, the reaction was continued for about 10 hours. 238 parts by mass (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Aldrich Co., Ltd.) and 0.53 parts by mass of hydroquinone monomethyl ether (manufactured by Aldrich Co., Ltd.) were added thereto, followed by further reacting for 10 hours. By confirming that the isocyanate disappeared by this, reaction was complete | finished and urethane acrylate (UA) was obtained. The number average molecular weight of obtained urethane acrylate (UA) was 3700.
(Preparation of vinyl compound having a phosphate group)
2- (meth) acryloyloxyethyl phosphate (brand name: Light ester P-2M, Kyoisha Chemical Co., Ltd. make) was prepared.
(Preparation of radical polymerization initiator)
T-hexyl peroxy-2-ethylhexanoate (brand name: perhexyl O, the Nichi-Yu Oil Industries Ltd. make) was prepared as a radical polymerization initiator.
(Production of conductive particles)
A nickel layer having a thickness of 0.2 μm was provided on the surface of the particles containing polystyrene as a nucleus, and a gold layer having a thickness of 0.02 μm was provided on the outside of the nickel layer to produce conductive particles having an average particle diameter of 4 μm and a specific gravity of 2.5.
(Examples 1 to 7, Comparative Examples 1 to 4)
It mix | blends as shown in Table 2 by solid weight ratio, and also mix | disperses 1.5 vol% of electroconductive particle, and apply | coats it on the 80-micrometer-thick fluororesin film using a coating apparatus, and it is 70 degreeC for 10-minute hot air drying. To obtain a film adhesive composition having a thickness of 20 μm.
[Measurement of connection resistance, adhesive strength]
The flexible adhesive circuit board (FPC) which has 500 copper circuits of the line width of 25 micrometers, the pitch of 50 micrometers, and the thickness of 18 micrometers on the polyimide film for the film adhesive composition of Examples 1-7 and Comparative Examples 1-4, and 0.2 micrometer It interposed between the glass (thickness 1.1mm, surface resistance 20 (ohm) / square) which formed the thin layer of ITO of. This was heat-pressurized at 160 degreeC and 3 MPa for 10 second using the thermocompression bonding apparatus (heating system: constant heat type, Toray Engineering Co., Ltd.), and it connected over 2 mm in width, and produced the connection body. The resistance value between adjacent circuits of this connection body was measured by a multimeter immediately after adhesion | attachment, after hold | maintaining for 240 hours in 85 degreeC and the high temperature high humidity tank of 85% RH (after test). The resistance value was expressed as the average of 37 resistance points between adjacent circuits.
Moreover, the adhesive strength of this connector was measured and evaluated by the 90 degree peeling method according to JIS-Z0237. Here, Tensilon UTM-4 (peel rate 50 mm / min, 25 degreeC) by Toyo Baldwin Co., Ltd. was used for the measurement apparatus of adhesive strength. The result of the measurement of the connection resistance and adhesive strength of the film adhesive composition performed as mentioned above is shown in Table 3 below.
The adhesive compositions obtained in Examples 1 to 7 had a good connection resistance of about 3? It has been clarified to exhibit good adhesive strength of at least N / m.
On the other hand, in Comparative Examples 1 and 2 in which the (c) branched polymer in the present invention is not used, a good connection resistance is shown immediately after adhesion, but after holding for 240 hours in a high temperature and high humidity bath at 85 ° C. After the test), it became clear that the connection resistance was high and the adhesive strength was lowered. Moreover, in Comparative Examples 3 and 4, it was evident that the connection resistance was high and the adhesive strength was low after holding for 240 hours (after the test) immediately after adhesion and in a high temperature and high humidity bath at 85 ° C and 85% RH.
Claims (14)
(b) radically polymerizable compounds,
(c) a branched polymer obtained by polymerizing a compound represented by the following formula (1), a branched polymer formed by polymerizing at least two compounds of the compounds represented by the following formulas (1), (2a) and (3b), or Branched polymers obtained by polymerizing at least two compounds of the compounds represented by the following formulas (1), (2b) and (3a), and
AR 20- (B) X. (One)
R 21- (A) 2 . (2a), R 21- (B) 2 . (2b)
R 22- (A) 3 . (3a), R 22- (B) 3 ... (3b)
[Wherein R 20 is a (1 + x) valent organic group, R 21 is a divalent organic group, R 22 is a trivalent organic group, x is an integer of 2 or more, A is a functional group reactive with B, B is a Each reactive functional group]
(d) contains a radical polymerization initiator,
Wherein said branched polymer has a urethane bond, an imide bond, or both.
The first and second circuit members are disposed via the connection member so that the first and second connection terminals face each other, the first and second connection terminals are electrically connected, and the connection member is firstly connected. The connection structure of a circuit member comprised from the hardened | cured material of the adhesive composition of Claim.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| JPJP-P-2009-169270 | 2009-07-17 | ||
| JP2009169270 | 2009-07-17 |
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| JP (1) | JP5338753B2 (en) |
| KR (1) | KR101211813B1 (en) |
| CN (1) | CN101955736B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101933271B1 (en) * | 2016-03-23 | 2018-12-27 | 삼성에스디아이 주식회사 | An anisotropic conductive film and a connecting structure using thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5418399B2 (en) * | 2009-07-17 | 2014-02-19 | 日立化成株式会社 | Adhesive composition and circuit member connection structure using the adhesive composition |
| KR101381118B1 (en) * | 2011-11-04 | 2014-04-04 | 제일모직주식회사 | A composition for use of an anisotropic conductive film and anisotropic conductive film using the same |
| JP5788923B2 (en) * | 2012-03-23 | 2015-10-07 | 富士フイルム株式会社 | Conductive composition, conductive member, method for manufacturing conductive member, touch panel and solar cell |
| JP6163824B2 (en) * | 2013-03-28 | 2017-07-19 | 日立化成株式会社 | Adhesive resin composition for image display device, adhesive sheet for image display device, method for producing image display device, and image display device |
| JP6056641B2 (en) * | 2013-05-07 | 2017-01-11 | 日立化成株式会社 | Adhesive sheet for image display device, method for manufacturing image display device, and image display device |
| DE102013222739A1 (en) * | 2013-06-17 | 2014-12-18 | Tesa Se | Reactive 2-component adhesive system in film form |
| CN110277559B (en) * | 2019-06-17 | 2022-02-01 | 南开大学 | Polyimide conductive binder for silicon-based negative electrode of lithium ion battery |
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| JP2006257200A (en) | 2005-03-16 | 2006-09-28 | Hitachi Chem Co Ltd | Adhesive composition, adhesive composition for circuit connection and circuit connection structure and semiconductor device using it |
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| JPH11193318A (en) * | 1997-11-04 | 1999-07-21 | Toyo Ink Mfg Co Ltd | Curable composition |
| JP2003277489A (en) * | 2002-03-27 | 2003-10-02 | Dainippon Ink & Chem Inc | Multi-branched polymer and method for producing the same |
| JP4231748B2 (en) * | 2003-07-10 | 2009-03-04 | 太陽インキ製造株式会社 | Prepreg for printed wiring board and multilayer printed wiring board produced using the same |
| CN1635039A (en) * | 2003-12-25 | 2005-07-06 | 左晓兵 | Method for preparing novel B level high speed polyurethane enamelled wire paint |
| JP4760070B2 (en) * | 2005-03-16 | 2011-08-31 | 日立化成工業株式会社 | Adhesive, adhesive for circuit connection, connector and semiconductor device |
| JP4872125B2 (en) * | 2006-06-28 | 2012-02-08 | Ｄｉｃ株式会社 | Curable resin composition for multilayer printed wiring board, thermosetting adhesive film, and multilayer printed circuit board |
| JP5292838B2 (en) * | 2007-08-30 | 2013-09-18 | 日立化成株式会社 | Adhesive and circuit member connection structure |
| CN101302395B (en) * | 2008-06-05 | 2011-03-16 | 吴江市太湖绝缘材料厂 | Water-soluble polyurethane finished enamel |
| JP5418399B2 (en) * | 2009-07-17 | 2014-02-19 | 日立化成株式会社 | Adhesive composition and circuit member connection structure using the adhesive composition |
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2010
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- 2010-07-14 CN CN201010230253.XA patent/CN101955736B/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006257200A (en) | 2005-03-16 | 2006-09-28 | Hitachi Chem Co Ltd | Adhesive composition, adhesive composition for circuit connection and circuit connection structure and semiconductor device using it |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101933271B1 (en) * | 2016-03-23 | 2018-12-27 | 삼성에스디아이 주식회사 | An anisotropic conductive film and a connecting structure using thereof |
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| JP2011038080A (en) | 2011-02-24 |
| CN101955736B (en) | 2014-08-27 |
| JP5338753B2 (en) | 2013-11-13 |
| TW201127927A (en) | 2011-08-16 |
| TWI437065B (en) | 2014-05-11 |
| KR20110007970A (en) | 2011-01-25 |
| CN101955736A (en) | 2011-01-26 |
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