KR20100009528A - Adhesive composition and bonded body - Google Patents

Abstract

Disclosed is an adhesive composition containing a crystalline resin (a) having a melting point of 40-80°C, a radically polymerizable compound (b) and a radical polymerization initiator (c). This adhesive composition is excellent in adhesive strength and handling property, while exhibiting stable performance after a reliability test.

Description

Adhesive composition and bonding agent {ADHESIVE COMPOSITION AND BONDED BODY}

The present invention relates to adhesive compositions and conjugates.

In semiconductor devices and liquid crystal display devices, various adhesive compositions are used for the purpose of bonding various members in the device. The properties required for the adhesive composition cover many aspects such as adhesion, heat resistance, reliability under high temperature and high humidity. The Examples of the adherend to be used in the adhesive, as well as printed circuit board or an organic substrate such as polyimide, copper, metal such as aluminum or ITO, SiN, SiO _2, etc. The substrate having a wide variety of surface conditions are used. Therefore, the adhesive composition needs the molecular design suited to each to-be-adhered body.

Conventionally, thermosetting resins, such as an epoxy resin which has high adhesiveness and shows high reliability, have been used as an adhesive composition for semiconductor elements and a liquid crystal display element (for example, refer patent document 1). As a component of such an adhesive composition, the heat latent catalyst which accelerates reaction of an epoxy resin, a hardening | curing agent, such as a phenol resin which has reactivity with an epoxy resin, and an epoxy resin and a hardening agent is generally used. Heat latent catalysts have become important factors in determining the curing temperature and curing rate, and various compounds have been used in terms of storage stability at room temperature and curing rate upon heating. In an actual process, desired adhesion is obtained by hardening for 1 to 3 hours at the temperature of 170-250 degreeC.

However, with the recent high integration of semiconductor elements and the high precision of liquid crystal elements, the pitch between elements and wirings is narrowed, and there is a concern that the heating at the time of curing hardly affects the peripheral members.

Moreover, in order to reduce cost, it is necessary to improve a throughput, and the adhesive composition hardened | cured at low temperature and a short time, in other words, the adhesive composition of "low temperature fast curing" is calculated | required. In order to achieve the low temperature fast curing of the adhesive composition, for example, a thermal latent catalyst having a low activation energy is sometimes used, in which case it is known that it is very difficult to have a storage stability near room temperature.

Moreover, as an adhesive composition responding to the demand for low temperature fast curing, in recent years, attention has been paid to radical curable adhesives using a radical polymerizable compound such as an acrylate derivative or a methacrylate derivative and a peroxide that is a radical polymerization initiator. Such an adhesive composition can be cured for a short time because radicals which are reactive active species are rich in reactivity (see Patent Document 2, for example). On the other hand, the adhesive of the radical curing system generally has a poor adhesive strength because of the fast curing reaction. On the other hand, the method of improving wettability by adding liquid rubber to an adhesive agent, and improving adhesive strength is proposed (for example, patent document 3).

Patent Document 1: Japanese Patent Application Laid-Open No. 1-13480

Patent Document 2: International Publication No. 98/44067

Patent Document 3: International Publication No. 04/50779

[Initiation of invention]

[Problem to Solve Invention]

However, in recent years, since higher performance is required for semiconductor devices, the adhesive composition obtained by the method of adding the liquid rubber described in Patent Document 3 should further improve adhesive properties such as elastic modulus after curing and glass transition temperature. Required. That is, improvement of characteristics, such as adhesive force and connection resistance, after a reliability test (for example, 85 degreeC / 85% RH standing) is calculated | required. In addition, there was room for improvement due to a decrease in handleability, a decrease in repairability and the occurrence of blocking due to an increase in the adhesiveness when using a liquid rubber.

An object of this invention is to provide the adhesive composition which can obtain the outstanding adhesive strength, can maintain stable performance even after a reliability test, and is excellent in handleability, and the circuit member using the same.

[Means for solving the problem]

The adhesive composition of this invention contains (a) crystalline resin whose melting | fusing point is 40 degreeC-80 degreeC, (b) radically polymerizable compound, and (c) radical polymerization initiator.

The adhesive composition of this invention can obtain the outstanding adhesive strength by having the structure mentioned above, and can maintain stable performance (adhesive strength, connection resistance, etc.) after a reliability test (for example, high temperature, high humidity test). Moreover, since the melting | fusing point of (a) crystalline resin is 40 degreeC-80 degreeC, since the surface tag force in the room temperature range (for example, 25-30 degreeC) of an adhesive composition becomes low, it is excellent in handleability. Moreover, the said resin generally has favorable wettability with respect to a to-be-adhered body when it heats more than melting | fusing point and makes it a liquid state. Accordingly, the adhesive composition containing the resin exhibits excellent adhesive strength.

In the adhesive composition of the present invention, the melting point of (a) crystalline resin is preferably 40 ° C to 75 ° C. (a) Since melting | fusing point of crystalline resin is 40 degreeC-75 degreeC, the said effect is exhibited more remarkably.

In the adhesive composition of the present invention, the (a) crystalline resin preferably contains a crystalline polyester resin. (a) Cohesion force improves because a crystalline resin contains a polyester resin, and the outstanding adhesive strength can be obtained.

It is preferable that the said crystalline polyester resin is a crystalline polyester resin which has a carbonate group or an ether group. By including such crystalline polyester resin, the adhesive composition which has appropriate flexibility and has the outstanding adhesive strength can be obtained, maintaining crystallinity.

It is preferable that the adhesive composition of this invention further contains the vinyl compound which has at least 1 or more phosphoric acid group in (d) molecule | numerator. By containing such a compound, the outstanding adhesive strength with respect to a board | substrate, especially a metal substrate can be obtained.

The adhesive composition of the present invention further comprises (e) at least one amorphous resin selected from the group consisting of phenoxy resins, polyurethane resins, urethane-modified polyester resins, butyral resins, acrylic resins, and polyimide resins. It is preferable. By including such an amorphous resin, heat resistance and adhesion can be improved, excellent adhesive strength can be obtained, and excellent properties can be maintained even after a reliability test (high temperature and high humidity test) by improving the heat resistance of the cured product.

It is preferable that the adhesive composition of this invention contains (f) electroconductive particle further. Thereby, favorable electroconductivity or anisotropic conductivity can be provided to an adhesive composition. Therefore, it becomes possible to use an adhesive composition especially preferably for adhesive use etc. of circuit members which have a connection terminal (circuit electrode). Moreover, the connection resistance between the connection terminals electrically connected through the said adhesive composition can fully be reduced.

The present invention further provides a first circuit member having a first connection terminal on a main surface of a first circuit board, a second circuit member having a second connection terminal on a main surface of a second circuit board, and first and second parts. A bonding body provided between the first and second circuit members in a state where a connecting terminal is opposed, and having a circuit joining member for electrically connecting the first and second connecting terminals, wherein the circuit joining member is the adhesive described above. It provides the joined body which consists of a composition or its hardened | cured material, and is electrically joined between the 1st and 2nd connection terminal.

The bonded body having such a structure is formed by joining two circuit members with the connection terminals facing each other by the circuit joining members to achieve electrical conduction, and the adhesive composition of the present invention or the cured product thereof can be applied as the circuit joining members. Therefore, the adhesive strength between circuit members can be made high enough, and the stable performance (adhesive strength and connection resistance) can be maintained even after a reliability test (for example, 85 degreeC / 85% RH standing).

[Effects of the Invention]

According to the present invention, excellent adhesive strength can be obtained and stable performance can be maintained even after a reliability test, and an adhesive composition excellent in handleability and a bonded member of a circuit member using the same can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the differential scanning calorimetry curve (DSC curve) of urethane modified polyester resin (UR-1400).

FIG. 2 is a diagram showing a differential scanning calorimetry curve (DSC curve) of poly (caprolactone) used in Examples. FIG.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described in detail. In the present invention, the crystalline resin means that the differential scanning calorimetry curve obtained by differential scanning calorimetry (hereinafter, sometimes referred to as "DSC") is not a stepped endothermic change but a clear endothermic peak. It says resin which has. In addition, melting | fusing point of crystalline resin means the temperature of the peak top in the said endothermic peak.

In the present invention, differential scanning calorimetry was performed using a differential scanning calorimeter (Perkin Elmer, Pyris DSC7). Measurement conditions can be made into the conditions which flow in air at a flow volume of 10 mL / min, hold | maintain at 25 degreeC, and heat up to 120 degreeC at 10 degreeC / min.

On the other hand, amorphous resin means resin in which the differential scanning calorimetry curve obtained by DSC does not show a clear endothermic peak.

In the present invention, (meth) acrylic acid refers to acrylic acid or methacrylic acid corresponding thereto, (meth) acrylate means acrylate or methacrylate corresponding thereto, and (meth) acryloyl group is acryl It means diary or methacrylo diary.

The adhesive composition of this invention contains (a) crystalline resin whose melting | fusing point is 40 degreeC-80 degreeC, (b) radically polymerizable compound, and (c) radical polymerization initiator. Hereinafter, each component is explained in full detail.

Melting | fusing point (a) melting | fusing point used by this invention is 40 degreeC-80 degreeC, The melting point measured by the above-mentioned DSC is 40 degreeC or more and 80 degrees C or less, and has crystallinity. The crystalline resin is an essential component for use in combination with the (b) radically polymerizable compound and (c) radical polymerization initiator to form a liquid or solid adhesive composition, and exhibits film forming ability when used as a film adhesive. (a) The crystalline resin having a melting point of 40 ° C. to 80 ° C. is compatible with (or can be mixed with) a radically polymerizable compound, and (c) may have a radical polymerization initiator, and has such properties. As long as it exists, arbitrary crystalline resin can be employ | adopted.

As for melting | fusing point of the said crystalline resin, it is more preferable that it is 40 degreeC-75 degreeC, It is still more preferable that it is 40 degreeC-70 degreeC, It is especially preferable that it is 40 degreeC-65 degreeC. When melting | fusing point of crystalline resin is less than 40 degreeC, the surface tag force of the adhesive composition before hardening increases, and there exists a tendency for handleability to deteriorate. Moreover, when melting | fusing point of crystalline resin exceeds 80 degreeC, there exists a tendency for the fluidity | liquidity of the adhesive composition before hardening to fall. Although there is no restriction | limiting in particular in the molecular weight of the said crystalline resin, Generally, the thing of the weight average molecular weights 2000-100000 is preferable, and the thing of 5000-80000 is more preferable. When this value is less than 2000, there exists a tendency for film formability to fall and when it exceeds 100000, there exists a tendency for compatibility with other components to worsen.

Here, the crystalline resin has a region of regular molecular structure in at least a part of the molecule, and the crystallinity is expressed by a strong function of intermolecular force and affinity between polymers in the vicinity.

Examples of the crystalline resins include crystalline polyester resins, crystalline polyurethane resins, crystalline polyurea resins, crystalline polyamide resins, crystalline polypropylene resins, crystalline polyacetal resins, and crystalline polyphenol resins. have. Although these may be used individually or in mixture of 2 or more types, it is especially preferable to contain a crystalline polyester resin.

As crystalline polyester resin, the linear polyester resin which has crystallinity is used, for example.

The linear polyester resin can be obtained, for example, by condensation polymerization of diols having hydroxyl groups at both ends of the linear aliphatic chain and bifunctional carboxylic acid having a carboxyl group at both ends of the linear aliphatic hydrocarbon chain. In addition, bifunctional carboxylic acid can also be used as a salt like bifunctional carboxylic acid chloride.

Specifically, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octa At least one of diols having a hydroxyl group at both ends of a linear aliphatic chain such as methylene glycol, nonamethylene glycol, decamethylene glycol, neopentyl glycol, 1,4-butadiene glycol, oxalic acid, malonic acid, succinic acid, glutaric acid Acid, adipic acid, pimelic acid, sperinic acid, glutamic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decandicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid , Mesaconic acid, citraconic acid, itaconic acid, isophthalic acid, terephthalic acid, n-dodecylsuccinic acid, n-dodecenylsuccinic acid, cyclohexanedicarboxylic acid, anhydrides of these acids or lower alkyl esters It can obtain by condensation polymerization etc. with at least 1 sort (s) of bifunctional carboxylic acid which has a carboxyl group in both terminal of an aliphatic hydrocarbon chain.

Linear polyester resin can also be obtained by superposing | polymerizing oxycarboxylic acid, such as (epsilon) -caprolactone, enanthlactone, and caprylolatone, or its anhydride, and esterified product.

Moreover, it is preferable that the crystalline polyester resin used for this invention contains a carbonate group or an ether group. Such a crystalline polyester resin can be obtained, for example, by using a low molecular or high molecular polyol containing an ether group or a carbonate group alone or simultaneously with other polyols as the diol component constituting the crystalline polyester resin.

Examples of the polyol containing an ether group include ether diols, and examples of the ether diols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, polyhepta methylene glycol and polydecamethylene glycol triethylene glycol. Can be mentioned. As polycarbonate diol, 1, 6- hexanediol, polycarbonate diol, and 1, 4- butanediol adipate are mentioned.

In the adhesive composition of the present invention, the content of the crystalline resin having a melting point of 40 ° C to 80 ° C is preferably 1 to 60% by weight, more preferably 3 to 50% by weight based on the total amount of the adhesive composition. desirable. When the said content is less than 1 weight%, the effect on the fluidity | liquidity improvement of an adhesive composition tends to become small, and when it exceeds 50 weight%, there exists a tendency for the fluidity of crystalline resin itself to deteriorate.

(b) A radically polymerizable compound is a compound which forms a polymer with the radical which generate | occur | produced from the (c) radical polymerization initiator. (b) A radically polymerizable compound can use a well-known thing without a restriction | limiting in particular. In addition, (b) radically polymerizable compound can be used individually by 1 type or in mixture of several types of compound as needed.

(b) As a radically polymerizable compound, For example, 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 trimethyl All propane 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, bispe Epoxy (meth) acrylic which added (meth) acrylic acid to the glycidyl group of the oxyethanol fluorene acrylate and bisphenol fluorene diglycidyl ether Glyci of epoxy (meth) acrylate and bisphenol fluorene diglycidyl ether which added (meth) acrylic acid to the glycidyl group of bisphenoxy ethanol fluorene acrylate and bisphenol fluorene diglycidyl ether The compound which introduce | transduced the (meth) acryloyloxy group into the compound which added ethylene glycol and propylene glycol to the diyl group, and the compound represented by following formula (A) and B are mentioned. In addition to using these compounds independently, you may mix and use a some compound as needed.

[Wherein, R ₁ and R ₂ each independently represent a hydrogen or methyl group, and k and l each independently represent an integer of 1 to 8]

[Wherein, R ₃ and R ₄ each independently represent a hydrogen or methyl group, and m and n each independently represent an integer of 0 to 8]

(b) As a radically polymerizable compound, when standing alone at 30 degreeC, the compound which shows a solid state without fluidity, such as a wax, a wax, a crystalline, a glass, and a powder, can also be used.

As such a compound, 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-methacryl Loyloxysuccinimide, N-acryloyloxysuccinate Imide, 2-naphthyl methacrylate, 2-naphthyl acrylate, pentaerythritol tetraacrylate, divinyl ethylene urea, divinyl propylene urea, vinyl caprolactam, vinyl carbazole, 2-polytyryl ethyl methacrylate Rate, N-phenyl-N '-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine, N-phenyl-N'-(3-acryloyloxy-2-hydroxy Propyl) -p-phenylenediamine, bis (4-vinylphenyl) sulfone, 2-t-butoxy-6-vinylnaphthalene, tetramethylpiperidyl methacrylate, tetramethylpiperidylacrylate, pentamethylpi Ferridyl methacrylate, pentamethylpiperidyl acrylate, octadecyl acrylate, Nt-butyl acrylamide, diacetone acrylamide, N- (hydroxymethyl) acrylamide, the following general formula C, D, E, F, The compound represented by G, H, I, J, K, and L is mentioned. These compounds can also be used individually or in mixture as needed.

[Wherein P1 represents an integer of 1 to 10]

[Wherein R ₅ is hydrogen or methyl group, R ₆ is hydrogen or methyl group, p represents an integer of 15 to 30]

[Wherein R ₇ is hydrogen or methyl group, R ₈ is hydrogen or methyl group, q represents an integer of 15 to 30]

[Wherein R ₉ represents hydrogen or a methyl group]

[Wherein R ₁₀ is hydrogen or a methyl group, r represents an integer of 1 to 10]

[Wherein R ₁₁ is hydrogen or a group represented by the following formula a or b, s represents an integer of 1 to 10]

<Formula a>

<Formula b>

[Wherein R ₁₂ represents hydrogen or a group represented by the following formula c or d, t represents an integer of 1 to 10]

<Formula c>

<Formula d>

[Where R ₁₃ represents hydrogen or a methyl group]

[Wherein, R ₁₄ represents hydrogen or a methyl group]

In the adhesive composition, the content of the (b) radically polymerizable compound is preferably 40 to 2400 parts by weight, more preferably to 100 parts by weight of the crystalline resin having a melting point of 40 ° C to 80 ° C. 60 to 1500 parts by weight. When the said content is less than 40 weight part, the heat resistance after hardening tends to fall, and when it exceeds 2400 weight part, there exists a tendency for film formability to fall when using as a film.

(c) A radical polymerization initiator is a compound which starts the polymerization reaction of (b) radically polymerizable compound by generating a radical. (c) As long as it has such a property, a radical polymerization initiator can use a well-known compound. (c) Although a peroxide, an azo compound, etc. are mentioned as a radical polymerization initiator, The peroxide whose half life temperature is 90-175 degreeC and molecular weight 180-1000 is preferable for 1 minute from the viewpoint of stability, reactivity, and compatibility. Here, "1 minute half life temperature" means the temperature which half life becomes 1 minute, and "half life" means the time until the density | concentration of a radically polymerizable compound decreases to half of an initial value.

(c) As a radical polymerization initiator, specifically, 1,1,3,3- tetramethylbutyl peroxy neodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethyl Hexyl) peroxydicarbonate, cumylperoxy neodecanoate, 1,1,3,3-tetramethylbutylperoxy neodecanoate, dilauroyl peroxide, 1-cyclohexyl-1-methylethyl Peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butylperoxy neodecanoate, t-butylperoxy pivalate, 1,1,3,3-tetramethylbutylperoxy-2 Ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethyl Hexanoate, t-butylperoxy neoheptanoate, t-amylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, t-amylperoxy-3,5,5 -Trimethylhexanoate, 3-hydroxy-1,1- Methylbutyl peroxy neodecanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy neodecanoate, t-amylperoxy-2-ethylhexa Noate, di (3-methylbenzoyl) peroxide, dibenzoylperoxide, di (4-methylbenzoyl) peroxide, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'- Azobis (1-acetoxy-1-phenylethane), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azo Bisisobutyronitrile, 4,4'-azobis (4-cyanovaleric acid), 1,1'-azobis (1-cyclohexanecarbonitrile), t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (3-methylbenzoylper Oxy) hexane, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-di (benzo Peroxy) hexane, t-butylperoxybenzoate, dibutyl peroxytrimethyl adipate, t-amylperoxy normal octoate, t-amyl peroxy isononanoate, t-amyl peroxy benzoate, etc. are mentioned. have. These compounds may be used alone or in combination of two or more kinds thereof.

Moreover, the compound which generate | occur | produces a radical by light irradiation of wavelength 150-750 nm can be used as (c) radical polymerization initiator. As such a compound, known compounds can be used without particular limitation, for example, Photoinitiation, Photopolymerization, and Photocuring, J.-P. [Alpha] -acetoaminophenone derivatives and phosphine oxide derivatives described in Fouassier, Hanser Publishers (1995), p17 to p35] are more preferred because of their high sensitivity to light irradiation. These compounds may be used alone or in combination with the above peroxides and azo compounds.

In the adhesive composition, the content of the radical polymerization initiator (c) is preferably 0.1 to 500 parts by weight, more preferably 1 to 300 parts by weight based on 100 parts by weight of the crystalline resin having a melting point of 40 ° C to 80 ° C. Do. When the said content is less than 0.1 weight part, a hardening shortage is anxious, and when it exceeds 500 weight part, there exists a possibility that the leaving stability may fall.

The adhesive composition may further comprise (d) a vinyl compound having at least one phosphoric acid group in the molecule. By including such a compound, adhesive strength and the like are improved.

(d) As a vinyl compound which has at least 1 or more phosphoric acid group in a molecule | numerator, the compound represented by following formula (M), N, and O is preferable. By using such a compound, the adhesive strength of an adhesive composition, etc. can be improved.

[Here, R <_15> represents a (meth) acryloyl group, R <_16> represents a hydrogen atom or a methyl group, u, v represents the integer of 1-8 each independently, In formula, R <_15> and R <_16> comrades , u and v may be the same or different.]

[Wherein, R ₁₇ represents a (meth) acryloyl group, w and x each independently represent an integer of 1 to 8, and in the formula, R ₁₇ , w and x may be the same or different, respectively. has exist]

[Wherein, R ₁₈ represents a (meth) acryloyl group, R ₁₉ represents a hydrogen atom or a methyl group, y and z each independently represent an integer of 1 to 8, and in the formula, R _{18 is} R ₁₉ May be identical to or different from each other.

(d) As the vinyl compound having at least one phosphoric acid group in the molecule, specifically, an acid phosphooxyethyl methacrylate, an acid phosphooxyethyl acrylate, an acid phosphooxypropyl methacrylate, an acid phosphooxypolyoxy Ethylene glycol monomethacrylate, acid phosphooxypolyoxypropylene glycol monomethacrylate, 2,2'-di (meth) acryloyloxydiethyl phosphate, EO modified dimethacrylate (ethylene oxide modified phosphate di) Methacrylate), phosphoric acid modified epoxy acrylate, vinyl phosphate, and the like.

In the adhesive composition, the content of the vinyl compound having at least one phosphoric acid group in the molecule (d) is preferably 0.1 to 150 parts by weight based on 50 parts by weight of the crystalline resin having a melting point of 40 ° C to 80 ° C. More preferably, it is 0.5-100 weight part. When the said content is less than 0.1 weight part, there exists a tendency for high adhesive strength to be difficult to be obtained, and when it exceeds 150 weight part, the physical property fall of the adhesive composition after hardening tends to occur, and there exists a possibility that reliability may fall.

The adhesive composition may further comprise an amorphous resin. By including amorphous resin, heat resistance, adhesiveness, etc. of an adhesive composition improve.

Although it can use without a restriction | limiting in particular as an amorphous resin, (e) A phenoxy resin, a polyurethane resin, a urethane modified polyester resin (preferably, a urethane modified copolymer polyester resin and urethane modified polyester resin are "polyester urethane" Resin "may be referred to), but at least one amorphous resin selected from the group consisting of butyral resin, acrylic resin, polyimide resin. When such resin is used, heat resistance and adhesiveness are further improved. These resins may be used singly or in combination of two or more kinds. When two or more kinds are mixed and used, it is preferable that the resins to be mixed are completely compatible with each other or microphase separation may occur and become cloudy. In addition, these resin may contain a siloxane bond and a fluorine substituent.

Moreover, the above-mentioned amorphous resin tends to be able to set the melt viscosity which becomes easy to obtain film formability, so that the molecular weight is large, and affects the fluidity | liquidity as an adhesive agent widely. In addition, although the said molecular weight is not restrict | limited especially, 5000-150000 are preferable as a weight average molecular weight, and 10000-80000 are more preferable. When this value is less than 5000, there exists a tendency for film formability to fall and when it exceeds 150000, there exists a tendency for compatibility with other components to worsen.

In an adhesive composition, it is preferable that it is 10-80 weight%, and, as for content of amorphous resin, based on an adhesive composition whole quantity, it is more preferable that it is 15-70 weight%. If it is less than 10 weight%, there exists a tendency for high adhesiveness to be difficult to be obtained, and when it exceeds 80 weight%, the fluidity | liquidity of an adhesive composition tends to deteriorate.

The adhesive composition may further include (f) conductive particles for the purpose of imparting conductivity or anisotropic conductivity.

(f) As electroconductive particle, metal particles, such as Au, Ag, Ni, Cu, solder, carbon etc. are mentioned, for example. In addition, a non-conductive glass, ceramic, plastic, or the like may be used as a nucleus, and the nucleus may be coated with the metal, metal particles, or carbon. (f) Since the conductive particles are made of plastic as a nucleus, the nucleus is coated with the metal, metal particles or carbon, or the hot-melt metal particles are deformable by heating and pressing, so that the contact area with the electrode is increased during bonding. This is preferable because the reliability is improved.

Moreover, the microparticles | fine-particles which coat | covered the surface of these electroconductive particle further with the polymeric resin etc. can suppress the short circuit by the contact of the particle | grains when the compounding quantity of electroconductive particle is increased, and can improve the insulation between electrode circuits. The microparticles | fine-particles which coat | covered the surface of electroconductive particle with polymeric resin etc. can be used individually or in mixture with other electroconductive particle, respectively.

(f) It is preferable that the average particle diameter of electroconductive particle is 1-18 micrometers. Such (f) electroconductive particle exhibits favorable dispersibility and electroconductivity. Therefore, the adhesive composition containing such (f) electroconductive particle can be used suitably as an anisotropically conductive adhesive agent.

Although content of the (f) electroconductive particle in an adhesive composition is not specifically limited, It is preferable to set it as 0.1-30 volume% based on the total volume of an adhesive composition, and it is more preferable to set it as 0.1-10 volume%. If this value is less than 0.1 volume%, there exists a tendency for electroconductivity to fall, and when it exceeds 30 volume%, there exists a tendency for a short circuit to occur easily. In addition, content (vol%) of electroconductive particle is determined based on the volume of each component before hardening at 23 degreeC. Here, the volume of each component can be converted from volume to volume using specific gravity. In addition, without dissolving or swelling the component to be measured for volume, a suitable solvent (water, alcohol, etc.) capable of wetting the component well is placed in a measuring cylinder, and the component to be measured is added thereto to increase the volume. May be obtained as the volume of the component.

The adhesive composition is, for the purpose of improving the crosslinking rate, if necessary, in addition to (b) a radically polymerizable compound and (d) a vinyl compound having at least one phosphoric acid group in the molecule, such as an allyl group, maleimide group, vinyl group, and the like. The compound which has a functional group superposing | polymerizing with an active radical may be included. Specific examples of the compound include N-vinylimidazole, N-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, N-vinylcaprolactam, 4,4'-vinylidenebis (N, N- Dimethylaniline), N-vinylacetamide, N, N-dimethylacrylamide, N-isopropylacrylamide, N, N-diethylacrylamide, acrylamide and the like.

The adhesive composition may further comprise a stabilizer. Although there are no particular limitations on the stabilizer that enables control of the curing rate and provision of storage stability by including the stabilizer, quinone derivatives such as benzoquinone and hydroquinone, 4-methoxyphenol and 4-t-butylcatechol, etc. Aminooxyl derivatives, such as a phenol derivative, 2,2,6,6- tetramethyl piperidine-1-oxyl, 4-hydroxy-2,2,6,6- tetramethyl piperidine-1-oxyl, tetra Hindered amine derivatives, such as methyl piperidyl methacrylate, are preferable.

Content of the stabilizer in an adhesive composition becomes like this. Preferably it is 0.01-30 weight part with respect to 100 weight part of adhesive compositions, More preferably, it is 0.05-10 weight part. When the said content is less than 0.01 weight part, the fall of a stabilization effect is anxious, and when it exceeds 30 weight part, there exists a possibility that compatibility with the other component in an adhesive composition may fall.

An adhesive composition may also contain adhesion | attachment adjuvant, such as a coupling agent represented by an alkoxysilane derivative and a silazane derivative, an adhesion improving agent, a leveling agent, as needed. Specifically, the compound represented by the following general formula (P) is preferable, and besides being used alone, two or more kinds of compounds may be mixed and used.

[Wherein R ₂₀ , R ₂₁ , R ₂₂ are independently hydrogen, 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, an aryl group, and R ₂₃ is a (meth) acryl Diary, 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, glycidyl group, A Represents an integer of 1 to 10]

An adhesive composition may use a rubber component together. By using a rubber component together, stress relaxation and adhesiveness improvement become easy. 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, and acryl Rubber, styrene-butadiene rubber, hydroxyl group styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylonitrile-butadiene rubber containing carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group at the polymer terminal, carboxylation Nitrile rubber, hydroxyl-terminated poly (oxypropylene), alkoxysilyl group-terminated poly (oxypropylene), poly (oxytetramethylene) glycol, polyolefin glycol.

As said rubber component, 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 is preferable. By including such a rubber component, adhesiveness further improves. As said rubber component, a liquid rubber is more preferable. By using liquid rubber, the fluidity of the adhesive composition can be further improved. Specific examples of the rubber component include liquid acrylonitrile-butadiene rubber containing liquid acrylonitrile-butadiene rubber, carboxyl group, hydroxyl group, (meth) acryloyl group or morpholine group at the polymer terminal, and liquid carboxylated nitrile rubber. have. In these rubber components, it is preferable that the acrylonitrile content which is a polar group is 10 to 60 weight%. These compounds can be used individually by 1 type or in mixture of 2 or more types.

An adhesive composition can also use organic fine particles together. By using organic fine particles together, stress relaxation and adhesiveness can be improved further. 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, carboxylated nitrile rubber, hydroxyl group terminated poly (oxypropylene), alkoxysilyl group terminated poly (oxy Propylene), poly (oxytetramethylene) glycol, polyolefin glycol (meth) alkyl acrylate-butadiene-styrene copolymer, alkyl (meth) acrylate-silicone copolymer, silicone (meth) -acrylic copolymer or composite Can be mentioned. These organic fine particles may be used alone or in combination of two or more thereof.

The adhesive composition may be used as a paste in the case of a liquid at normal temperature (for example, 25 to 30 ° C). In the case of a solid at normal temperature, in addition to heating, it can also be pasteurized using a solvent. The solvent that can be used is not particularly limited as long as it is not reactive with the adhesive composition (including the additive) and exhibits sufficient solubility, but the boiling point at normal pressure is preferably 50 to 150 ° C. If the boiling point is less than 50 ° C, there is a risk of volatilization if left at room temperature, the use of the open system is limited. Moreover, when a boiling point exceeds 150 degreeC, it is difficult to volatilize a solvent and it may have a bad influence on the reliability after adhesion.

The adhesive composition may be formed into a film and used. When forming an adhesive composition into a film form, the solution obtained by adding a solvent etc. to an adhesive composition as needed is apply | coated on peelable base materials, such as a fluororesin film, a polyethylene terephthalate film, a release paper, or a nonwoven fabric, etc. The solution can be impregnated with a substrate, placed on a peelable substrate, and formed into a film by removing a solvent or the like. If the adhesive composition of this invention is formed in a film form and used, it will become more convenient in terms of handleability.

An adhesive composition can adhere | attach adherends normally using a combination of heating and pressurization. Although heating temperature in particular is not restrict | limited, It is preferable that it is the temperature of 100-250 degreeC. The pressure is not particularly limited as long as it does not cause damage to the adherend, but in general, it is preferably 0.1 to 10 MPa. It is preferable to perform these heating and pressurization in the range for 0.5 second-120 second. According to the adhesive composition of the present invention, it is possible to sufficiently adhere the adherends even by heating and pressing for 10 seconds under the conditions of, for example, 140 to 200 ° C and 3 MPa.

The adhesive composition can be used as an adhesive for heterogeneous adherends having different coefficients of thermal expansion. Specifically, it can be used as a semiconductor element adhesive material represented by a circuit bonding member (circuit connection material) represented by an anisotropic conductive adhesive, a silver paste, a silver film, etc., an elastomer for CSP, an underfill material for CSP, a LOC tape, or the like.

Hereinafter, an example in the case of bonding the circuit members in which the connection terminal was formed on the main surface of a circuit board using the anisotropic conductive film manufactured using an adhesive composition and electroconductive particle is demonstrated. The anisotropic conductive film is disposed between the connecting terminals facing each other on the circuit board, and heated and pressurized to bond the electrical connection between the connecting terminals and the circuit board to face each other, and the circuit members can be bonded to each other. Here, as a circuit board which forms a connection terminal, each combination of these composites, such as inorganic substance, such as a semiconductor, glass, and ceramics, organic materials, such as polyimide and polycarbonate, and glass / epoxy, is applicable. Moreover, when joining so that opposing connection terminals may directly contact, even if the said electroconductive particle is not used, it can electrically connect between connection terminals.

By the method mentioned above, the 1st circuit member which has a 1st connection terminal on the main surface of a 1st circuit board, the 2nd circuit member which has a 2nd connection terminal on the main surface of a 2nd circuit board, A junction body provided between a first and a second circuit member in a state where the first and second connection terminals are opposed to each other, and having a circuit joining member for electrically connecting the first and second connection terminals. The joined body which consists of the adhesive composition of this invention or its hardened | cured material, and is electrically joined by the said circuit joining member between the 1st and 2nd connection terminal can be obtained.

Since such a bonded body is constituted by the cured product of the adhesive composition of the present invention, the circuit bonding member to be bonded to the pair of circuit members can sufficiently increase the adhesive strength between the circuit members and at the same time, a reliability test (for example, For example, stable performance can be maintained even after leaving 85 ° C / 85% RH).

Hereinafter, although this invention is demonstrated further more concretely based on an Example and a comparative example, this invention is not limited to a following example.

[(e) Preparation of Amorphous Resin Solution]

As an amorphous resin solution, a phenoxy resin solution, a urethane modified polyester resin solution, and a polyurethane solution were prepared. The manufacturing method is shown below.

(Preparation of phenoxy resin solution)

40 g of phenoxy resins (YP-50, manufactured by Toto Kasei Co., Ltd.) were dissolved in 60 g of methyl ethyl ketone to prepare a phenoxy resin solution having a solid content of 40% by weight.

(Production of Urethane Modified Polyester Resin Solution)

Urethane-modified polyester resin (UR-1400, manufactured by Toyobo Co., Ltd.) was dissolved in a mixed solvent in which methyl ethyl ketone and toluene were mixed at a ratio of 1: 1 (weight), and the urethane-modified polyester resin powder was 30% by weight. Phosphorous solution was prepared. In addition, the differential scanning calorimetry curve (DSC curve) of the urethane modified polyester resin (UR-1400) is shown in FIG. As can be seen from FIG. 1, the differential scanning calorimetry curve of the resin did not have a peak.

(Production of Polyurethane Solution)

15 g of a polyurethane resin (Milactran P22M, softening point: 64 ° C. Nippon Polyurethane Co., Ltd.) was dissolved in 85 g of methyl ethyl ketone to prepare a polyurethane solution having a solid content of 15% by weight.

[Preparation of Liquid Rubber Component]

As a liquid rubber component, a liquid nitrile rubber (Nipol 1312 Nihon Xeon Co., Ltd. brand name) was prepared.

[Production of Crystalline Resin (Polyester Resin) Solution]

As the crystalline resin, poly (caprolactone) (Wako Pure Chemical Industries, Ltd. make, Mw: 40000, mp: 53 ° C), Bylon GA-6400 (Mw: 30000, mp: 71 ° C, Toyoko Company brand) and Bylon GA-6300 (Mw: 30000, mp: 101 degreeC, the brand name of Toyo Bow Co., Ltd. product) were prepared. Next, 30 g of the above-mentioned three kinds of crystalline resins were dissolved in 70 g of toluene, respectively, to prepare a crystalline resin (polyester resin) solution having a solid content of 30% by weight. Moreover, the differential scanning calorimetry curve (DSC curve) of the used poly (caprolactone) is shown in FIG. As can be seen from FIG. 2, the differential scanning calorimetry curve of the resin had a peak.

[(b) Preparation of Radical Polymerizable Compound]

Isocyanuric acid EO modified diacrylate (M-215, the Toagosei Co., Ltd. brand name) was prepared as a radically polymerizable compound. Moreover, urethane acrylate (UA) was synthesize | combined as a radically polymerizable compound.

(Synthesis of urethane acrylate (UA))

860 parts by weight (1.00 mol) of poly (hexamethylene carbonate) diol (manufactured by Aldrich) 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 weight of dibutyltin dilaurate (manufactured by Aldrich) were added. Subsequently, after introducing nitrogen gas sufficiently, it heated at 70-75 degreeC, 666 weight part (3.00 mol) of isophorone diisocyanate (made by Aldrich) was dripped uniformly in 3 hours, and it was made to react. After completion of the dropping, the reaction was continued for about 10 hours. 238 parts by weight (2.05 mol) of 2-hydroxyethyl acrylate (manufactured by Aldrich) and 0.53 part by weight of hydroquinone monomethyl ether (manufactured by Aldrich) were added thereto, and the mixture was further reacted for 10 hours, and isocyanate was measured by IR. Confirmed that disappeared, reaction was complete | finished, and urethane acrylate (UA) was obtained. The number average molecular weight of obtained urethane acrylate (UA) was 3700.

[(d) Preparation of vinyl compound having at least one or more phosphoric acid group in the molecule (hereinafter referred to as "phosphate-containing compound" in some cases)]

(d) As a vinyl compound which has at least 1 or more phosphoric acid group in a molecule | numerator, 2- (meth) acryloyloxyethyl phosphate (light ester P-2M, Kyoeisha Co., Ltd. brand name) was prepared.

[(c) Preparation of Radical Polymerization Initiator]

T-hexyl peroxy-2-ethylhexanoate (perhexyl O, the Nippon Yushi Chemical Co., Ltd. brand name) was prepared as a radical polymerization initiator.

[(f) Production of Electroconductive 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 prepare conductive particles having an average particle diameter of 4 μm and a specific gravity of 2.5.

[Examples 1 to 6 and Comparative Examples 1 to 5]

The material prepared by the above-mentioned method was mix | blended so that it might become the ratio shown in Table 1 and 2 by solid weight ratio, ie, the weight ratio in the case of excluding a solvent, and also 1.5 volume% of electroconductive particle was mix | blended and dispersed, and the adhesive composition solution was prepared. The obtained adhesive composition solution is apply | coated to a 80-micrometer-thick fluororesin film using a coating apparatus, hot air dried at 70 degreeC for 10 minutes, and is 20 micrometers-thick film adhesive composition (henceforth a "film adhesive composition"). Got.

(Evaluation of Adhesive Composition and Conjugate)

[Measurement of Connection Resistance and Adhesive Strength]

Using a film adhesive composition obtained by the above production method, a flexible circuit board (FPC) having 500 copper circuits having a line width of 25 μm, a pitch of 50 μm, and a thickness of 18 μm, and a thin layer of 0.2 μm of indium oxide (ITO) were used. The formed glass (thickness 1.1 mm, surface resistance 20 Ω / □) was heated at 160 ° C. for 10 seconds at a temperature of 160 ° C. using a thermocompression bonding apparatus (heating method: constant heat type, manufactured by Toray Engineering Co., Ltd.). It heated and pressurized and bonded together and manufactured the joined body. The resistance value between adjacent circuits of this joined body was measured immediately by the multimeter after holding for 250 hours immediately after adhesion | attachment in a high temperature, high humidity tank of 85 degreeC and 85% RH, and it was set as the connection resistance value. In addition, the connection resistance value was shown by the average of 37 resistance points between adjacent circuits. The lower the connection resistance is, the better.

In addition, the adhesive strength of this joined body 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 higher the adhesive strength, the better.

[Measurement of surface tack force]

Using the film adhesive composition obtained by the said manufacturing method, the surface tag force of the film adhesive composition was evaluated by the probe tag test according to JISZ0237-1991. Here, the measuring device of the surface tack force is manufactured by Resuka Co., Ltd. (probe diameter: Φ 5.1 mm, contact speed: 2.0 mm / sec, peeling rate: 10 mm / sec, contact load: 100 gf / cm ² , contact time : 1.0 second, measurement temperature: 30 degreeC). The lower the surface tagging force, the better the handleability of the adhesive composition.

Table 3 shows the measurement results of the connection resistance, the adhesive strength, and the surface tag force of the joined body measured by the above method.

The adhesive compositions obtained in Examples 1 to 6 exhibit good connection resistance and adhesive strength even after holding at a heating temperature of 160 ° C. for 250 hours immediately after adhesion and in a high temperature and high humidity bath at 85 ° C. and 85% RH for a wide range of heating temperatures. It turned out that it shows favorable characteristics. In addition, it was found that the surface tagging force was also appropriately low and workability and repairability were good. Compared with these, in Comparative Example 1 using a crystalline resin having a melting point of 101 ° C, since (a) the crystalline resin having a melting point of 40 ° C. to 80 ° C. was not used, compatibility with other compositions was poor. Aggregate precipitated and the handleability worsened. Moreover, in Comparative Examples 2 and 3 using an amorphous resin having a softening point of 64 ° C., sufficient fluidity was not obtained, and the connection resistance value immediately after bonding and after high temperature and high humidity treatment was high. Furthermore, in Comparative Examples 4 and 5 using liquid rubber, it was found that the increase in connection resistance and the surface tag force after high temperature and high humidity were high, and workability, namely, handleability was deteriorated.

As described above, according to the present invention, an adhesive composition having excellent adhesive strength and maintaining stable performance (adhesive strength and connection resistance) even after a reliability test (high temperature and high humidity test), and excellent in handleability, and using the same The joined body of a circuit member can be provided.

According to the present invention, excellent adhesive strength can be obtained and stable performance can be maintained even after a reliability test, and an adhesive composition excellent in handleability and a bonded member of a circuit member using the same can be provided.

Claims (8)

Adhesive composition containing (a) crystalline resin whose melting | fusing point is 40 degreeC-80 degreeC, (b) radically polymerizable compound, and (c) radical polymerization initiator. The adhesive composition of Claim 1 whose melting | fusing point of (a) crystalline resin is 40 degreeC-75 degreeC. The adhesive composition according to claim 1 or 2, wherein (a) the crystalline resin comprises a crystalline polyester resin. The adhesive composition according to claim 3, wherein the crystalline polyester resin is a crystalline polyester resin having a carbonate group or an ether group. The adhesive composition according to any one of claims 1 to 4, further comprising (d) a vinyl compound having at least one phosphoric acid group in the molecule. (E) At least 1 sort (s) selected from the group which consists of (e) a phenoxy resin, a polyurethane resin, a urethane modified polyester resin, butyral resin, an acrylic resin, and a polyimide resin. Adhesive composition containing the amorphous resin of the. The adhesive composition of any one of Claims 1-6 which further contains (f) electroconductive particle. A first circuit member having a first connection terminal on a main surface of the first circuit board, A second circuit member having a second connection terminal on a main surface of the second circuit board, A junction body provided between the first and second circuit members in a state where the first and second connection terminals are opposed to each other, and having a circuit joining member for electrically connecting the first and second connection terminals. The said circuit joining member consists of the adhesive composition as described in any one of Claims 1-7, or its hardened | cured material, and the 1st and 2nd connection terminal is a joined body electrically bonded.

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