JP2003286390A - Epoxy resin composition, varnish, film adhesive made by using epoxy resin composition, and its cured material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition useful as e.g. an adhesive for an insulating resin layer of a build-up multilayer printed-wiring board, and an adhesive for connecting a semiconductor element to a substrate, a film adhesive, and a cure material. <P>SOLUTION: The epoxy resin composition contains (A) an epoxy resin, (B) a curing agent, (C) a phenoxy resin, (D) a rubber component, and (E) a cure accelerator, wherein the curing agent (B) comprises a polyhydroxy resin represented by HO-A-[-CR<SB>2</SB>-Z-CR<SB>2</SB>-A(OH)-]<SB>n</SB>-H (wherein A is a benzene ring or a naphthalene ring; and Z is phenylene or biphenylene), the component (C) comprises a bisphenol A or F phenoxy resin, the component (D) comprises an elastomer obtained by the polycondensation of an aromatic polyamide oligomer having terminal amino groups with a butadiene/acrylonitrile copolymer having terminal carboxyl groups, and the content of the phenoxy resin and the elastomer are each 5-50 wt.%. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition, a varnish obtained by varnishing the same, a film-like adhesive obtained by forming the varnish into a film, and a cured product thereof. This epoxy resin composition, varnish, and film adhesive are used as an adhesive for connecting a semiconductor element such as an insulating resin layer of a build-up multilayer printed wiring board or a flip chip to a substrate, or a semiconductor element as a lead frame or a TAB tape. Suitable for die-bonding adhesive etc.

[0002]

2. Description of the Related Art In recent years, with the rapid miniaturization and high performance of electric and electronic devices, the density of printed wiring boards has been increasing. In this situation, for example, in a multilayer wiring board, a build-up method has been extended in which conductive circuit layers and insulating resin layers are alternately laminated, and blind holes are used for conduction only in a portion where interlayer connection is required.
In this build-up multilayer wiring board, through-hole plating,
Via hole plating is used, but due to the expansion and contraction stress when a thermal cycle is applied, the through hole part,
It is important that the via holes do not crack or peel. Further, in the build-up multilayer wiring board, semiconductor components are mounted by solder reflow or the like, but it is important that peeling does not occur between the conductor circuit layer and the insulating resin layer during solder mounting. Therefore, it is important that the insulating resin layer has a performance that satisfies these conditions. The method of forming via holes in these build-up multilayer wiring boards is a laser via method in which a thermosetting resin is used for the insulating resin layer to form vias by laser processing, and a via is formed by exposure and development using a photosensitive resin. Although there is a photo via method for forming, a laser via method using a thermosetting resin is currently widely used in terms of reliability, material cost, and the like.

Further, even higher density packaging is required for semiconductor elements, and the flip-chip method is drawing attention as a packaging method. In this flip-chip type board connection, the electrodes of the wiring board and the flip-chip are electrically connected to each other by applying heat and pressure using an adhesive. Therefore, it is important that the adhesive used has excellent solder heat resistance during mounting and excellent connection reliability after connection. Further, with the miniaturization of semiconductor packages such as CSP, it has become necessary for die bond adhesives to have excellent stress relaxation and solder heat resistance.

What is common to all of these uses is that stress relaxation property against cooling / heating cycle, reliability and solder heat resistance are important characteristics. Particularly, regarding solder heat resistance, more excellent characteristics are required due to the rise in solder reflow temperature accompanying the recent trend of lead-free solder. In order to achieve excellent cooling / heating cycle reliability and solder heat resistance, adhesion with the members,
It is important to have excellent heat resistance, mechanical strength, low stress (low thermal expansion, low elastic modulus).

On the other hand, in any of these build-up insulating materials, adhesives for semiconductor elements such as flip chips, and adhesives for die bonding, the material form is liquid varnish, liquid paste or film. However, from the viewpoints of handleability, cleanliness (low contamination), and cost reduction (high material usage efficiency), film materials are desired.

Conventionally, as a film material, for example, as a build-up insulating material, a film obtained by combining a binder polymer such as an epoxy resin, an epoxy curing agent, and a phenoxy resin as described in JP-A-11-1547 and JP-A-11-87927. Materials have been proposed. However, it does not have sufficient adhesion, mechanical strength, and low elastic modulus with the members, and therefore, in the areas where high density and high reliability are especially required, the thermal cycle reliability and solder heat resistance are sufficiently satisfied. The current situation is that it has not been done. In addition, the film support property before curing is not sufficient.

Film materials of epoxy resin compositions have been proposed as adhesives for semiconductor elements such as flip chips, adhesives for die bonding, and adhesives for other electronic parts. However, since the epoxy resin, which is an inherently brittle material, must be used to develop the film support in the pre-curing stage, the thermoplastic resin is designed in a considerable proportion. Therefore, the heat resistance and the mechanical strength are not sufficient, and there are problems in the thermal cycle reliability and the solder heat resistance.

[0008]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide excellent thermal cycle reliability, solder heat resistance, and moisture resistance reliability, and in particular adhesion to members, heat resistance, mechanical strength, and low stress ( An object of the present invention is to provide an epoxy resin composition which provides an adhesive excellent in low thermal expansion property and low elastic modulus). Another object is to provide an epoxy resin composition which gives a film adhesive having excellent film support in the pre-curing stage. Another object is to provide a film adhesive having the above characteristics. Moreover, it aims at providing the varnish and hardened | cured material of the said epoxy resin composition. Furthermore, an insulating resin layer of a build-up multilayer printed wiring board in which conductor circuit layers and insulating resin layers are alternately stacked, an adhesive for connecting a semiconductor element such as a flip chip to a substrate, or a semiconductor element as a lead frame or a TAB tape. It is an object of the present invention to provide an epoxy resin composition or a film-like adhesive suitable for a die-bonding adhesive or the like to be mounted on, for example.

[0009]

Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventors have found that an epoxy resin, a curing agent having a specific structure, a phenoxy resin having a specific molecular weight range and a structure,
It has been found that the above object can be achieved by combining a rubber component having a specific molecular weight range and a structure, and a curing accelerator, and the present invention has been completed.

That is, the present invention provides an epoxy resin composition containing (A) an epoxy resin, (B) a curing agent, (C) a phenoxy resin, (D) a rubber component and (E) a curing accelerator. ) The curing agent is represented by the following general formula (1)

[Chemical 11] (However, A represents a hydrocarbon group-substituted or unsubstituted benzene ring or naphthalene ring, l represents 1 or 2, and these may be the same or different. R _{1 to} R ₄ are independently, A hydrogen atom or a methyl group, and n represents a number of 1 to 15), and the curing agent contains 10 to 100% by weight of a polyvalent hydroxy resin curing agent, and (C) a phenoxy resin. Is the following general formula (2)

[Chemical 12] (However, X ₁ represents —C (CH ₃ ) ₂ — or —CH ₂ — and may be the same or different. R _{5 to} R ₁₂ independently represent a hydrogen atom or a bromine atom, and n is The weight average molecular weight of the repeating unit represented by 1) is 1 or more.
It contains a phenoxy resin of 20,000 to 200,000 as an essential component, and has a weight average molecular weight of 10,000 to 200,000 mainly composed of repeating units represented by the general formula (2).
The phenoxy resin content of 00 is (A) epoxy resin,
5 to 50 wt% of the total of (B) curing agent, (C) phenoxy resin, (D) rubber component and (E) curing accelerator,
(D) The rubber component has a weight average molecular weight of 10,000 to 1,000 obtained by polycondensation of an aromatic polyamide oligomer having amino groups at both ends and a butadiene-acrylonitrile copolymer having carboxyl groups at both ends. ,
000 elastomer as an essential component, and the content of the elastomer is (A) epoxy resin, (B)
The epoxy resin composition is characterized by being 5 to 50% by weight of the total of the curing agent, the (C) phenoxy resin, the (D) rubber component and the (E) curing accelerator.

Here, the polyhydric hydroxy resin curing agent is a phenol biphenylaralkyl type resin represented by the following general formula (3), or the elastomer is represented by the following general formula (4) with amino at both ends. The elastomer obtained by polycondensation of an aromatic polyamide oligomer having a group and a butadiene-acrylonitrile copolymer having a carboxyl group at both ends represented by the following general formula (5) is an elastomer of a preferred embodiment of the present invention. Is one.

[Chemical 13] (However, n shows the number of 1 to 15.)

[Chemical 14] (However, a and b are average polymerization degrees, and a>
0, b> 0, and a + b ≧ 1. The individual components are independent of each other, can be arranged arbitrarily, and may be present in a block form or a random form. )

[Chemical 15] (However, c and d are average polymerization degrees, respectively, and c ≧
1, and d ≧ 1. The individual components are independent of each other, can be arranged arbitrarily, and may be present in a block form or a random form. )

The epoxy resin (A) contains at least one epoxy resin selected from the epoxy resins represented by the following general formulas (6) to (10) in an amount of 20 to 100% by weight in the epoxy resin. It is also preferable that it is contained.

[Chemical 16] (However, X ₂ is _{-C (CH 3) 2 -,} - CH 2 - or a single bond, a good .R ₁₃ to R ₁₆ be the same or different is independently, a hydrogen atom or a methyl group And n is a number from 0 to 15.)

[Chemical 17]

[Chemical 18] (However, n shows the number of 1 to 15.)

[Chemical 19] (However, R ₁₇ represents a hydrogen atom or an alkyl group, and may be the same or different. N represents a number of 1 to 15.)

[Chemical 20] (However, i shows 1 or 2, n shows the number of 0-10. Moreover, bromine content is 10-80 weight%.) In general formula (6)-(10), G Represents a glycidyl group.

The present invention also provides a varnish obtained by dissolving this epoxy resin composition in a solvent. Further, the present invention is
A film adhesive obtained by forming the epoxy resin composition into a film. Furthermore, the present invention is a cured product obtained by curing this epoxy resin composition.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The epoxy resin (A) used in the present invention is necessary for obtaining sufficient insulation, adhesiveness, heat resistance, mechanical strength and the like. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, biphenyl novolac type Epoxy resins having two or more epoxy groups in the molecule such as epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, alicyclic epoxy resin, and brominated epoxy resin can be used. These epoxy resins may be used either individually or in combination of two or more. Among them, the general formula (6)
It is preferable to use one kind or two or more kinds of the epoxy resin represented by (10) to (10), and the use ratio thereof is 20 to 100% by weight, preferably 50 to 100% by weight of the total epoxy resin. It is good to say The epoxy resin preferably has a small amount of ionic impurities and hydrolyzable chlorine from the viewpoint of improving the moisture resistance reliability.

The (B) curing agent used in the present invention contains a polyvalent hydroxy resin curing agent represented by the general formula (1) as an essential component. In the general formula (1), A represents a hydrocarbon group-substituted or unsubstituted benzene ring or naphthalene ring. R ₁ ~
R ₄ independently represents a hydrogen atom or a methyl group, l represents 1 or 2, and n represents a number of 1 to 15. In one molecule, n + 1 is represented by A and l is represented by n, which may be all the same or partly or totally different.

Examples of the polyvalent hydroxy resin curing agent represented by the general formula (1) include phenol phenyl aralkyl type resin, phenol biphenyl aralkyl type resin, naphthol phenyl aralkyl type resin and naphthol biphenyl aralkyl type resin. Among them, the phenol biphenyl aralkyl type resin represented by the general formula (3) is preferable.

The proportion of the polyvalent hydroxy resin curing agent represented by the general formula (1) is 10 to 100% by weight, preferably 50 to 100% by weight, more preferably 80 to 1% by weight based on the total curing agent.
It is 00% by weight. If it is out of this range, the thermal cycle reliability, solder heat resistance, moisture resistance reliability, adhesion to members, heat resistance, mechanical strength, low stress (low thermal expansion, low elastic modulus), pre-curing stage An epoxy resin composition which simultaneously exhibits excellent film support cannot be obtained.

The (B) curing agent used in the present invention includes
In addition to the curing agent represented by the general formula (1) which is an essential component,
As long as the object of the present invention is not impaired, a known phenolic hydroxyl group-containing substance can be used as an epoxy resin curing agent. Examples of such curing agents include bisphenol A, bisphenol F, bisphenol S, divalent phenols such as naphthalene diol, phenol novolac, o-cresol novolac, triphenylmethane type phenol resin, dicyclopentadiene type phenol resin and the like. Trivalent or higher phenols, bisphenol A
Examples thereof include polyhydric hydroxy compounds obtained by condensation of dihydric phenols such as and aldehydes such as formaldehyde, and triazine structure-containing phenol novolac resins obtained from phenols, triazine ring-containing compounds and aldehydes. These curing agents may be used alone or in combination of two or more.

The preferred ratio of the epoxy resin and the curing agent in the epoxy resin composition of the present invention is such that the equivalent ratio of epoxy resin / curing agent is 0.7 to 1.3, more preferably 0.8.
~ 1.2.

The phenoxy resin (C) used in the present invention contains a repeating unit represented by the general formula (2) as a main constituent, preferably 90% by weight or more, and more preferably substantially all the constituents. The thing is an essential ingredient. Specific examples include bisphenol A-type phenoxy resin, bisphenol F-type phenoxy resin, brominated bisphenol A-type phenoxy resin, and brominated bisphenol F-type phenoxy resin. The brominated phenoxy resin can be a partially brominated phenoxy resin. General formula (2)
The weight average molecular weight of the phenoxy resin having a repeating unit represented by is 10,000 to 200,000, preferably 20,000 to 100,000. When the weight average molecular weight is less than 10,000, the heat resistance, mechanical strength and flexibility of the epoxy resin composition are deteriorated.
When it is more than 2,000, workability such as solubility in organic solvent and compatibility with epoxy resin is deteriorated. The weight average molecular weight here is a value converted into polystyrene by GPC measurement. Further, the weight average molecular weight mainly of the repeating unit represented by the general formula (2) is 10,000 to 200,
A phenoxy resin other than 000 phenoxy resins can be used in combination as long as the amount is small, but it is preferable to limit the amount to 20% by weight or less of the total phenoxy resin.

The content of the phenoxy resin having a weight average molecular weight of 10,000 to 200,000 mainly composed of the repeating unit represented by the general formula (2) is the above-mentioned (A) epoxy resin,
It is 5 to 50% by weight, preferably 10 to 40% by weight based on the total weight of the (B) curing agent, (C) phenoxy resin, (D) rubber component and (E) curing accelerator. If the content is less than 5% by weight, the adhesion to members, mechanical strength and flexibility will be deteriorated, and if it is more than 50% by weight, work such as solubility in organic solvents and compatibility with epoxy resin will be performed. And the heat resistance of the epoxy resin composition.

The rubber component (D) used in the present invention is essentially an elastomer obtained by polycondensation of an aromatic polyamide oligomer having amino groups at both ends and a butadiene-acrylonitrile copolymer having carboxyl groups at both ends. As an ingredient. Among them, an aromatic polyamide oligomer having amino groups at both ends represented by the general formula (4),
It is preferable to use an elastomer represented by the general formula (5) obtained by polycondensation with a butadiene-acrylonitrile copolymer having carboxyl groups at both ends.
In the general formulas (4) and (5), a, b, c,
d is the average degree of polymerization, a> 0, b> 0, a +
b ≧ 1, c ≧ 1, and d ≧ 1. The individual components do not need to be arranged in the order shown in the general formula (4) and the general formula (5), and they can be arranged independently of each other and can be arranged arbitrarily, and may exist in a block shape or a random shape. . Regarding the molar ratio of a and b, the range of a / (a + b) = 0.05 to 0.95, and for the molar ratio of c and d, c / (c + d) = 0.05.
A range of ~ 0.95 is good.

The aromatic polyamide oligomer having amino groups at both ends is obtained by polycondensation of an aromatic diamine component and an aromatic dicarboxylic acid component. Amino groups at both end groups of the oligomer can be achieved by subjecting the aromatic diamine component to a condensation reaction in an excess amount over the aromatic dicarboxylic acid component. Examples of the aromatic diamine component used for producing the aromatic polyamide oligomer having amino groups at both ends include, for example, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenyl ether and 3,4′-diamino. Examples thereof include, but are not limited to, diphenyl ether and the like. Preferred is 3,4'-diaminodiphenyl ether. These aromatic diamine components may be used alone or in combination of two or more.

As the aromatic dicarboxylic acid component,
For example, phthalic acid, isophthalic acid, terephthalic acid, 4,
Examples thereof include 4'-biphenyldicarboxylic acid, 5-hydroxyisophthalic acid, 2-hydroxyterephthalic acid, etc., but are not limited thereto. Preferred are isophthalic acid and 5-hydroxyisophthalic acid. These aromatic dicarboxylic acid components may be used either individually or in combination of two or more.

An elastomer obtained by polycondensation of an aromatic polyamide oligomer having amino groups at both ends and a butadiene-acrylonitrile copolymer having carboxyl groups at both ends has a weight average molecular weight of 10,000 to 1,
, 000,000, preferably 20,000 to 500,000
It is 0. When the weight average molecular weight is less than 10,000, not only the heat resistance, mechanical strength and flexibility of the epoxy resin composition are deteriorated, but also the film support property before curing is deteriorated. If it is more than 1,000,000, workability such as solubility in an organic solvent and compatibility with an epoxy resin is deteriorated. The weight average molecular weight here is GP
It is a value converted into polystyrene by C measurement.

The weight average molecular weight obtained by polycondensation of an aromatic polyamide oligomer having amino groups at both ends and a butadiene-acrylonitrile copolymer having carboxyl groups at both ends has a weight average molecular weight of 10,000 to 1,000,000.
The content of the elastomer of the above (A) epoxy resin,
It is 5 to 50% by weight, preferably 15 to 30% by weight, based on the total weight of the (B) curing agent, (C) phenoxy resin, (D) rubber component and (E) curing accelerator. When the amount is less than 5% by weight, the epoxy resin composition causes a decrease in mechanical properties such as elongation at break, and also a decrease in film support property before the curing. When it is more than 50% by weight, solubility in organic solvent, workability such as compatibility with epoxy resin, and heat resistance and mechanical strength of the epoxy resin composition decrease.

The rubber component (D) used in the present invention is obtained by polycondensing an essential component, an aromatic polyamide oligomer having amino groups at both ends, and a butadiene-acrylonitrile copolymer having carboxyl groups at both ends. The obtained weight average molecular weight is 10,000 to 1,000,
Other than 000 elastomers, known rubbers may be used within a range not impairing the object of the present invention, preferably within a range of 20% by weight or less based on all rubber components. Examples of such rubber include polybutadiene rubber and acrylonitrile-
Examples thereof include butadiene rubber, modified acrylonitrile-butadiene rubber, and acrylic rubber. These rubbers may be used alone or in combination of two or more. Regarding the purity of the rubber used as the rubber component (D) of the present invention, a rubber having a small amount of ionic impurities is preferable from the viewpoint of improving the moisture resistance reliability.

The curing accelerator (E) used in the present invention is necessary to give the epoxy resin a sufficient curing rate, heat resistance, mechanical strength and the like. For example, there are imidazoles, organic phosphines, amines and the like, and specifically, 2-
Methylimidazole, 2-undecylimidazole, 2
-Heptadecyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 2-phenyl-
4,5-dihydroxymethylimidazole, 2-phenyl
-4-Methyl-5-hydroxymethylimidazole, 2,4
-Diamino-6- [2'-methylimidazolyl- (1 ')]-
Ethyl-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine
Examples include isocyanuric acid adducts, triphenylphosphine, tetraphenylphosphonium / tetraphenylborate, and the like. Further, those obtained by encapsulating these can be used. These curing accelerators are 1
One kind or two or more kinds can be used.

The compounding amount of the (E) curing accelerator is preferably in the range of 0.02 to 10 parts by weight based on 100 parts by weight of the total amount of the (A) epoxy resin and the (B) curing agent. If it is less than 0.02 parts by weight, the curing acceleration effect is not sufficient, and if it is more than 10 parts by weight, the curing acceleration effect is not increased, but rather the properties of the epoxy resin composition are deteriorated.

In addition to the above-mentioned essential components, the epoxy resin composition of the present invention contains a fluorine-based or silicone-based defoaming agent and a leveling agent from the viewpoints of void reduction and smoothness improvement to improve the adhesion to the member. From the viewpoint of, silane coupling agent,
An adhesion promoter such as a thermoplastic oligomer can be added.

Inorganic fillers and organic fillers can be used in the epoxy resin composition of the present invention depending on the purpose. As the inorganic filler used, silica, alumina,
Examples of the organic filler include calcium carbonate, magnesium carbonate, magnesium oxide, and the like. Silicon powder, nylon powder, acrylonitrile-butadiene-based crosslinked rubber, and the like can be used, and these can be used alone or in combination of two or more.

In particular, when the epoxy resin composition of the present invention is used for an insulating resin layer of a buildup multilayer printed wiring board in which conductor circuit layers and insulating resin layers are alternately stacked,
By using an oxidizer-soluble filler as the above-mentioned inorganic filler or organic filler, curing is performed through a step of roughening the cured product with an oxidizing agent such as permanganate, dichromate, or ozone. Minute irregularities can be formed on the surface of the object.
After that, a conductor layer is formed by electroless plating or electrolytic plating, and an annealing treatment is performed at 150 to 180 ° C. for 30 to 60 minutes to obtain an excellent conductor layer and a resin layer due to an excellent anchoring effect due to minute irregularities on the surface of the cured product. Adhesion is obtained.

Further, the epoxy resin composition of the present invention comprises
If necessary, a colorant such as phthalocyanine green, phthalocyanine blue, carbon black or the like can be added.

The varnish of the epoxy resin composition of the present invention is
The (A) epoxy resin, (B) curing agent, (C) phenoxy resin, (D) rubber component and (E) curing accelerator
Alternatively, it can be obtained by dissolving the epoxy resin composition of the present invention obtained by mixing these with other additives in a solvent.
Among the (E) curing accelerator and other additives, the inorganic filler, the organic filler, the colorant and the like do not necessarily have to be dissolved in the solvent as long as they are uniformly dispersed in the varnish. As the solvent used, N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-
Amide solvents such as methyl-2-pyrrolidone (NMP), 1
Examples thereof include ether solvents such as methoxy-2-propanol, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, aromatic solvents such as toluene and xylene. These solvents may be used alone or in combination of two or more.

In the film adhesive of the present invention, the above-mentioned varnish dissolved in a solvent is applied to a base film as a supporting material so that the thickness after drying becomes a predetermined thickness, and then the solvent is dried. Can be obtained by Regarding the film support of the film adhesive (before curing),
The higher the residual solvent ratio, the better the film supportability, but if the residual solvent ratio is too high, the film adhesive (before curing) may be tacked or foamed during curing. Therefore, the residual solvent ratio is preferably 10% by weight or less. The solvent residual rate here is a value obtained by measuring the weight loss rate after drying for 60 minutes in a 200 ° C atmosphere.

In addition, the film adhesive of the present invention may be obtained by applying the solvent-free epoxy resin composition of the present invention onto a base film as a supporting material in a heated and molten state and then cooling it. is there.

As the support material used, polyethylene terephthalate (PET), polyethylene, aluminum foil,
Examples include copper foil and release paper. The thickness of the support material is 1
It is generally 0 to 100 μm.

Further, the film adhesive of the present invention is laminated on a base film as a supporting material, and then the other surface which is not laminated is covered with a film as a protective material and wound into a roll. Often stored.

Examples of the protective material used include polyethylene terephthalate, polyethylene, release paper and the like. The thickness of the protective material is generally 10 to 100 μm.

Next, a production example using the film adhesive of the present invention in a multilayer printed wiring board will be described. First,
An inner layer circuit in which the film adhesive of the present invention is patterned using a batch-type or continuous-type vacuum laminator under the conditions of a pressure bonding temperature of 60 to 150 ° C., a pressure bonding pressure of 0.1 to 1.0 MPa, and an atmospheric pressure of 2 kPa or less. Laminate on substrate.
At that time, when the film adhesive is covered with a film as the protective material, after peeling off the protective material,
Under heating conditions, pressure is applied from the side of the base film as a support material to laminate on the inner layer circuit board. Inner layer circuit boards include glass epoxy boards, metal boards, polyimide boards,
A BT resin substrate, a thermosetting polyphenylene ether substrate, or the like can be used. In the film adhesive, after laminating, cooling to room temperature, peeling the support material, and then heating and curing. The curing condition is 120 to 20
20 to 90 minutes at 0 ° C is suitable.

Next, after making a via hole or the like with a laser or the like, a roughening treatment with an oxidizing agent such as permanganate, dichromate or ozone is carried out for the purpose of removing smear and forming fine irregularities. do. After that, a conductor layer is formed by electroless plating or electrolytic plating, and 30 to 60 at 150 to 180 ° C.
By the minute annealing treatment, excellent adhesion between the conductor layer and the resin layer can be obtained due to the excellent anchoring effect due to the minute irregularities on the surface of the cured product. A multi-stage buildup layer can be formed on the conductor circuit layer thus obtained by further repeating the above-mentioned production method using the film adhesive of the present invention.

[0042]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to this. The raw materials used to obtain the epoxy resin composition and their abbreviations are shown below.

(A) Epoxy resin Epoxy resin (1): Bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin, EPCOAT 828EL; epoxy equivalent 189, liquid)

[Chemical 21] (However, G represents a glycidyl group (the same applies to the following formula).) Epoxy resin (2): Biphenyl type epoxy resin (manufactured by Japan Epoxy Resin, YX4000HK; epoxy equivalent 195,
(Melting point 105 ° C)

[Chemical formula 22]

Epoxy resin (3): Bisphenol F type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., YSLV-80XY; epoxy equivalent 193, melting point 78 ° C)

[Chemical formula 23] Epoxy resin (4): bifunctional naphthalene type epoxy resin (Dainippon Ink and Chemicals, HP-4032; epoxy equivalent 15
0, semi-solid, 70% by weight or more of the following structure)

[Chemical formula 24]

Epoxy resin (5): Biphenyl novolac type epoxy resin (Nippon Kayaku, NC-3000S-H; epoxy equivalent 291, softening point 71 ° C)

[Chemical 25] Epoxy resin (6): triphenylmethane type epoxy resin (Nippon Kayaku, EPPN-501H; epoxy equivalent 167, softening point 54 ° C)

[Chemical formula 26] Epoxy resin (7): novolak type brominated epoxy resin (Nippon Kayaku, BREN-304; epoxy equivalent 310, softening point
70 ℃, Br content 44.0wt%)

[Chemical 27]

Epoxy resin (8): novolac type brominated epoxy resin (Nippon Kayaku, BREN-105; epoxy equivalent)
275, softening point 64 ℃, Br content 35.5wt%)

[Chemical 28] Epoxy resin (9): o-cresol novolac type epoxy resin (Nippon Kayaku, EOCN-1020-80; epoxy equivalent 2
00, softening point 80 ℃)

[Chemical 29] Epoxy resin (10): dicyclopentadiene type epoxy resin (Nippon Kayaku, XD-1000-L; epoxy equivalent 248,
(Softening point 65 ℃)

[Chemical 30]

(B) Curing agent Curing agent (1): Phenol biphenyl aralkyl type resin (MEH-7851-3H manufactured by Meiwa Kasei; phenolic hydroxyl group equivalent)
229, softening point 105 ℃)

[Chemical 31] Curing agent (2): Phenol phenyl aralkyl type resin (Maywa Kasei, MEH-7800-3H; phenolic hydroxyl group equivalent)
183, softening point 105 ℃)

[Chemical 32] Hardener (3): Naphthol phenyl aralkyl type resin (Nippon Steel Chemicals Co., SN-485; phenolic hydroxyl equivalent 21
0, softening point 85 ℃)

[Chemical 33]

Curing agent (4): Phenol novolak (manufactured by Gunei Chemical Industry Co., Ltd., PSM-6200; equivalent of phenolic hydroxyl group 10)
5, softening point 81 ℃)

[Chemical 34] Curing agent (5): triphenylmethane type resin (MEH-7500 manufactured by Meiwa Kasei; epoxy equivalent 97, softening point 110 ° C)

[Chemical 35] Curing agent (6): dicyclopentadiene type resin (Nippon Petrochemical, DPP-M; phenolic hydroxyl group equivalent 169, softening point
94 ° C)

[Chemical 36]

(C) Phenoxy resin Phenoxy resin (1): (manufactured by Tohto Kasei Co., YP-50P; weight average molecular weight 60, 000, repeating unit represented by the following formula)

[Chemical 37] Phenoxy resin (2): (YPB-40PXM40 manufactured by Tohto Kasei;
Weight-average molecular weight 33,000, repeating unit represented by the following formula) (However, YPB-40PXM40 is the solid content of the material 40
Varnish with a total solvent content of 60% by weight of methyl ethyl ketone, xylene and 1-methoxy-2-propanol)

[Chemical 38]

(D) Rubber component Synthetic rubber (1): Polycondensation of aromatic polyamide oligomer (X) having amino groups at both ends and butadiene-acrylonitrile copolymer (Y) having carboxyl groups at both ends. Elastomer (Nippon Kayaku, weight average molecular weight 50,000)

[Chemical Formula 39]

Synthetic rubber (2) Acrylonitrile-butadiene rubber: (Nippon Zeon, N
ipol FN4002; weight average molecular weight 280000)

[Chemical 40] Synthetic rubber (3): carboxylated acrylonitrile-butadiene rubber (manufactured by JSR, PNR-1H; weight average molecular weight 300000, provided that PNR-1HSK is a varnish having a solid content of 17% by weight of the material and 83% by weight of methyl ethyl ketone).
(Used in 17 forms)

[Chemical 41]

Synthetic rubber (4) Acrylic ester copolymer: (manufactured by Nagase Chemtex, WS-023DR; weight average molecular weight 450000)

[Chemical 42] In each chemical formula of the synthetic rubber, a, b, c, d,
j, k, l, m and n are numbers representing the average degree of polymerization.

(E) Curing Accelerator Curing Accelerator (1): 2-Ethyl-4-methylimidazole (Curezole 2E4MZ, manufactured by Shikoku Chemicals)

[Chemical 43]

The synthetic rubber (1) used in this example
Used the one manufactured based on the method described in Japanese Patent Laid-Open No. 2001-49082. That is, it is obtained by polycondensation of an aromatic polyamide oligomer having amino groups at both ends and a butadiene-acrylonitrile copolymer having carboxyl groups at both ends. That is, a predetermined amount of isophthalic acid, 3,4′-oxydianiline, 5-hydroxyisophthalic acid, lithium chloride, calcium chloride, N-methyl-2-pyrrolidone (NMP),
After stirring and dissolving pyridine in a container equipped with a stirrer, triphenyl phosphite was added and reacted at 90 ° C. for a predetermined time to produce an aromatic polyamide oligomer having amino groups at both ends. . In addition to this, a butadiene-acrylonitrile copolymer having a carboxyl group at both ends (Hycar CTBN, manufactured by BF Goodrich,
Butadiene-acrylonitrile component contained in the acrylonitrile component is 17 mol%, a molecular weight of about 3600) in NMP was added to the solution, and the mixture was further reacted for a predetermined time, cooled to room temperature, and the reaction solution was added to methanol. The synthetic rubber (1) used in this example was deposited.
The precipitated polymer was further purified by washing with methanol and refluxing with methanol. The intrinsic viscosity of this polymer was 0.49 dl / g (dimethylacetamide, 25 ° C.). As the other synthetic rubbers (2) to (4), commercially available products were used.

The above raw materials were blended in the proportions shown in Tables 1 to 7,
Dissolve with N, N-dimethylformamide (DMF) in a container equipped with a stirrer (when a commercially available solvent-containing material is used, only the content of the solvent, part of which is methyl ethyl ketone (MEK)) , 1-methoxy-2-propanol and xylene were included) and filtered to prepare an epoxy resin composition solution (varnish). This epoxy resin composition solution is applied on a PET (polyethylene terephthalate) film (thickness 50 μm) so that the thickness after drying becomes 50 μm, and dried at 80 ° C. to 130 ° C. for 5 minutes to form a film-like adhesive. I got an agent.

HAST (Highly Accelerated tem)
perature and humidity Stress Test), TS (Thermal
The film adhesive used for the Shock) and solder heat resistance tests had a thickness of 30 μm after drying. Using the film adhesive obtained in this way,
After obtaining various test pieces, they were subjected to measurement of physical properties. The results are shown in Table 8
~ 12. In addition, each physical property measurement of Tables 8-12 is based on the following evaluation methods.

(Film Supporting Property) The film adhesive (before curing) was evaluated by the occurrence of cracks when bent 180 degrees. When the crack did not occur, it was indicated by ⊚, when it was cracked but did not lead to continuous cracks, it was treated as a film, and when it was handled as a film, it was broken, and when it could not be treated as a film, it was indicated as ×. In the film adhesive (before curing), a state of being placed on a PET film (thickness: 50 μm) (in the columns in Tables 8 to 12, PET is shown in the columns
In both the state of being present) and the state of being peeled off from the PET film (indicated by PET in the columns of Tables 8 to 12),
The film support was evaluated. The film support of the film adhesive (before curing) is greatly affected by the residual solvent ratio, and the higher the residual solvent ratio, the better the film support tends to be. Therefore, the solvent residual ratio of the film adhesive (before curing) was 3 in all the examples and comparative examples.
It was confirmed that the content was not more than weight%. Solvent residual rate is 20
It was determined by measuring the weight loss rate after drying for 60 minutes in an atmosphere of 0 ° C.

(Coefficient of thermal expansion, glass transition temperature) A film-like adhesive was cured at 180 ° C. for 1 hour to obtain a test piece. Using a thermomechanical analyzer (TMA),
It was determined under the condition that the temperature rising rate was 10 ° C / min. The thermal expansion coefficient α ₁ was defined as the average rate of change of 60 to 100 ° C.

(Tensile test) The film adhesive was applied at 180 ° C.
A test piece was obtained by curing for 1 hour. Tensile speed of 5 mm by tensile test using Tensilon tester
The elastic modulus, strength and elongation at break were determined under the condition of / min.

A test piece was obtained by curing the (flame retardant) film adhesive at 180 ° C. for 1 hour. The test piece had a size of width 12.7 mm × length 127 mm (thickness 50 μm). A simple method was used to ignite the end of the test piece with a burner and evaluate the flammability. A UL94V-0 certified known material and a UL94V-1 certified known material were simultaneously tested in the same manner to perform a graded evaluation of Examples and Comparative Examples. That is, when the self-extinguishing property is equal to or higher than that of the known material of UL94V-0 certification, V-0 and UL94V-1 are equal to or higher than that of the known material of UL94V-1 certification and less than the equivalent of UL94V-0. Those that did not meet the requirements were marked with x. The film adhesive may or may not be required to have flame retardancy as its intended use.
Examples 1 to 14 and Comparative Examples 1 to 12 are blends assuming the case where flame retardancy is required, and therefore, a brominated epoxy resin or a brominated phenoxy resin is blended. The flame retardance was evaluated in these Examples 1 to 14 and Comparative Example 1
Only about -12 was carried out.

(Copper foil peel strength) The film adhesive was
Using a batch type vacuum laminator, press-bonding temperature is 70-
In the range of 120 ° C, the temperature is set so that the materials can be laminated without fusion, and the pressure is 0.3 MPa.
Under conditions of atmospheric pressure of 400 Pa or less, S of copper foil with a thickness of 18 μm
The surface (shiny surface) was laminated on one side. The film adhesive with a copper foil thus obtained was cured at 180 ° C. for 1 hour. Further, in the thus obtained cured product with copper foil, the surface on the resin cured product side was adhered to a rigid substrate as a supporting material using an adhesive. JIS
Based on C6481 (peel strength), create a test piece of an appropriate shape, and use a strograph tester,
The 90-degree copper foil peel strength was measured by pulling the copper foil in the 90-degree direction at a speed of 50 mm / min.

(Moisture resistance reliability test: HAST) A film adhesive having a thickness after drying of 30 μm was prepared. Using a batch-type vacuum laminator, this film adhesive is set to a temperature at which the pressure bonding can be laminated without fusion of the materials within a range of 70 to 120 ° C., and a pressure bonding pressure of 0.3 MPa and a pressure of 400 Pa or less. Insulation plate with a comb-shaped electrode for HAST (anode, cathode 1
By combining a pair of comb-shaped electrodes (copper wiring), an anode and a cathode were alternately laminated to an insulating plate on which copper wiring having a thickness of 18 μm was placed at L / S = 150 μm / 150 μm). The resin-laminated insulating plate with the comb-shaped electrode thus obtained was cured at 180 ° C. for 1 hour to obtain a test piece. This test piece is 130 ° C / 85
By applying a voltage of 10 V under the environment of% RH and measuring the presence or absence of a short circuit over time, the moisture resistance reliability (HA
ST) was evaluated. Tables 8 to 12 show (number of defective test pieces / number of trial test pieces).

(Thermal shock reliability test: TS) A film adhesive having a thickness after drying of 30 μm was prepared. Using a batch type vacuum laminator, this film adhesive is set to a temperature at which the pressure bonding can be performed without fusing the materials within a range of 70 to 120 ° C., and the pressure bonding is 0.3 MPa and the pressure is 400 Pa.
The test plate for TS was laminated on one side under the following conditions. The resin-laminated TS test plate thus obtained was cured at 180 ° C. for 1 hour to obtain a test piece. When this test piece was subjected to a liquid phase immersion −65 ° C., 5 minutes, and a 150 ° C., 5 minute cooling / heating cycle using a thermal shock tester, the occurrence of resin cracks at each cumulative cycle number was observed. The thermal shock reliability (TS) was evaluated by measuring. Tables 8 to 12 show (number of defective test pieces / number of trial test pieces). The TS test plate was obtained by mounting a copper dumbbell pattern having a thickness of 18 μm on FR-4, and the number of copper dumbbells per test piece was 1350. 14 or more resin cracks near the dumbbell per test piece (13
The test piece was regarded as defective when it became 1% or more out of 50 pieces.

(Solder Heat Resistance Test) A film adhesive having a thickness after drying of 30 μm was prepared. Using a batch-type vacuum laminator, this film adhesive is set to a temperature at which the pressure bonding can be laminated without fusion of the materials within a range of 70 to 120 ° C., and a pressure bonding pressure of 0.3 MPa and a pressure of 400 Pa or less. Under the conditions described above, one side was laminated on the S side (shiny side) of a copper foil having a thickness of 18 μm. The film adhesive with a copper foil thus obtained was cured at 180 ° C. for 1 hour. Furthermore, the cured product with the copper foil thus obtained was cut into 50 mm square pieces to prepare test pieces, and the test pieces were prepared under the conditions of 85 ° C. and 85% RH.
It was allowed to absorb moisture for 00 hours. When the cured product with the copper foil is put into a moisture absorber, the copper foil side is temporarily fixed to a rigid substrate as a supporting material with a double-sided adhesive tape to prevent warping (when dipping the solder, the rigid substrate is fixed). So that the cured product with copper foil can be peeled off). After absorbing moisture under predetermined conditions, a test piece of the cured product with a copper foil peeled from the rigid substrate was immersed in a solder bath at 260 ° C. for 60 seconds, and the presence or absence of blistering or peeling of the copper foil surface was visually inspected. Tables 8 to 12 show (number of defective test pieces / number of trial test pieces).

The results are shown in Tables 8 to 12, and all Examples 1 to 28 satisfying the conditions specified in the present invention are excellent in the thermal cycle reliability, the solder heat resistance and the moisture resistance reliability, and particularly the member (copper foil). It can be seen that the film has excellent adhesion to, heat resistance, mechanical strength, low stress (low thermal expansion, low elastic modulus), and the like, and also provides excellent film support before curing. On the other hand, Comparative Examples 1 to 20, which do not satisfy the conditions specified in the present invention, are not as excellent in these characteristics at the same time as the Examples. In other words, the thermal shock reliability (TS) of all the comparative examples is not as good as that of the examples.
Copper foil peel strength (S-plane), elongation at break, elastic modulus, coefficient of thermal expansion, which is considered to have a high correlation with thermal shock reliability,
It is estimated that the Tg is not as good as the examples at the same time.

In Tables 1 to 7, the numerical values in the tables indicate the blending amount (parts by weight). Although the phenoxy resin (2) and the synthetic rubber (3) are in a solution form, the compounding amount as a solid content is shown in the table. Since the compounding amount of the curing accelerator (1) was constant at 0.10 (parts by weight) in all the examples and comparative examples, the description is omitted. Solvents are DMF, MEK
(Methyl ethyl ketone), MP (1-methoxy-2-propanol) or XY (xylene) was used, and the contained ones were indicated by ◯.

[0067]

[Table 1]

[0068]

[Table 2]

[0069]

[Table 3]

[0070]

[Table 4]

[0071]

[Table 5]

[0072]

[Table 6]

[0073]

[Table 7]

[0074]

[Table 8]

[0075]

[Table 9]

[0076]

[Table 10]

[0077]

[Table 11]

[0078]

[Table 12]

[0079]

The epoxy resin composition of the present invention is used for connecting to a substrate an insulating resin layer of a build-up multilayer printed wiring board in which a conductor circuit layer and an insulating resin layer are alternately stacked and a semiconductor element such as a flip chip. When used as an adhesive, or a die-bonding adhesive for mounting semiconductor elements on lead frames, TAB tapes, etc., it has excellent thermal cycle reliability, solder heat resistance, and moisture resistance reliability, and in particular adhesion to members. A film-like adhesive having excellent heat resistance, mechanical strength, low stress (low thermal expansion, low elastic modulus) and the like, and further having excellent film support in the pre-curing stage.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 21/00 C08L 21/00 71/10 71/10 77/06 77/06 C09D 109/02 C09D 109 / 02 161/12 161/12 163/00 163/00 171/10 171/10 177/06 177/06 C09J 109/02 C09J 109/02 161/12 161/12 163/00 163/00 171/10 171 / 10 177/06 177/06 (72) Inventor Hironobu Kawasato 1 Tsukiji, Kisarazu-shi, Chiba Nippon Steel Chemical Co., Ltd. Electronic Materials Research Laboratory F-term (reference) 4J002 AC07Z CD02W CD04W CD05W CD06W CD07W CD11W CD12W CE00X CH08Y CL07Z EU116 EU186 EW016 EW176 FD010 FD14X FD156 GH01 4J031 AA29 AA55 AB01 AC07 AF12 BA28 4J036 AA01 AC01 AD08 AE05 DA01 DA02 FB05 FB06 FB12 FB13 JA05 JA06 4J0J062J062DB2 DB06 DB2 DB06 DB02 DB06 DB02 DB061 DB02 DB061 DB02 DB061 DB02 DB061 DB02 DB061 DB02 DB061 DB02 DB061 DB061 DB02 DB061 DB071 4 MA07 MA09 MA14 NA04 NA11 NA12 NA14 NA21 4J040 CA071 CA072 EB062 EC001 EC002 EC061 EC062 EC071 EC072 EC261 EC262 EE061 EE062 EG021 EG022 HC24 HC25 HD27 HD39 JA09 KA16 KA17 LA06 LA07 LA08 NA20

Claims (7)

[Claims] 1. An epoxy resin (A), a curing agent (B),
In an epoxy resin composition containing (C) a phenoxy resin, (D) a rubber component and (E) a curing accelerator, (B)
The curing agent is represented by the following general formula (1): (However, A represents a hydrocarbon group-substituted or unsubstituted benzene ring or naphthalene ring, l represents 1 or 2, and these may be the same or different. R _{1 to} R ₄ are independently, A hydrogen atom or a methyl group, and n represents a number of 1 to 15), and the curing agent contains 10 to 100% by weight of a polyvalent hydroxy resin curing agent, and (C) a phenoxy resin. Is the following general formula (2) (However, X ₁ represents —C (CH ₃ ) ₂ — or —CH ₂ — and may be the same or different. R _{5 to} R ₁₂ independently represent a hydrogen atom or a bromine atom, and n is The weight average molecular weight of the repeating unit represented by 1) is 1 or more.
It contains a phenoxy resin of 20,000 to 200,000 as an essential component, and has a weight average molecular weight of 10,000 to 200,000 mainly composed of repeating units represented by the general formula (2).
The phenoxy resin content of 00 is (A) epoxy resin,
5 to 50 wt% of the total of (B) curing agent, (C) phenoxy resin, (D) rubber component and (E) curing accelerator,
(D) The rubber component has a weight average molecular weight of 10,000 to 1,000 obtained by polycondensation of an aromatic polyamide oligomer having amino groups at both ends and a butadiene-acrylonitrile copolymer having carboxyl groups at both ends. ,
000 elastomer as an essential component, and the content of the elastomer is (A) epoxy resin, (B)
An epoxy resin composition comprising 5 to 50% by weight of the total amount of a curing agent, (C) phenoxy resin, (D) rubber component and (E) curing accelerator. 2. The epoxy resin composition according to claim 1, wherein the polyhydric hydroxy resin curing agent is a phenol biphenyl aralkyl type resin represented by the following general formula (3). [Chemical 3] (However, n shows the number of 1 to 15.) 3. The elastomer comprises an aromatic polyamide oligomer having amino groups at both ends represented by the following general formula (4) and butadiene-acrylonitrile having carboxyl groups at both ends represented by the following general formula (5). An elastomer obtained by polycondensation with a copolymer.
Or the epoxy resin composition according to 2. [Chemical 4] (However, a and b are average polymerization degrees, and a>
0, b> 0, and a + b ≧ 1. The individual components are independent of each other, can be arranged arbitrarily, and may be present in a block form or a random form. ) [Chemical 5] (However, c and d are average polymerization degrees, respectively, and c ≧
1, and d ≧ 1. The individual components are independent of each other, can be arranged arbitrarily, and may be present in a block form or a random form. ) 4. The epoxy resin (A) comprises at least one epoxy resin selected from the epoxy resin group represented by the following general formulas (6) to (10) in an amount of 20 to 100% by weight in the epoxy resin. It contains 1 to 3.
The epoxy resin composition according to any one of 1. [Chemical 6] (However, X ₂ is _{-C (CH 3) 2 -,} - CH 2 - or a single bond, a good .R ₁₃ to R ₁₆ be the same or different is independently, a hydrogen atom or a methyl group And n is a number from 0 to 15.) [Chemical 8] (However, n represents a number of 1 to 15.) (However, R ₁₇ represents a hydrogen atom or an alkyl group and may be the same or different. N represents a number of 1 to 15.) (However, i shows 1 or 2, n shows the number of 0-10. Moreover, bromine content is 10-80 weight%. In addition, in General formula (6)-(10), G is Indicates a glycidyl group.) 5. A varnish obtained by dissolving the epoxy resin composition according to any one of claims 1 to 4 in a solvent. 6. A film adhesive obtained by forming the epoxy resin composition according to any one of claims 1 to 4 into a film. 7. A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 4.