JPWO2014087882A1 - Metal layer with resin layer, laminate, circuit board, and semiconductor device - Google Patents

Abstract

The metal layer (1) with a resin layer for a circuit board includes a resin layer (11) and a metal layer (12) provided on the resin layer (11). The resin layer (11) is thermosetting. The storage elastic modulus E′RT at 25 ° C. of the resin layer (11) after thermosetting the resin layer (11) at 190 ° C. for 2 hours is 0.1 GPa or more and 1.5 GPa or less. Furthermore, the storage elastic modulus E′HT at 175 ° C. of the resin layer (11) after thermosetting the resin layer (11) at 190 ° C. for 2 hours is 10 MPa or more and 0.7 GPa or less.

Description

  The present invention relates to a metal layer with a resin layer, a laminate, a circuit board, and a semiconductor device.

  Conventionally, a semiconductor device in which semiconductor elements are stacked on a circuit board has been used. For example, Patent Document 1 discloses a semiconductor device including a circuit board and a semiconductor element, and connecting the semiconductor element and the circuit board with a wire.

JP-A-8-55867

Such a semiconductor device is required to have high connection reliability that can withstand various environmental temperature changes between the semiconductor element and the circuit board.
In patent document 1, the connection reliability is improved by adjusting the glass transition point of a circuit board and a linear expansion coefficient.
On the other hand, the present inventor has devised an invention that solves such problems from a new viewpoint.

  As a result of intensive studies by the present inventors, an average linear expansion coefficient of the semiconductor element and an average linear expansion coefficient of the circuit board are obtained by providing a layer having a relatively low elastic modulus on the surface side layer of the circuit board. It was found that the stress caused by the difference between the two can be relaxed. Thereby, the connection reliability between a semiconductor element and a circuit board can be improved.

  The present invention has been invented based on such knowledge.

That is, according to the present invention,
It is a metal layer with a resin layer for circuit boards used for circuit boards,
The resin layer is thermosetting;
The storage elastic modulus E ′ _RT at 25 ° C. of the resin layer after thermosetting the resin layer at 190 ° C. for 2 hours is 0.1 GPa or more and 1.5 GPa or less,
The resin layer 190 ° C., the storage modulus E _'HT of 175 ° C. of the resin layer after providing thermally cured in 2 hours or more 10 MPa, a resin layer with a metal layer is less than 0.7GPa is provided.

190 ° C., 2 hours '1.5 GPa or less _RT, the storage elastic modulus E of 175 ° C.' storage modulus E of 25 ° C. of the resin layer after providing thermally cured at has less 0.7GPa the _HT, 25 ° C., At any temperature of 175 ° C., the storage elastic modulus of the resin layer is low.
Thereby, when this metal layer with a resin layer is used for a circuit board and a semiconductor element is mounted, the connection reliability between the semiconductor element and the circuit board in various temperature environments can be improved.

  Furthermore, according to this invention, the laminated body using the metal layer with a resin layer mentioned above and also a circuit board can be provided.

That is, according to the present invention, the metal layer with a resin layer obtained by curing the resin layer of the metal layer with a resin layer described above,
A laminated body for a circuit board including the insulating resin layer disposed on the resin layer side of the metal layer with a resin layer can be provided.

Moreover, a circuit board comprising a layer obtained by curing the resin layer of the metal layer with a resin layer and a circuit layer formed by selectively removing the metal layer of the metal layer with a resin layer,
The circuit layer can also provide a circuit board disposed in the outermost layer among the circuit layers formed on the circuit board.
Furthermore, a semiconductor device provided with this circuit board can also be provided.

  ADVANTAGE OF THE INVENTION According to this invention, the metal layer with a resin layer for circuit boards which can improve the connection reliability of a semiconductor element and a circuit board, a laminated body using the same, a circuit board, and a semiconductor device are provided.

  The above-described object and other objects, features, and advantages will become more apparent from the preferred embodiments described below and the accompanying drawings.

It is sectional drawing of the metal layer with a resin layer for circuit boards concerning one Embodiment of this invention, and is sectional drawing along the thickness direction of the metal layer with resin layers for circuit boards. (A) And (B) is sectional drawing which shows the manufacturing process of a circuit board, and is sectional drawing along the direction orthogonal to a board | substrate surface. It is sectional drawing of a circuit board. It is sectional drawing which shows the semiconductor device which uses a circuit board. (A) And (B) is sectional drawing which shows the laminated body to which the metal layer with a resin layer is applied.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same components are denoted by the same reference numerals, and detailed description thereof is appropriately omitted so as not to overlap.
First, with reference to FIG. 1, the metal layer with the resin layer for circuit boards of this embodiment is demonstrated.
The metal layer 1 with a resin layer for a circuit board includes a resin layer 11 and a metal layer 12 provided on the resin layer 11.
The resin layer 11 is thermosetting. After the resin layer 11 is thermally cured at 190 ° C. for 2 hours, the storage elastic modulus E ′ _RT at 25 ° C. of the resin layer 11 is 0.1 GPa or more and 1.5 GPa or less. Furthermore, after the resin layer 11 is thermally cured at 190 ° C. for 2 hours, the storage elastic modulus E ′ _HT at 175 ° C. of the resin layer 11 is 10 MPa or more and 0.7 GPa or less.

The metal layer 12 becomes a circuit layer in the circuit board, and is made of, for example, Cu. The thickness of the metal layer 12 is, for example, 10 to 30 μm.
The resin layer 11 is a B stage (semi-cured). And the thickness of the resin layer 11 is 5 micrometers or more and 30 micrometers or less, for example, Preferably, they are 10 micrometers or more and 20 micrometers or less. The resin layer 11 functions as a stress relaxation layer when the circuit board is formed. By making the thickness of the resin layer 11 5 μm or more, the stress relaxation effect can be surely exhibited. On the other hand, the thickness of the circuit board can be suppressed by setting the thickness of the resin layer 11 to 30 μm or less.

The resin layer 11 is obtained by semi-curing a resin composition containing a resin component (A) containing a thermosetting resin (excluding the curing agent (B)). The resin layer 11 may further include a curing agent (B) and an inorganic filler (C) as long as the effects of the present invention are not impaired.
The resin component (A) preferably contains a thermosetting resin (A2) having at least one of an aromatic ring structure and an alicyclic structure (alicyclic carbocyclic structure) as a thermosetting resin.
By using such a thermosetting resin (A2), the glass transition point (Tg) can be increased.
Examples of the thermosetting resin (A2) having an aromatic ring or alicyclic structure include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, and bisphenol M type epoxy. Resin, bisphenol P type epoxy resin, bisphenol type epoxy resin such as bisphenol Z type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, novolak type epoxy resin such as tetraphenol ethane novolak type epoxy resin, biphenyl type epoxy Resin, arylalkylene type epoxy resin such as phenol aralkyl type epoxy resin having biphenylene skeleton, and epoxy resin such as naphthalene type epoxy resin That. One of these can be used alone, or two or more can be used in combination.
Together we can be further increased glass transition temperature among these, from the viewpoint of lowering the storage modulus E _'RT and the storage modulus E' _HT, naphthalene type epoxy resins are preferred. Here, the naphthalene type epoxy resin refers to one having a naphthalene ring skeleton and having two or more glycidyl groups.
Any of the following formulas (5) to (8) can be used as the naphthalene type epoxy resin. In the formula (6), m and n represent the number of substituents on the naphthalene ring, and each independently represents an integer of 1 to 7. In Formula (7), Me represents a methyl group, and l, m, and n are integers of 1 or more. However, l, m, and n are preferably 10 or less.

  In addition, as a compound of Formula (6), it is preferable to use any 1 or more types of the following.

  Moreover, as a naphthalene type epoxy resin, the naphthylene ether type epoxy resin represented by the following formula | equation (8) can also be used.

（上記式（８）式において、ｎは１以上２０以下の整数であり、ｌは１以上２以下の整数であり、Ｒ_１はそれぞれ独立に水素原子、ベンジル基、アルキル基または下記式（９）で表される構造であり、Ｒ_２はそれぞれ独立に水素原子またはメチル基である。）

(In the above formula (8), n is an integer of 1 or more and 20 or less, l is an integer of 1 or more and 2 or less, and R ₁ is independently a hydrogen atom, a benzyl group, an alkyl group, or the following formula (9 And R ₂ is independently a hydrogen atom or a methyl group.)

（上記式（９）式において、Ａｒはそれぞれ独立にフェニレン基またはナフチレン基であり、Ｒ_２はそれぞれ独立に水素原子またはメチル基であり、ｍは１又は２の整数である。）

(In the above formula (9), Ar is each independently a phenylene group or a naphthylene group, R ₂ is each independently a hydrogen atom or a methyl group, and m is an integer of 1 or 2.)

  Examples of the naphthylene ether type epoxy resin represented by the above formula (8) include those represented by the following formula (10).

（上記式（１０）式において、ｎは１以上２０以下の整数であり、好ましくは１以上１０以下の整数であり、より好ましくは１以上３以下の整数である。Ｒはそれぞれ独立に水素原子または下記式（１１）で表される構造であり、好ましくは水素原子である。）

(In the above formula (10), n is an integer of 1 to 20, preferably an integer of 1 to 10, more preferably an integer of 1 to 3. Each R is independently a hydrogen atom. Or a structure represented by the following formula (11), preferably a hydrogen atom.)

（上記式（１１）式において、ｍは１又は２の整数である。）

(In the above formula (11), m is an integer of 1 or 2.)

  Examples of the naphthylene ether type epoxy resin represented by the above formula (10) include those represented by the following formulas (12) to (16).

  In addition, you may use cyanate resin as a thermosetting resin (A2). For example, a novolak type cyanate resin, a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, a tetramethylbisphenol F type cyanate resin, and the like may be used, and any one or more of these may be used. Among these, it is preferable to use a novolac type cyanate resin.

Moreover, it is preferable that the resin component (A) contains the reactive group (for example, glycidyl group) contained in the thermosetting resin (A2) and the compound (A1) having a reactive group that reacts.
Examples of such a compound (A1) include an aliphatic epoxy resin having no aromatic ring structure and an alicyclic structure (alicyclic carbocyclic structure), a copolymer of acrylonitrile and butadiene containing a carboxyl group at the terminal. (CTBN, for example, represented by the following formula (17), where x is 0.05 or more and 0.2 or less, y is 0.8 or more and 0.95 or less (x and y indicate a molar ratio, x + y = 1), a compound in which z is from 50 to 70. For example, a trade name CTBN1300X (manufactured by Ube Industries), a phenolic hydroxyl group-containing aromatic polyamide-poly (butadiene-acrylonitrile) block copolymer (for example, a product) Any one or more selected from the group consisting of the name KAYAFLEX BPAM-155 (manufactured by Nippon Kayaku Co., Ltd., terminal is an amide group) can be used. By using such a compound (A1) appropriately selected and, while maintaining the value of the glass transition point of the resin layer 11, the storage modulus E _{'RT, E'} of the resin layer 11 can reduce the _HT it can.

From the viewpoint of reducing the storage elastic moduli E ′ _RT, E ′ _HT of the resin layer 11 to the predetermined range described above, the aliphatic epoxy resin is an aliphatic epoxy resin having no cyclic structure other than the glycidyl group. It is preferable. In addition, from the viewpoint of setting the storage elastic moduli E ′ _{RT and} E ′ _HT of the resin layer 11 to the predetermined ranges described above, bifunctional or higher aliphatic epoxy resins having two or more glycidyl groups are preferable.
The aliphatic epoxy resins as described above are preferably those represented by the chemical formulas (18) to (27), preferably include at least one of them, and particularly include those represented by the chemical formula (18). preferable. Such an aliphatic epoxy resin is excellent because an epoxy group is not easily oxidized and an elastic modulus is hardly increased due to thermal history.

（式（１８）において、ｌ，ｍ，ｎ，ｐ，ｑ，ｒは０以上の整数、ただし、ｌ、ｍ、ｎがすべて０の場合を除く。また、ｐ、ｑ、ｒがすべて０の場合も除く。なかでも、ｌ＝１〜５、ｍ＝５〜２０、ｎ＝０〜８、ｐ＝０〜８、ｑ＝３〜１２、ｒ＝０〜４が好ましい。）

(In Expression (18), l, m, n, p, q, and r are integers of 0 or more, except when l, m, and n are all 0. Also, p, q, and r are all 0. (In particular, l = 1 to 5, m = 5 to 20, n = 0 to 8, p = 0 to 8, q = 3 to 12, and r = 0 to 4 are preferable.)

（式（２６）において、ｌ、ｍ、ｎは０以上の整数、ただし、ｌ、ｍ、ｎがすべて０の場合を除く。なかでも、ｌ＝１〜１２、ｍ＝８〜３０、ｎ＝０〜１０が好ましい。）

(In the formula (26), l, m, and n are integers of 0 or more, except when l, m, and n are all 0. Especially, l = 1 to 12, m = 8 to 30, and n = 0-10 are preferred.)

（式（２７）において、ｎは１以上の整数であり、なかでも、２〜１５であることが好ましい。）

(In Formula (27), n is an integer greater than or equal to 1, and it is preferable that it is 2-15 especially.)

Then, while achieving a high glass transition point of the resin layer 11, the content of the storage modulus E _{'RT, E'} of the resin layer 11 from the viewpoint of lowering the _HT, compound (A1) constituting the resin layer 11 resin 3 mass% or more and 45 mass% or less are preferable with respect to 100 mass% of total solid content of a composition, 5 mass% or more and 40 mass% or less are more preferable, and content of a thermosetting resin (A2) is the resin layer 11. 30 mass% or more and 65 mass% or less are preferable with respect to 100 mass% of total solid of the resin composition to comprise, and 33 mass% or more and 60 mass% or less are more preferable.
When the thermosetting resin (A2) and the compound (A1) are used in combination, the mass ratio represented by the total of the compound (A1) / the total of the thermosetting resin (A2) is 0.1 or more. It is preferably 5 or less, and more preferably 0.1 or more and 1.1 or less.
Further, the resin component (A) containing the thermosetting resin (A2) and the compound (A1) is 50% by mass or more and 90% by mass with respect to 100% by mass of the total solid content of the resin composition constituting the resin layer 11. In particular, it is preferably 60% by mass or more and 80% by mass or less.

  Examples of the curing agent (B) (curing catalyst) include organic metals such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), and trisacetylacetonate cobalt (III). Salts; tertiary amines such as triethylamine, tributylamine, diazabicyclo [2,2,2] octane; 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, Imidazoles such as 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl-4,5-dihydroxyimidazole; triphenylphosphine, tri-p-tolylphosphine, tetraphenyl Phosphonium tetraf Organic phosphorus compounds such as nylborate, triphenylphosphine / triphenylborane, 1,2-bis- (diphenylphosphino) ethane; phenolic compounds such as phenol, bisphenol A and nonylphenol; acetic acid, benzoic acid, salicylic acid, paratoluenesulfonic acid Or an organic acid such as, or a mixture thereof. As the curing catalyst, one kind including these derivatives can be used alone, or two or more kinds including these derivatives can be used in combination.

The content of the curing catalyst is not particularly limited, but is preferably 0.05% by mass or more and 5% by mass or less, particularly 0.2% by mass with respect to 100% by mass of the total solid content of the resin composition constituting the resin layer 11. The content is preferably 2% by mass or less.
Moreover, as a hardening | curing agent (B), a phenol type hardening | curing agent may be used and you may use together with a hardening catalyst. As the phenol-based curing agent, known or commonly used ones such as phenol novolak resin, alkylphenol novolak resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, zyloc type phenol resin, terpene modified phenol resin, polyvinylphenols, etc. These can be used in combination.
When the epoxy resin is contained in the resin component (A), the compounding amount of the phenol-based curing agent is preferably 0.1 to 1.0 as the equivalent ratio with the epoxy resin (phenolic hydroxyl group equivalent / epoxy group equivalent). . As a result, there remains no unreacted phenol curing agent, and the moisture absorption heat resistance is improved.
Although content of a phenol type hardening | curing agent is not specifically limited, 5 mass% or more and 45 mass% or less are preferable with respect to 100 mass% of total solids of the resin composition which comprises the resin layer 11, 10 mass% or more and 40 mass% % Or less is more preferable, and 15 mass% or more and 35 mass% or less is further more preferable.

  Examples of the inorganic filler (C) include silicates such as talc, fired clay, unfired clay, mica and glass, oxides such as titanium oxide, alumina, silica and fused silica; calcium carbonate, magnesium carbonate and hydrotal Carbonates such as sites; hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide; sulfates or sulfites such as barium sulfate, calcium sulfate, calcium sulfite; zinc borate, barium metaborate, aluminum borate And borate salts such as calcium borate and sodium borate; nitrides such as aluminum nitride, boron nitride, silicon nitride and carbon nitride; titanates such as strontium titanate and barium titanate. One of these can be used alone, or two or more can be used in combination.

Among these, aluminum hydroxide is preferable in that the effect of imparting flame retardancy is excellent.
Among these, silica is particularly preferable, and fused silica (especially spherical fused silica) is preferable in terms of excellent low thermal expansion.
The average particle diameter of the inorganic filler (C) is not particularly limited, but is preferably 0.01 μm or more and 5 μm or less, and particularly preferably 0.5 μm or more and 2 μm or less. By setting the particle size of the inorganic filler (C) to 0.01 μm or more, the varnish can be made low in viscosity and handleability can be improved. Moreover, sedimentation etc. of an inorganic filler (C) can be suppressed in varnish by setting it as 5 micrometers or less. This average particle diameter can be measured by, for example, a particle size distribution meter (manufactured by Shimadzu Corporation, product name: laser diffraction particle size distribution measuring device SALD series).

  In addition, the inorganic filler (C) is not particularly limited, but an inorganic filler having a monodispersed average particle diameter can also be used, and an inorganic filler having a polydispersed average particle diameter can be used. Furthermore, one type or two or more types of inorganic fillers having an average particle size of monodisperse and / or polydisperse can be used in combination.

  Furthermore, spherical silica (especially spherical fused silica) or aluminum hydroxide having an average particle size of 5 μm or less is preferable, and spherical fused silica or aluminum hydroxide having an average particle size of 0.5 μm or more and 2 μm or less is particularly preferable. Thereby, the filling property of an inorganic filler (C) can be improved. Moreover, the film thickness uniformity of the resin layer 11 can be improved.

The content of the inorganic filler (C) contained in the resin layer 11 is preferably 30% by mass or less, more preferably 20% by mass or less, based on 100% by mass of the entire resin layer. It is particularly preferable that the content is not more than mass%. Thus, the storage modulus E _{'RT, E'} of the resin layer 11 with reducing the _HT, it is possible to improve the circuit workability.

  Moreover, it is preferable that an inorganic filler (C) is 5 to 60 mass parts with respect to 100 weight part of resin components (A). Especially, it is preferable that they are 10 mass parts or more and 50 mass parts or less. By setting it as 5 mass parts or more, the average linear expansion coefficient of the resin layer 11 can be reduced, and it can be set as the low water absorption resin layer 11 by setting it as 60 mass parts or less.

  Furthermore, the composition used as the resin layer 11 may contain a coupling agent (D). The coupling agent (D) improves the wettability of the interface between the resin component (A) and the inorganic filler (C).

As the coupling agent (D), any commonly used one can be used. Specifically, an epoxy silane coupling agent, a cationic silane coupling agent, an aminosilane coupling agent, a titanate coupling agent, and a silicone oil type. It is preferable to use one or more coupling agents selected from coupling agents.
The addition amount of the coupling agent (D) depends on the specific surface area of the inorganic filler (C) and is not particularly limited, but is 0.05 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the filler (C). In particular, 0.1 parts by mass or more and 2 parts by mass or less are preferable.

  The resin layer 11 can be formed by adding the above-described composition to an organic solvent to form a varnish and applying the varnish to the metal layer 12. Although it does not specifically limit as a coating method, For example, the method of apply | coating with a coater or the method of spraying with a spray is employable. Thereafter, heating is performed to remove the solvent, and the resin layer 11 is semi-cured.

In such a resin layer with a metal layer 1, a resin layer 11 190 ° C., 2 hours at the storage modulus E _'RT for 25 ° C. of the resin layer 11 in After thermal curing or 0.1 GPa, 1.5 GPa or less It is.
Among them, the storage modulus E _'RT is above 0.3 GPa, preferably not more than 1.0 GPa.
In addition, after the resin layer 11 is thermally cured at 190 ° C. for 2 hours, the resin layer 11 is in a C stage.
Further, after the resin layer 11 is thermally cured at 190 ° C. for 2 hours, the storage elastic modulus E ′ _HT at 175 ° C. of the resin layer 11 is 10 MPa or more and 0.7 GPa or less. Among them, the storage modulus E _'HT is more than 100 MPa, preferably not more than 0.65GPa.

In order to achieve such storage elastic modulus, the amount of the inorganic filler (C) and the amounts of the compound (A1) and the thermosetting resin (A2) described above may be appropriately adjusted.
In addition, the said storage elastic modulus is measured with the dynamic viscoelasticity measuring apparatus.
The storage elastic modulus E ′ _RT is obtained by applying a tensile load to the resin layer 11 cured at 190 ° C. for 2 hours and measuring from −50 ° C. to 300 ° C. at a frequency of 1 Hz and a temperature increase rate of 5 to 10 ° C./min. The value of the storage elastic modulus at 25 ° C.
The storage elastic modulus E ′ _HT is obtained by applying a tensile load to the resin layer 11 cured at 190 ° C. for 2 hours and measuring from −50 ° C. to 300 ° C. at a frequency of 1 Hz and a temperature increase rate of 5 to 10 ° C./min. It is a value of a storage elastic modulus at 175 ° C.

Here, (a E _'RT> E' _HT, E _'RT -E' _HT) difference 'and _RT storage modulus E' The storage modulus E and _HT is preferably at most 1 GPa. Thus, the difference 'between _RT storage modulus E' The storage modulus E and _HT is set to be lower than or equal 1 GPa, you are possible to suppress a change in storage modulus due to temperature changes. Thereby, even if an abrupt change occurs in the environmental temperature, the stress generated due to the difference in linear expansion coefficient generated between the circuit board and the semiconductor element can be stably relaxed by the resin layer 11.
The lower limit value of the difference 'between _RT storage modulus E' The storage modulus E and _HT is not particularly limited, for example, not less than 0.05 GPa.

Furthermore, the resin layer 11 preferably has a glass transition point Tg of 120 ° C. or higher after thermosetting the resin layer 11 at 190 ° C. for 2 hours, in particular, 130 ° C. or higher, more preferably 140 ° C. or higher, Furthermore, it is preferable that it is 175 degreeC or more. Further, the upper limit value of the glass transition point Tg is not particularly limited, but Tg is preferably 200 ° C. or less, and particularly preferably 190 ° C. or less. Since the resin layer 11 has a relatively high glass transition point Tg of 120 ° C. or higher, the glass transition point is higher than those of the other insulating layers 22 and 211 (see FIG. 3) constituting the general-purpose circuit board.
Therefore, when a heat cycle test or the like is performed on the circuit board, the resin layer 11 is rubbery before the other insulating layers 22 and 211 (see FIG. 3) constituting the circuit board in the temperature rising process. In other words, the physical properties of the resin layer 11 are maintained, so that the stress generated between the circuit board and the semiconductor element by the resin layer 11 can be further relaxed. In addition, by setting the glass transition point within the above range, the semiconductor element 31 can be further prevented from sinking to the circuit board 2 side when the semiconductor element 31 is mounted on the circuit board 2.

  In addition, after the resin layer 11 is thermally cured at 190 ° C. for 2 hours, the average linear expansion coefficient in the in-plane direction of the resin layer 11 at the glass transition point from 25 ° C. of the resin layer 11 is 200 ppm / ° C. or less. Is preferred.

Next, with reference to FIG. 2, the manufacturing method of the circuit board using such a metal layer 1 with a resin layer is demonstrated.
First, as shown in FIG. 2A, an inner layer circuit board to be the core layer 21 is prepared. The core layer 21 includes an insulating layer 211, a circuit layer 212 formed on the front and back surfaces of the insulating layer 211, and a via 213 connecting the circuit layers 212.
The insulating layer 211 includes a fiber base (not shown) and a resin layer impregnated in the fiber base.
The fiber substrate is not particularly limited,
Glass fiber base materials such as glass woven fabric and glass nonwoven fabric, polyamide resin fiber, aromatic polyamide resin fiber, polyamide resin fiber such as wholly aromatic polyamide resin fiber, polyester resin fiber, aromatic polyester resin fiber, wholly aromatic polyester Synthetic fiber substrate, craft paper, cotton linter paper, or linter and kraft pulp composed of woven or non-woven fabric mainly composed of polyester resin fiber such as resin fiber, polyimide resin fiber or fluororesin fiber Examples thereof include organic fiber base materials such as paper base materials mainly composed of mixed paper. Any of these can be used. Among these, a glass woven fabric is preferable. Thereby, the core layer 21 having low water absorption, high strength and low thermal expansion can be obtained.

The resin layer has a C-stage shape and includes a thermosetting resin.
Although it does not specifically limit as a thermosetting resin, For example, an epoxy resin, a melamine resin, a urea resin, cyanate resin etc. are mention | raise | lifted. And one or more of these can be used. Among these, an epoxy resin or a cyanate resin is preferable.
Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol E type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, and bisphenol Z type epoxy resin. Bisphenol type epoxy resin, phenol novolak type epoxy resin, novolac type epoxy resin such as cresol novolak type epoxy resin, biphenyl type epoxy resin, arylalkylene type epoxy resin such as phenol aralkyl type epoxy resin having biphenylene skeleton, naphthalene type epoxy resin, Anthracene type epoxy resin, phenoxy type epoxy resin, dicyclopentadiene type epoxy resin, norbornene type epoxy resin, adamant Emission type epoxy resins, such as epoxy resins and fluorene type epoxy resins. One of these can be used alone, or two or more can be used in combination.
Although it does not specifically limit as a kind of cyanate resin, For example, bisphenol-type cyanate resin, such as a novolak-type cyanate resin, a bisphenol A-type cyanate resin, a bisphenol E-type cyanate resin, a tetramethylbisphenol F-type cyanate resin, etc. can be mentioned. Among these, novolac-type cyanate resins are preferable from the viewpoint of low thermal expansion. Furthermore, other cyanate resins may be used alone or in combination of two or more, and are not particularly limited.

  The resin layer may contain a filler. As a filler, the thing similar to the inorganic filler (C) mentioned above can be used.

Next, as shown in FIG. 2B, a B-stage prepreg (insulating layer 22) is laminated on one surface of the core layer 21, and the metal layer 1 with a resin layer is laminated on the prepreg. At this time, the metal layer 1 with a resin layer is laminated so that the prepreg and the resin layer 11 face each other and come into contact with each other.
The prepreg includes a fiber base material and a thermosetting resin layer impregnated in the fiber base material. However, it is good also as what consists only of a resin layer without including a fiber base material.
As a fiber base material and a resin layer, the thing similar to the core layer 21 can be used.
Further, the prepreg may contain the same filler as that of the core layer 21.
Next, the prepreg (insulating layer 22) and the metal layer 1 with a resin layer are similarly laminated on the other surface of the core layer 21.

  Then, for example, the laminate is heated at 190 ° C. for 2 hours while being pressed in the stacking direction. Thereby, the laminated body in which the insulating layer 22 and the resin layer 11 became the C stage is obtained.

Next, a hole penetrating the metal layer 12, the resin layer 11, and the insulating layer 22 is formed by a laser or the like. A portion that penetrates the resin layer 11 and the insulating layer 22 becomes a via hole.
Thereafter, a seed layer (not shown) is formed on the surface of the hole and the metal layer 12, and a mask is formed on the seed layer. A part of the opening of the mask communicates with the hole, and the surface of the seed layer is exposed from the other part of the opening.
Next, a conductive film is formed in the hole through a part of the opening of the mask by plating, and a conductive film (for example, a Cu film) is formed in the other part of the opening of the mask.
The conductive film in the via hole becomes the via 23 in FIG. Thereafter, the mask is removed, and the portion of the metal layer 12 and the seed layer covered with the mask is removed by etching, whereby the circuit layer 24 shown in FIG. 3 is formed. The circuit layer 24 includes an etched metal layer 12 and a conductive film (for example, Cu film) 241 provided on the metal layer 12. The conductive film 241 is connected to the via 23 and connected to the circuit layer 212 of the core layer 21.

In the circuit board 2, a buildup layer is formed by the cured body of the resin layer 11 and the cured body of the prepreg (insulating layer 22).
Thereafter, as shown in FIG. 3, a solder resist SR is provided on the circuit layer 24. In the circuit board 2 of the present embodiment, the solder resist SR is directly provided on the resin layer 11. Therefore, the circuit layer 24 formed by etching the metal layer 12 becomes the outermost circuit layer in the circuit board 2.

In the circuit board 2 thus formed, the average linear expansion coefficient from 25 ° C. to the glass transition point of the insulating layer 211 of the core layer 21 is, for example, 10 to 50 ppm / ° C. Similarly, the average linear expansion coefficient from 25 ° C. to the glass transition point of the insulating layer 22 is, for example, 10 to 50 ppm / ° C.
As described above, the solder resist SR, the layer obtained by curing the resin layer 11, the circuit layer 24 obtained by selectively removing the metal layer 12, the insulating layer 22, and the core layer 21 are provided. A circuit board 2 is obtained.

Next, the semiconductor device 3 using such a circuit board 2 will be described with reference to FIG.
As shown in FIG. 4, the semiconductor device 3 includes a circuit board 2 and a semiconductor element 31.
The semiconductor element 31 is fixed on the solder resist SR of the circuit board 2 via an adhesive 32. The semiconductor element 31 is connected to the circuit board 2 by bonding wires W.
The bonding wire W is connected to the semiconductor element 31 and is soldered to a part (pad) of the circuit layer 24 of the circuit board 2.

The semiconductor device 3 is, for example, an electronic control unit mounted on a vehicle such as a hybrid vehicle, a fuel cell vehicle, and an electric vehicle, a power conversion inverter unit, a processor unit mounted on a portable terminal such as a smartphone, or the like.
The resin layer 11 can relieve stress generated due to a difference in linear expansion coefficient generated between the circuit board 2 and the electronic component 31 even when the resin layer 11 is left for a long time in an environment where the temperature changes drastically. This is particularly effective when used for a semiconductor device used in an engine room of an automobile.

Such a semiconductor device 3 has high connection reliability between the semiconductor element 31 and the circuit board 2.
This is because the resin layer 11 is provided on the circuit board 2.
As described above, 190 ° C., 2 hours at 25 ° C. storage modulus E of the resin layer 11 after providing thermally cured _'RT is 1.5GPa or less, the storage modulus of 175 ° C. E' _HT is less 0.7GPa The storage elastic modulus is low at both 25 ° C. and 175 ° C.
Thereby, the stress generated due to the difference in linear expansion coefficient between the semiconductor element 31 and the circuit board 2 due to the temperature change can be relaxed by the resin layer 11.
The circuit board 2 has an average linear expansion coefficient larger than that of the semiconductor element 31, and is greatly expanded and contracted by a temperature change. On the other hand, since the amount of expansion and contraction of the semiconductor element 31 is small, a load is applied to the bonding wire W and the connection portion between the bonding wire W and the pad portion of the circuit layer 24. However, since the resin layer 11 has a low storage elastic modulus, the deformation applied to the resin layer 11 can absorb the load applied to the bonding wire W and the connection portion between the bonding wire W and the circuit layer 24.
Therefore, for example, as the insulating layers 22 and 211 constituting the circuit board 2, insulation having a relatively high linear expansion coefficient, for example, an average linear expansion coefficient from 25 ° C. to the glass transition point is 25 ppm / ° C. or more. Even if a layer is used, the connection reliability between the circuit board 2 and the semiconductor element 31 can be improved.
In addition, by setting the storage elastic modulus E ′ _RT to 0.1 GPa or more and the storage elastic modulus E ′ _HT to 10 MPa or more, physical polishing resistance when manufacturing the circuit board 2 (brushes, scrubs, buffs) Resistance). That is, it is possible to prevent the resin layer from being scraped by polishing in the manufacturing process of the circuit board 2.
Furthermore, by setting the storage elastic modulus E ′ _RT to 0.1 GPa or more and the storage elastic modulus E ′ _HT to 10 MPa or more, the resin layer 11 does not become too soft, and the semiconductor element 31 with respect to the circuit board 2. Can be prevented from being displaced. Thereby, the connection reliability of the semiconductor element 31 and the circuit board 2 can be improved.
Further, by setting the storage elastic modulus E ′ _RT to 0.1 GPa or more and the storage elastic modulus E ′ _HT to 10 MPa or more, the semiconductor element 31 is mounted on the circuit board 2 when the semiconductor element 31 is mounted on the circuit board 2. It can also be prevented from sinking to the side.

  Furthermore, in the present embodiment, since the resin layer 11 is disposed immediately below the outermost circuit layer 24 to which the bonding wires W are connected in the circuit board 2, the stress relaxation effect of the resin layer 11 is effectively exhibited. Can be made.

In order to increase the connection reliability between the semiconductor element 31 and the circuit board 2, a method of applying a large amount of solder used for bonding the bonding wire W and the circuit board 2, A method is conceivable in which a resin is applied to the joining portion and hardened.
However, when a large amount of solder is applied or when resin is applied, the pad portion of the circuit board 2 needs to be enlarged. For this reason, it is difficult to reduce the size of the circuit board 2.
On the other hand, in the present embodiment, by providing the resin layer 11, the connection reliability between the semiconductor element 31 and the circuit board 2 can be increased, so that downsizing of the circuit board 2 is not hindered.

It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.
For example, in the above embodiment, the metal layer with the resin layer is laminated on the inner circuit board on which the circuit layer 212 is formed, but this is not restrictive.
For example, as shown in FIG. 5A, a prepreg (insulating layer 22) is disposed on the front and back surfaces of the insulating layer 211 where no circuit layer is formed, and the metal layer 1 with a resin layer is disposed outside the prepreg. Good. The resin layer 11 of the metal layer 1 with a resin layer is in contact with the insulating layer 22.
In this case, a prepreg is disposed on the front and back surfaces of the insulating layer 211 serving as the core material, a metal layer with a resin layer is laminated on the outer side, and the laminate is formed by pressurizing and heating in the same manner as in the above embodiment. .
Furthermore, as shown in FIG. 5B, the metal layer 1 with a resin layer may be provided directly on the insulating layer 211. The resin layer 11 of the metal layer 1 with a resin layer is in contact with the insulating layer 211. Also in this case, after the metal layer 1 with a resin layer is disposed on the front and back surfaces of the insulating layer 211, the laminate is formed by applying pressure and heating in the same manner as in the above embodiment.
In either case, the resin layer 11 is a C stage.
Through holes are formed in these laminates, and the metal layer 12 is etched so as to be a circuit layer, the inside of the through holes is filled, and the circuit layers are connected to form a circuit board. .

  Moreover, in the said embodiment, although the semiconductor element and the circuit board were connected with the bonding wire, it is not restricted to this. For example, the semiconductor element and the circuit board may be connected by solder bumps.

Next, examples of the present invention will be described.
Example 1
(Manufacture of metal layer with resin layer)
A metal layer with a resin layer having a resin layer having the composition shown in Table 1 was produced. In addition, the unit of the quantity of each material shown by Table 1 is a mass part.
Specifically, it is as follows.
First, 37 parts by mass of liquid epoxidized polybutadiene (manufactured by Daicel, trade name EPL-PB3600: compound represented by chemical formula (18)), naphthalene type epoxy resin (manufactured by DIC, trade name HP4710: chemical formula (6-3)) 22 parts by mass of the compound shown), 12 parts by mass of bisphenol A type epoxy resin (trade name Epicoat 828EL, manufactured by Mitsubishi Chemical Corporation), tetraphenol group ethane novolac type epoxy resin (CAS 30621-65-9, manufactured by Nanya Plastic Co., Ltd., product name) NPPN431) 0.6 parts by mass, phenol novolak resin (manufactured by Sumitomo Bakelite Co., Ltd., trade name PR51714) 28 parts by mass, 2-phenyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2P4MZ) 0.4 parts by mass in methyl ethyl ketone Dissolved (mixed with inorganic filler), solid content concentrated 60 mass% of the resin varnish was prepared. After applying the obtained resin varnish to a metal layer (trade name YGP-18, manufactured by Nippon Electrolytic Co., Ltd., thickness 18 μm), the resin varnish was dried at 100 ° C. for 2 minutes and 180 ° C. for 4 minutes to obtain a resin having a thickness of 30 μm. A layer was obtained. The resin layer was in a semi-cured state.
(Manufacture of circuit boards)
Next, an inner layer circuit board was prepared. As the inner layer circuit board (core layer 21), the following was used.
Insulating layer 211: halogen-free FR-4 equivalent material (manufactured by Sumitomo Bakelite), thickness 0.4 mm
Circuit layer 212: Copper foil thickness 18 μm, L / S = 120/180 μm, clearance holes 1 mmφ, 3 mmφ, slit 2 mm
A prepreg (EI-6765, manufactured by Sumitomo Bakelite Co., Ltd.) was superimposed on the front and back surfaces of the inner layer circuit board, and a metal layer with a resin layer was disposed so that the resin layer was in contact with each prepreg. Thereafter, vacuum hot press molding was performed for 60 seconds at a pressure of 0.5 MPa and a temperature of 100 ° C. using a vacuum pressurizing laminator apparatus. Further, it was cured by heating in a hot air dryer at a temperature of 190 ° C. for 2 hours. Thereafter, copper was plated by a general additive method to form a via 23 and a circuit layer 24. A solder resist SR (manufactured by Taiyo Ink, PSR4000 / AUS308) was formed on the surface of the circuit layer 24 to obtain a circuit board 2.

(Manufacture of semiconductor devices)
A semiconductor element 31 was mounted on the surface of the obtained circuit board 2, and the circuit layer 24 and the semiconductor element 31 were connected by a bonding wire W. An adhesive 32 was provided between the semiconductor element 31 and the circuit board 2. The wire W and the circuit layer 24 of the circuit board 2 were joined via lead-free solder.
Wire bonding was performed under the following conditions.
Wire bonder: Eagle 60 (manufactured by ASM)
Gold wire: SGS-H, 25 μm (manufactured by Sumitomo Metal Mining Co., Ltd.)
Wire bond temperature: 130 ° C
Bonding load: 45g
Ultrasonic power: 120 (128 kHz)

(Example 2)
(Manufacture of metal layer with resin layer)
A metal layer with a resin layer having a resin layer having the composition shown in Table 1 was produced.
Specifically, it is as follows.
First, 12 parts by mass of liquid epoxidized polybutadiene (manufactured by Daicel, trade name EPL-PB3600: compound represented by chemical formula (18)), naphthalene type epoxy resin (manufactured by DIC, trade name HP4710: chemical formula (6-3)) 35 parts by mass of the compound shown), 20 parts by mass of bisphenol A type epoxy resin (trade name Epicoat 828EL, manufactured by Mitsubishi Chemical Corporation), tetraphenol group ethane novolac type epoxy resin (CAS 30621-65-9, manufactured by Nanya Plastic Co., Ltd., product name) NPPN431) 0.6 parts by mass, phenol novolak resin (manufactured by Sumitomo Bakelite Co., Ltd., trade name PR51714) 32 parts by mass, 2-phenyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2P4MZ) 0.4 parts by mass in methyl ethyl ketone Dissolved (mixed with inorganic filler), solid content concentrated 60 mass% of the resin varnish was prepared. After applying the obtained resin varnish to a metal layer (trade name YGP-18, manufactured by Nippon Electrolytic Co., Ltd., thickness 18 μm), the resin varnish was dried at 100 ° C. for 2 minutes and 180 ° C. for 4 minutes to obtain a resin having a thickness of 30 μm. A layer was obtained. The resin layer was in a semi-cured state.
Subsequent steps are the same as those in the first embodiment.

(Example 3)
(Manufacture of metal layer with resin layer)
A metal layer with a resin layer having a resin layer having the composition shown in Table 1 was produced.
Specifically, it is as follows.
First, 33 parts by mass of liquid epoxidized polybutadiene (manufactured by Daicel, trade name EPL-PB3600: compound represented by chemical formula (18)), naphthalene type epoxy resin (manufactured by DIC, trade name HP4710: chemical formula (6-3)) 23 parts by mass of the compound shown), 12 parts by mass of bisphenol A type epoxy resin (trade name Epicoat 828EL, manufactured by Mitsubishi Chemical Corporation), tetraphenol group ethane novolac type epoxy resin (CAS 30621-65-9, manufactured by Nanya Plastic Co., Ltd., product name) NPPN431) 0.6 parts by mass, phenol novolac resin (manufactured by Sumitomo Bakelite Co., Ltd., trade name PR51714) 31 parts by mass, 2-phenyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2P4MZ) 0.4 parts by mass in methyl ethyl ketone Dissolved (mixed with inorganic filler), solid content concentrated 60 mass% of the resin varnish was prepared. After applying the obtained resin varnish to a metal layer (trade name YGP-18, manufactured by Nippon Electrolytic Co., Ltd., thickness 18 μm), the resin varnish was dried at 100 ° C. for 2 minutes and 180 ° C. for 4 minutes to obtain a resin having a thickness of 30 μm. A layer was obtained. The resin layer was in a semi-cured state.
Subsequent steps are the same as those in the first embodiment.

Example 4
(Manufacture of metal layer with resin layer)
A metal layer with a resin layer having a resin layer having the composition shown in Table 1 was produced.
Specifically, it is as follows.
First, liquid epoxidized polybutadiene (manufactured by Daicel, trade name EPL-PB3600: compound represented by chemical formula (18)) 16 parts by mass, naphthalene type epoxy resin (manufactured by DIC, trade name HP4710: chemical formula (6-3)) 33 parts by mass of the compound shown), 19 parts by mass of bisphenol A type epoxy resin (trade name Epicoat 828EL, manufactured by Mitsubishi Chemical Co., Ltd.), tetraphenol group ethane novolac type epoxy resin (CAS 30621-65-9, manufactured by Nanya Plastic Co., Ltd., product name) NPPN431) 0.6 parts by mass, phenol novolac resin (manufactured by Sumitomo Bakelite Co., Ltd., trade name PR51714) 31 parts by mass, 2-phenyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2P4MZ) 0.4 parts by mass in methyl ethyl ketone Dissolved (mixed with inorganic filler), solid content concentrated 60 mass% of the resin varnish was prepared. After applying the obtained resin varnish to a metal layer (trade name YGP-18, manufactured by Nippon Electrolytic Co., Ltd., thickness 18 μm), the resin varnish was dried at 100 ° C. for 2 minutes and 180 ° C. for 4 minutes to obtain a resin having a thickness of 30 μm. A layer was obtained. The resin layer was in a semi-cured state.
Subsequent steps are the same as those in the first embodiment.

(Example 5)
(Manufacture of metal layer with resin layer)
A metal layer with a resin layer having a resin layer having the composition shown in Table 1 was produced.
Specifically, it is as follows.
First, liquid epoxidized polybutadiene (manufactured by Daicel, trade name EPL-PB3600: compound represented by chemical formula (18)) 6 parts by mass, naphthalene type epoxy resin (manufactured by DIC, trade name HP4710: chemical formula (6-3)) 37 parts by mass of the compound shown), 22 parts by mass of a bisphenol A type epoxy resin (trade name Epicoat 828EL, manufactured by Mitsubishi Chemical Corporation), a tetraphenol group ethane novolac type epoxy resin (CAS 30621-65-9, manufactured by Nanya Plastic Co., Ltd., product name) NPPN431) 0.6 parts by mass, phenol novolac resin (manufactured by Sumitomo Bakelite Co., Ltd., trade name PR51714) 34 parts by mass, 2-phenyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2P4MZ) 0.4 parts by mass in methyl ethyl ketone Dissolved (inorganic filler mixed), solid content concentration 0% by weight of the resin varnish was prepared. After applying the obtained resin varnish to a metal layer (trade name YGP-18, manufactured by Nippon Electrolytic Co., Ltd., thickness 18 μm), the resin varnish was dried at 100 ° C. for 2 minutes and 180 ° C. for 4 minutes to obtain a resin having a thickness of 30 μm. A layer was obtained. The resin layer was in a semi-cured state.
Subsequent steps are the same as those in the first embodiment.

(Comparative Example 1)
(Manufacture of metal layer with resin layer)
A metal layer with a resin layer having a resin layer having the composition shown in Table 1 was produced.
Specifically, it is as follows.
First, liquid epoxidized polybutadiene (manufactured by Daicel, trade name EPL-PB3600: compound represented by chemical formula (18)) 46 parts by mass, cresol novolac type epoxy resin (DIC, trade name N690) 13 parts by mass, bisphenol A Type epoxy resin (Mitsubishi Chemical Corporation, trade name Epicoat 828EL) 8 parts by mass, tetraphenol group ethane novolac type epoxy resin (CAS 30621-65-9, Nanya Plastics Co., Ltd., product name NPPN431) 0.4 parts by mass, phenol novolac Resin (Sumitomo Bakelite Co., Ltd., trade name PR51714) 32 parts by mass, 2-phenyl-4-methylimidazole (Shikoku Kasei Kogyo Co., Ltd., 2P4MZ) 0.6 parts by mass dissolved in methyl ethyl ketone (inorganic filler mixed), Prepare a resin varnish with a solid content of 60% by mass It was. The obtained resin varnish was applied to a metal layer (trade name YGP-18, manufactured by Nippon Electrolytic Co., Ltd., thickness 18 μm), and then dried at 100 ° C. for 2 minutes and at 180 ° C. for 4 minutes to obtain a resin having a thickness of 30 μm. A layer was obtained. The resin layer was in a semi-cured state.
Subsequent steps are the same as those in the first embodiment.

(Comparative Example 2)
(Manufacture of metal layer with resin layer)
A metal layer with a resin layer having a resin layer having the composition shown in Table 1 was produced.
Specifically, it is as follows.
First, 10 parts by mass of liquid epoxidized polybutadiene (manufactured by Daicel, trade name EPL-PB3600: compound represented by chemical formula (18)), naphthalene type epoxy resin (manufactured by DIC, trade name HP4710: chemical formula (6-3)) 20 parts by mass of the compound shown), 11 parts by mass of bisphenol A type epoxy resin (trade name Epicoat 828EL, manufactured by Mitsubishi Chemical Corporation), tetraphenol group ethane novolac type epoxy resin (CAS 30621-65-9, manufactured by Nanya Plastics Co., Ltd., product name) NPPN431) 0.6 parts by mass, phenol novolak resin (manufactured by Sumitomo Bakelite Co., Ltd., trade name PR51714) 18 parts by mass, 2-phenyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2P4MZ) 0.3 parts by mass in methyl ethyl ketone Dissolve and add inorganic filler (silica Error (Admatechs Co., Ltd., trade name SO25R)) 40 parts by weight, the coupling agent were added 0.1 part by weight. Thereby, a resin varnish with a solid content concentration of 50% by mass was prepared. After applying the obtained resin varnish to a metal layer (trade name YGP-18, manufactured by Nippon Electrolytic Co., Ltd., thickness 18 μm), the resin varnish was dried at 100 ° C. for 2 minutes and 180 ° C. for 4 minutes to obtain a resin having a thickness of 30 μm. A layer was obtained. The resin layer was in a semi-cured state.
Subsequent steps are the same as those in the first embodiment.

(Comparative Example 3)
A metal layer with a resin layer having a resin layer having the composition shown in Table 1 was produced.
Specifically, it is as follows.
30 parts by mass of a hydroxyl group-containing polyamide resin (product name: KAYAFLEX BPAM01, manufactured by Nippon Kayaku Co., Ltd.), 40 parts by mass of a methoxynaphthalene aralkyl type epoxy resin (product name: HP-5000, manufactured by DIC), phenol novolac type cyanate resin (manufactured by Lonza Japan) , Primaset PT-30) 20 parts by mass, 2-phenyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2P4MZ) 0.3 part by mass is dissolved in methyl ethyl ketone, and further, inorganic filler (nanosilica filler, average particle diameter) 56 nm) 9.5 parts by mass and 0.2 parts by mass of a coupling agent were added. A resin varnish having a solid content concentration of 60% by mass was prepared. After applying the obtained resin varnish to a metal layer (trade name YGP-18, manufactured by Nippon Electrolytic Co., Ltd., thickness 18 μm), the resin varnish was dried at 100 ° C. for 2 minutes and 180 ° C. for 4 minutes to obtain a resin having a thickness of 30 μm. A layer was obtained. The resin layer was in a semi-cured state.
Subsequent steps are the same as those in the first embodiment.

(Measurement)
(Storage modulus)
The resin layer of the metal layer with a resin layer obtained in each example and comparative example was peeled from the metal layer, and the resin layer was cured at 190 ° C. for 2 hours. Thereafter, the resin layer was cut to obtain an 8 × 20 mm test piece. Using this test piece, the dynamic viscoelasticity measuring device was used to measure in a temperature range of −50 ° C. to 300 ° C. as a tensile mode, a frequency of 1 Hz, and a temperature rising rate of 5 ° C./min. And storage elastic modulus E'RT of 25 degreeC and storage elastic modulus _E'HT of 175 _degreeC were obtained.
(Glass transition point)
The resin layer of the metal layer with a resin layer obtained in each example and comparative example was peeled from the metal layer, and the resin layer was cured at 190 ° C. for 2 hours. Thereafter, the resin layer was cut to obtain a 5 × 20 mm test piece. The test piece was measured with TMA / 2940 manufactured by TA Instruments Inc. under a load of 3 g and a temperature range of −50 ° C. to 300 ° C. under a temperature increase rate of 10 ° C./min, and the glass transition point Tg was determined. Obtained.

(Evaluation)
For each example and each comparative example, 10 semiconductor devices were prepared and a heat cycle test was performed. The heat cycle test was performed 30000 times with one cycle of −40 ° C. 7 minutes to + 125 ° C. 7 minutes. The solder joint between the bonding wire after the heat cycle test and the circuit board was observed with a microscope, and the number of cracks generated was counted.
The results are shown in Table 1.
◎ indicates that 10 cracks did not occur in 10 semiconductor devices, ◯ indicates that 6 to 9 cracks did not occur in 10 semiconductor devices, and × indicates the semiconductor device 10 It shows that 0 to 5 cracks were not generated.
In Examples 1 to 5, the occurrence of cracks was suppressed, and the connection reliability between the semiconductor element and the circuit board in the semiconductor device was good. In particular, Examples 1-3, Example 5, 25 the difference between the storage modulus E _'RT and 175 ° C. The storage modulus E of' _HT of ° C. or less and a very small 1 GPa, a glass transition point 120 ° C. or higher As a result, good results were obtained.
On the other hand, in Comparative Example 1, the storage elastic modulus E ′ _{RT at} 25 ° C. and the storage elastic modulus E ′ _{HT at} 175 ° C. are small and the resin layer is very soft. It is thought that cracks occurred due to this.
In Comparative Examples 2 and 3, since the storage elastic modulus E _'RT and 175 ° C. The storage modulus E of' _HT of 25 ° C. was very large, not obtained stress relaxation effect by the resin layer, a crack occurs and Conceivable.

  This application claims the priority on the basis of Japanese application Japanese Patent Application No. 2012-266008 for which it applied on December 5, 2012, and takes in those the indications of all here.

Claims (8)

It is a metal layer with a resin layer for circuit boards used for circuit boards,
The resin layer is thermosetting;
The storage elastic modulus E ′ _RT at 25 ° C. of the resin layer after thermosetting the resin layer at 190 ° C. for 2 hours is 0.1 GPa or more and 1.5 GPa or less,
The resin layer 190 ° C., 2 hours at the storage modulus E _'HT of 175 ° C. of the resin layer after providing a thermoset or more 10 MPa, a resin layer with a metal layer is less than 0.7 GPa. In the metal layer with a resin layer according to claim 1,
Resin layer with the metal layer difference is less 1GPa of _HT 'the storage modulus E and _RT' the storage modulus E. In the metal layer with a resin layer according to claim 1 or 2,
The metal layer with a resin layer whose glass transition point of the said resin layer after thermosetting the said resin layer at 190 degreeC for 2 hours is 120 degreeC or more. In the metal layer with a resin layer according to any one of claims 1 to 3,
The resin layer is a metal layer with a resin layer including a thermosetting resin and an inorganic filler. In the metal layer with a resin layer according to any one of claims 1 to 4,
The metal layer with a resin layer whose thickness of the said resin layer is 30 micrometers or less. A metal layer with a resin layer obtained by curing the resin layer of the metal layer with a resin layer according to any one of claims 1 to 5,
A laminate for a circuit board including an insulating resin layer disposed on the resin layer side of the metal layer with a resin layer. A layer obtained by curing the resin layer of the metal layer with a resin layer according to any one of claims 1 to 5, and a circuit layer formed by selectively removing the metal layer of the metal layer with a resin layer; A circuit board comprising:
The circuit layer is a circuit board disposed in an outermost layer among circuit layers formed on the circuit board. A circuit board according to claim 7;
A semiconductor device comprising a semiconductor element provided on the circuit board,
A semiconductor device in which the semiconductor element and the circuit layer of the outermost layer of the circuit board are connected by a bonding wire.

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