TW201429346A - Metal layer with resin layer, laminate, circuit substrate, and semiconductor device - Google Patents

Abstract

The metal layer (1) with a resin layer for a circuit board of the present invention includes a resin layer (11) and a metal layer (12) provided on the resin layer (11). The resin layer (11) is thermosetting. The storage modulus E'RT at 25 ° C of the resin layer (11) which was thermally cured at 190 ° C for 2 hours was 0.1 GPa or more and 1.5 GPa or less. Further, the resin layer (11) was thermally cured at 190 ° C for 2 hours, and the storage modulus E'HT of the resin layer (11) at 175 ° C was 10 MPa or more and 0.7 GPa or less.

Description

Metal layer with resin layer, laminate, circuit substrate, and semiconductor device

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

Previously, a semiconductor device in which a semiconductor element was laminated on a circuit substrate was 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 by a wire.

Patent Document 1: Japanese Patent Laid-Open No. Hei 8-55867

In such a semiconductor device, it is required to withstand high connection reliability between various semiconductor elements and the circuit board.

In Patent Document 1, the connection reliability is improved by adjusting the glass transition point or the linear expansion coefficient of the circuit board.

On the other hand, the inventors of the present invention have proposed an invention for solving such a problem from a new viewpoint.

As a result of intensive studies, the inventors of the present invention have found that by providing a layer having a relatively low modulus of elasticity on the surface side of the circuit substrate, the average linear expansion coefficient of the semiconductor element and the average linear expansion coefficient of the circuit substrate can be alleviated. The stress caused by the difference. Thereby, the connection reliability between the semiconductor element and the circuit board can be improved.

The present invention has been made based on such findings.

That is, according to the present invention, there is provided a metal layer with a resin layer which is used for a metal layer of a resin layer for a circuit board of a circuit board, wherein the resin layer is thermosetting, and the resin layer is subjected to 190 ° C. The storage modulus E' _RT at 25 ° C of the resin layer after the hour heat curing is 0.1 GPa or more and 1.5 GPa or less, and the storage modulus of the resin layer after the resin layer is thermally cured at 190 ° C for 2 hours is 175 ° C. E' _HT is 10 MPa or more and 0.7 GPa or less.

The storage modulus E' _RT of 25 ° C of the resin layer which was thermally cured at 190 ° C for 2 hours was set to 1.5 GPa or less, and the storage modulus E' _{HT of} 175 ° C was set to 0.7 GPa or less, and at 25 ° C, 175 ° At °C, the storage modulus of the resin layer is reduced.

Therefore, when the metal layer of the resin layer is used for the circuit board and the semiconductor element is mounted, the connection reliability between the semiconductor element and the circuit board in various temperature environments can be improved.

Further, according to the present invention, it is possible to provide a laminated body using the metal layer with the above-mentioned resin layer, and further to provide a circuit board.

According to the present invention, there is provided a laminate for a circuit board, comprising: a metal layer with a resin layer obtained by curing the resin layer of the metal layer of the resin layer; and a resin layer disposed on the resin layer An insulating resin layer on the resin layer side of the metal layer.

Moreover, a circuit board including a layer obtained by curing the resin layer of the metal layer of the resin layer and a metal layer formed by selectively removing the metal layer of the resin layer may be provided. Layer, The circuit layer is disposed on the circuit layer of the circuit board and disposed on the outermost layer.

Further, a semiconductor device including the circuit board can be provided.

According to the present invention, there is provided a metal layer with a resin layer for a circuit board which can improve the connection reliability between a semiconductor element and a circuit board, a laminated body using the same, a circuit board, and a semiconductor device.

1‧‧‧Metal layer with resin layer

2‧‧‧ circuit board

3‧‧‧Semiconductor device

11‧‧‧ resin layer

12‧‧‧metal layer

21‧‧‧ core layer

22, 211‧‧‧ insulation

23, 213‧‧‧through holes

24, 212‧‧‧ circuit layer

31‧‧‧Semiconductor components

32‧‧‧Adhesive

241‧‧‧Electrical film

SR‧‧‧ solder mask

W‧‧‧ bonding wire

The above and other objects, features and advantages of the present invention will become more apparent from

1 is a cross-sectional view showing a metal layer of a resin layer for a circuit board according to an embodiment of the present invention, and is a cross-sectional view in the thickness direction of a metal layer with a resin layer for a circuit board.

2(A) and 2(B) are cross-sectional views showing the steps of manufacturing the circuit board, and are cross-sectional views in a direction orthogonal to the substrate surface.

Figure 3 is a cross-sectional view of a circuit substrate.

4 is a cross-sectional view showing a semiconductor device using a circuit board.

5(A) and 5(B) are cross-sectional views showing a laminate in which a metal layer with a resin layer is applied.

Hereinafter, embodiments of the present invention will be described based on the drawings. In the drawings, the same components are denoted by the same reference numerals, and the detailed description thereof will be omitted as appropriate.

First, a metal layer with a resin layer for a circuit board of the present embodiment will be described with reference to Fig. 1 .

The metal layer 1 with a resin layer for the circuit board is provided with a resin layer 11 and is provided on the resin layer. The metal layer 12 on the 11th.

The resin layer 11 is thermosetting. The storage modulus E' _RT of the resin layer 11 after the resin layer 11 was thermally cured at 190 ° C for 2 hours was 0.1 GPa or more and 1.5 GPa or less. Further, the storage layer E' _HT of the resin layer 11 at 175 ° C after the resin layer 11 was thermally cured at 190 ° C for 2 hours was 10 MPa or more and 0.7 GPa or less.

The metal layer 12 is a circuit layer in a circuit board, and is made of, for example, Cu or the like. The thickness of the metal layer 12 is, for example, 10 to 30 μm.

The resin layer 11 is B-stage (semi-hardened). Further, the thickness of the resin layer 11 is, for example, 5 μm or more and 30 μm or less, and preferably 10 μm or more and 20 μm or less. This resin layer 11 functions as a stress relaxation layer when forming a circuit board. By setting the thickness of the resin layer 11 to 5 μm or more, the stress relieving effect can be surely exhibited. On the other hand, by setting the thickness of the resin layer 11 to 30 μm or less, the thickness of the circuit board can be suppressed.

The resin layer 11 is obtained by semi-curing a resin composition containing a resin component (A) (a curing agent (B)) containing a thermosetting resin. The resin layer 11 may further contain a curing agent (B) and an inorganic filler (C) within a range not impairing the effects of the present invention.

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.

Further, examples of the thermosetting resin (A2) having an aromatic ring or an alicyclic structure include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol. E-type epoxy resin, bisphenol M type epoxy resin, bisphenol P type epoxy resin, bisphenol type epoxy resin and other bisphenol type epoxy resin, phenolic novolak type epoxy resin, cresol novolac Novolac type epoxy resin such as epoxy resin, tetraphenol ethane novolac type epoxy resin, biphenyl type epoxy resin, aryl aralkyl group such as phenol aralkyl type epoxy resin having a benzene skeleton Type epoxy resin, epoxy resin such as naphthalene type epoxy resin. One of these may be used alone or in combination of two on.

Among these, a glass transition point can be further increased, and a naphthalene type epoxy resin is preferable from the viewpoint of lowering the storage modulus E' _RT and the storage modulus E' _HT . Here, the naphthalene type epoxy resin refers to a group having a naphthalene ring skeleton and having two or more epoxy propyl groups.

As the naphthalene type epoxy resin, any of the following formulas (5) to (8) can be used. Further, 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. Further, in the formula (7), Me represents a methyl group, and l, m, and n are integers of 1 or more. Among them, it is preferable that l, m, and n be 10 or less.

m, n are integers from 1 to 7

l, m, n is a natural number of 1 or more

In addition, as the compound of the formula (6), it is preferred to use at least one of the following.

Further, as the naphthalene type epoxy resin, a naphthyl ether type epoxy resin represented by the following formula (8) can also be used.

(In the formula (8), n is an integer of 1 or more and 20 or less, and 1 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 a formula represented by the following formula (9) Structure, R _{2 is} independently a hydrogen atom or a methyl group)

(In the above formula (9), Ar is independently a phenyl or anthracene group, and R _{2 is} independently a hydrogen atom or a methyl group, and m is an integer of 1 or 2)

The naphthyl ether type epoxy resin represented by the above formula (8) is exemplified by the following formula (10).

(In the above formula (10), n is an integer of 1 or more and 20 or less, preferably an integer of 1 or more and 10 or less, more preferably an integer of 1 or more and 3 or less. R is independently a hydrogen atom or a formula (11) The structure represented by hydrogen atom is preferred)

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

The naphthyl ether type epoxy resin represented by the above formula (10) is exemplified by those represented by the following formulas (12) to (16).

Further, a cyanate resin can also be used as the thermosetting resin (A2). For example, a novolac type cyanate resin, a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, a tetramethyl bisphenol F type cyanate resin, etc. may be mentioned, among these, etc. Use any one or more of them. Among them, a novolac type cyanate resin is preferably used.

Further, the resin component (A) preferably contains a reactive group (for example, a glycidyl group) contained in the thermosetting resin (A2) and a compound (A1) having a reactive group reactive.

As such a compound (A1), an aliphatic epoxy resin having no aromatic ring structure and an alicyclic structure (alicyclic carbon ring structure) and a copolymer of acrylonitrile having a carboxyl group at the terminal and butadiene can be used. (CTBN, for example, represented by the following formula (17), 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 are molar ratios, x + y = 1), and z is 50 or more and 70 or less. For example, the product name CTBN1300X (manufactured by Ube Industries, Ltd.), an aromatic polyamine-poly(butadiene-acrylonitrile) block copolymer containing a phenolic hydroxyl group (for example, trade name KAYAFLEX BPAM-155) Any one or more of the group consisting of (manufactured by Nippon Kayaku Co., Ltd., having a terminal amine group). By appropriately selecting and using the compound (A1), the storage modulus E' _RT and E' _{HT of the} resin layer 11 can be lowered while maintaining the value of the glass transition point of the resin layer 11.

From the viewpoint of reducing the storage modulus E' _RT and E' _HT of the resin layer 11 to the above specific range, it is preferred that the aliphatic epoxy resin has no cyclic structure other than the epoxy propyl group. Aliphatic epoxy resin. Further, from the viewpoint of setting the storage modulus E' _RT and E' _{HT of the} resin layer 11 to the above specific range, it is preferably an aliphatic epoxy having two or more epoxy groups and two or more functional groups. Resin.

The aliphatic epoxy resin as described above is preferably represented by the chemical formulas (18) to (27), and preferably contains at least one or more, and particularly preferably includes those represented by the chemical formula (18). Since such an epoxy epoxy resin is not easily oxidized, it is less likely to cause an increase in the elastic modulus due to a heat history, and thus is excellent.

(In the formula (18), l, m, n, p, q, and r are integers of 0 or more, in which all of l, m, and n are removed. Further, all of p, q, and r are also removed. In the case, it is preferably l=1~5, m=5~20, n=0~8, p=0~8, q=3~12, r=0~4)

(In the formula (26), l, m, and n are integers of 0 or more, wherein all of l, m, and n are removed. The situation. Among them, it is preferably l=1~12, m=8~30, n=0~10)

(In the formula (27), n is an integer of 1 or more, and preferably 2 to 15)

Further, in terms of achieving a higher glass transition point of the resin layer 11 and lowering the storage modulus E' _RT , E' _HT of the resin layer 11, the content of the compound (A1) is relative to the resin constituting the resin layer 11. The total solid content of the composition is 100% by mass, preferably 3% by mass or more and 45% by mass or less, more preferably 5% by mass or more and 40% by mass or less, and the content of the thermosetting resin (A2) is relative to the constituent resin layer 11 The total solid content of the resin composition is 100% by mass, preferably 30% by mass or more and 65% by mass or less, more preferably 33% by mass or more and 60% by mass or less.

When the thermosetting resin (A2) and the compound (A1) are used in combination, the mass ratio expressed by the total of the compound (A1) / the thermosetting resin (A2) is preferably 0.1 or more and 1.5. Hereinafter, it is more preferably set to 0.1 or more and 1.1 or less.

In addition, the resin component (A) containing the thermosetting resin (A2) and the compound (A1) is preferably 100% by mass or more and 90% by mass based on 100% by mass of the total solid content of the resin composition constituting the resin layer 11. Hereinafter, it is preferably 60% by mass or more and 80% by mass or less.

Examples of the curing agent (B) (hardening catalyst) include zinc naphthenate, cobalt naphthenate, stannous octoate, cobalt octoate, cobalt (II) acetoacetate, and cobalt (III) triethyl sulfonium hydride. And other organic metal salts; tertiary amines such as triethylamine, tributylamine, diazabicyclo[2,2,2]octane; 2-phenyl-4-methylimidazole, 2-ethyl-4- Methylimidazole, 2-ethyl-4-ethylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl-4,5- Imidazoles such as dihydroxyimidazole; triphenylphosphine, tri-p-tolylphosphine, tetraphenylphosphonium-tetraphenylborate, triphenylphosphine-triphenylborane, 1,2-bis-(diphenyl Organophosphorus compounds such as phosphine; phenolic compounds such as phenol, bisphenol A, nonylphenol; acetic acid, benzoic acid, An organic acid such as salicylic acid or p-toluenesulfonic acid, or a mixture thereof. The curing catalyst may be used alone or in combination of the above-mentioned derivatives, or may be used in combination of two or more kinds thereof.

The content of the curing catalyst is not particularly limited, and is preferably 0.05% by mass or more and 5% by mass or less, and particularly preferably 0.2% by mass or more and 2% by mass based on 100% by mass of the total solid content of the resin composition constituting the resin layer 11. %the following.

Further, as the curing agent (B), a phenol-based curing agent may be used, and it may be used in combination with a curing catalyst. As the phenolic curing agent, a phenol novolak resin, an alkylphenol novolak resin, a bisphenol A novolak resin, a dicyclopentadiene type phenol resin, a neophenol resin (xylok resin) type phenol resin, and a terpene can be modified. A known pharmaceutically acceptable phenol resin or a polyvinyl phenol is used alone or in combination of two or more.

When the amount of the phenolic curing agent is contained in the resin component (A), if the equivalent ratio to the epoxy resin (phenolic hydroxyl equivalent/epoxy equivalent) is 0.1 to 1.0, good. Thereby, the residue of the unreacted phenol curing agent disappears, and the moisture absorption heat resistance is improved.

The content of the phenolic curing agent is not particularly limited, and is preferably 5% by mass or more and 45% by mass or less, and more preferably 10% by mass or more, based on 100% by mass of the total solid content of the resin composition constituting the resin layer 11. The mass% or less is further preferably 15% by mass or more and 35% by mass or less.

Examples of the inorganic filler (C) include oxides such as talc, calcined clay, uncalcined clay, mica, glass, etc., oxides such as titanium oxide, aluminum oxide, cerium oxide, and molten cerium oxide; calcium carbonate and carbonic acid; Carbonate such as magnesium or hydrotalcite; hydroxide such as aluminum hydroxide, magnesium hydroxide or calcium hydroxide; sulfate or sulfite such as barium sulfate, calcium sulfate or calcium sulfite; zinc borate and barium metaborate Boric acid such as aluminum borate, calcium borate or sodium borate; nitride such as aluminum nitride, boron nitride, tantalum nitride or carbon nitride; titanate such as barium titanate or barium titanate. One of these may be used alone or two or more of them may be used in combination.

Among these, aluminum hydroxide is preferred from the viewpoint of imparting excellent effects on flame retardancy.

Further, among these, it is particularly preferable that the cerium oxide and the molten cerium oxide (especially the spherical molten cerium oxide) are excellent in low thermal expansion property.

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 diameter of the inorganic filler (C) to 0.01 μm or more, the varnish can be made low in viscosity and workability can be improved. Further, by setting it to 5 μm or less, precipitation of the inorganic filler (C) in the varnish or the like can be suppressed. The average particle diameter can be measured, for example, by a particle size distribution meter (manufactured by Shimadzu Corporation, product name: laser diffraction type particle size distribution measuring apparatus SALD series).

Further, the inorganic filler (C) is not particularly limited, and an inorganic filler having an average particle diameter of monodisperse may be used, or an inorganic filler having an average particle diameter of polydisperse may be used. Further, one type of the inorganic filler having an average particle diameter of monodisperse and/or polydisperse may be used, or two or more kinds may be used in combination.

Further, spherical cerium oxide (especially spherical molten cerium oxide) or aluminum hydroxide having an average particle diameter of 5 μm or less is preferable, and spherical molten cerium oxide having an average particle diameter of 0.5 μm or more and 2 μm or less is particularly preferable. Aluminum hydroxide. Thereby, the filling property of the inorganic filler (C) can be improved. Further, the film thickness uniformity of the resin layer 11 can be improved.

When the total content of the resin layer is 100% by mass, 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, and particularly preferably 8% by mass. %the following. Thereby, the storage modulus E' _RT , E' _{HT of the} resin layer 11 can be lowered, and circuit workability can be improved.

In addition, the inorganic filler (C) is preferably 5 parts by mass or more and 60 parts by mass or less based on 100 parts by weight of the resin component (A). Among them, it is preferably 10 parts by mass or more and 50 parts by mass or less. When the amount is 5 parts by mass or more, the average linear expansion coefficient of the resin layer 11 can be lowered, and when it is 60 parts by mass or less, the resin layer 11 having low water absorbability can be produced.

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

The coupling agent (D) can be used as a general user. Specifically, it is preferably selected from the group consisting of an epoxy decane coupling agent, a cationic decane coupling agent, an amino decane coupling agent, and a titanate system. One or more coupling agents of the coupling agent and the polyoxygenated oil type coupling agent.

The amount of the coupling agent (D) to be added is not particularly limited as long as it depends on the specific surface area of the inorganic filler (C), and is preferably 0.05 parts by mass or more and 3 parts by mass or less based on 100 parts by mass of the filler (C). It is 0.1 part by mass or more and 2 parts by mass or less.

The resin layer 11 can be formed by adding the above composition to an organic solvent to form a varnish, and applying the varnish to the metal layer 12. The coating method is not particularly limited, and for example, a method of coating by a coater or a method of blowing by a sprayer can be employed. Thereafter, heating is performed to remove the solvent, and the resin layer 11 is semi-hardened.

In the metal layer 1 with such a resin layer, the storage modulus E' _RT of the resin layer 11 after the resin layer 11 is thermally cured at 190 ° C for 2 hours is 0.1 GPa or more and 1.5 GPa or less.

Among them, it is preferable that the storage modulus E' _RT is 0.3 GPa or more and 1.0 GPa or less.

Further, after the resin layer 11 was thermally cured at 190 ° C for 2 hours, the resin layer 11 was in the C stage.

Moreover, the storage modulus E' _HT of the resin layer 11 at 175 ° C after the resin layer 11 was thermally cured at 190 ° C for 2 hours was 10 MPa or more and 0.7 GPa or less. Among them, it is preferable that the storage modulus E' _HT is 100 MPa or more and 0.65 GPa or less.

In order to achieve such a storage modulus, the amount of the inorganic filler (C) or the amount of the compound (A1) and the thermosetting resin (A2) may be appropriately adjusted.

Further, the storage modulus is measured by a dynamic viscoelasticity measuring device.

The storage modulus E' _RT is a tensile load applied to the resin layer 11 which is hardened at 190 ° C for 2 hours, and is stored at 25 ° C at a frequency of 1 Hz, a temperature increase rate of 5 to 10 ° C / min, and a temperature of -50 ° C to 300 ° C. The value of the modulus.

The storage modulus E' _HT is a tensile load applied to the resin layer 11 which is hardened at 190 ° C for 2 hours, and is stored at 175 ° C at a frequency of 1 Hz, a temperature increase rate of 5 to 10 ° C / min, and a temperature of -50 ° C to 300 ° C. The value of the modulus.

Here, it is preferable that the difference between the storage modulus E' _RT and the storage modulus E' _HT (E' _RT >E' _HT , E' _{RT -} E' _HT ) is 1 GPa or less. Thus, by the storage modulus E 'and _RT storage modulus E' is set to the difference of _HT 1GPa or less, change in the number of storage can be suppressed due to temperature variation of the mold. Thereby, even if the environmental temperature changes rapidly, the resin layer 11 can stably alleviate the stress generated by the difference in linear expansion coefficient between the circuit board and the semiconductor element.

Further, the lower limit of the difference between the storage modulus E' _RT and the storage modulus E' _HT is not particularly limited, and is, for example, 0.05 GPa or more.

Further, the resin layer 11 preferably has a glass transition point Tg of 120 ° C or more after the resin layer 11 is thermally cured at 190 ° C for 2 hours, and preferably 130 ° C or more, further 140 ° C or more, and further Above 175 ° C. Further, the upper limit of the glass transition point Tg is not particularly limited, and Tg is 200 ° C or lower, and particularly preferably 190 ° C or lower. In the resin layer 11, since the glass transition point Tg is relatively high at 120 ° C or higher, the glass transition point is higher than that of the other insulating layers 22 and 211 (see FIG. 3) constituting the common circuit board.

Therefore, when the circuit board is subjected to a heat cycle test or the like, the resin layer 11 is not rubberized before the other insulating layers 22 and 211 (see FIG. 3) constituting the circuit board, and the physical properties of the resin layer 11 are maintained. Therefore, the stress generated between the circuit board and the semiconductor element can be further alleviated by the resin layer 11. Moreover, by setting the glass transition point to the above range, it is possible to further prevent the semiconductor element 31 from sinking to the circuit board 2 side when the semiconductor element 31 is mounted on the circuit board 2.

Further, after the resin layer 11 is thermally cured at 190 ° C for 2 hours, it is preferably an average linear expansion coefficient of the resin layer 11 in the in-plane direction of the resin layer 11 from 25 ° C to the glass transition point. It is 200 ppm/°C or less.

Next, a method of manufacturing a circuit board using the metal layer 1 with such a resin layer will be described with reference to Fig. 2 .

First, as shown in FIG. 2(A), an inner layer circuit substrate 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 hole 213 connecting the circuit layers 212.

The insulating layer 211 includes a fiber base material (not shown) and a resin layer impregnated into the fiber base material.

The fiber base material is not particularly limited, and examples thereof include a glass fiber base material such as a glass woven fabric or a glass nonwoven fabric, and a polyamide resin fiber, an aromatic polyamide resin fiber, a wholly aromatic polyamide resin fiber, or the like. Polyamide-based resin fiber, polyester resin fiber such as polyester resin fiber, aromatic polyester resin fiber, or wholly aromatic polyester resin fiber, polyimine resin fiber, or fluororesin fiber as a main component A synthetic fiber base material composed of a woven fabric or a non-woven fabric, or an organic fiber base material such as a paper base material containing kraft paper, cotton linter paper, or a mixed paper of cotton velvet and kraft pulp as a main component. Any of these may be used. Among these, a glass woven fabric is preferred. Thereby, the core layer 21 having low water absorption, high strength, and low thermal expansion property can be obtained.

Further, the resin layer is C-staged and contains a thermosetting resin.

The thermosetting resin is not particularly limited, and examples thereof include an epoxy resin, a melamine resin, a urea resin, and a cyanate resin. Further, one or more of these may be used. Among them, an epoxy resin or a cyanate resin is preferred.

Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol E epoxy resin, and bisphenol M epoxy resin. Bisphenol type epoxy resin such as bisphenol P type epoxy resin, bisphenol Z type epoxy resin, novolac type epoxy resin such as phenol novolak type epoxy resin or cresol novolak type epoxy resin, biphenyl Epoxy resin, aryl aralkyl type epoxy resin such as phenol aralkyl type epoxy resin having a benzene skeleton, naphthalene type Epoxy resin, bismuth epoxy resin, phenoxy epoxy resin, dicyclopentadiene epoxy resin, norbornene epoxy resin, adamantane epoxy resin, fluorene epoxy resin, etc. Oxygen resin, etc. One of these may be used alone or two or more of them may be used in combination.

The type of the cyanate resin is not particularly limited, and examples thereof include a novolak type cyanate resin, a bisphenol A type cyanate resin, a bisphenol E type cyanate resin, and a tetramethylbisphenol F type cyanate. A bisphenol type cyanate resin such as an acid ester resin. Among these, the novolac type cyanate resin is preferred from the viewpoint of low thermal expansion property. In addition, one type of the other cyanate resin may be used, or two or more types may be used in combination, and it is not particularly limited.

Further, the resin layer may also contain a filler. As the filler, the same as the above inorganic filler (C) can be used.

Next, as shown in Fig. 2(B), a metal layer 1 with a resin layer is laminated on the prepreg on the prepreg (insulating layer 22) of the layer B of one of the core layers 21. At this time, the metal layer 1 with the resin layer is laminated so that the prepreg and the resin layer 11 face each other.

The prepreg comprises a fibrous base material and a thermosetting resin layer impregnated with the fibrous base material. However, it is also possible to use a resin substrate without a fibrous base material.

As the fiber base material or the resin layer, the same as the core layer 21 can be used.

Further, the prepreg may also contain the same filling material as the core layer 21.

Next, on the other surface of the core layer 21, a prepreg (insulating layer 22) and a metal layer 1 with a resin layer are laminated in the same manner.

Thereafter, the laminate is pressurized in the lamination direction, and heated at 190 ° C for 2 hours, for example. Thereby, the laminated body in which the insulating layer 22 and the resin layer 11 become a C stage can be obtained.

Next, holes penetrating through the metal layer 12, the resin layer 11, and the insulating layer 22 are formed by laser or the like. A portion penetrating the resin layer 11 and the insulating layer 22 serves as a through hole.

Thereafter, a seed layer (not shown) is formed on the surface of the hole and the metal layer 12, and the seed layer is formed on the seed layer A mask is formed. The opening portion of one of the masks communicates with the above-mentioned hole, and the surface of the seed layer is exposed from the opening portion of the other portion.

Next, a conductive film is formed in the hole through the opening portion of one portion of the mask by plating, and a conductive film (for example, a Cu film) is formed in the opening portion of the other portion of the mask.

The conductive film in the via hole becomes the through hole 23 of FIG. Thereafter, the mask is removed, and the metal layer 12 and the seed layer which are covered by the mask are removed by etching, thereby forming the circuit layer 24 shown in FIG. The circuit layer 24 is composed of an etched metal layer 12 and a conductive film (for example, a Cu film) 241 provided on the metal layer 12. The conductive film 241 is connected to the through hole 23 and connected to the circuit layer 212 of the core layer 21.

Further, on the circuit board 2, a build-up layer is formed by using a cured body of the resin layer 11 and a cured body of the prepreg (insulating layer 22).

Thereafter, as shown in FIG. 3, a solder resist film SR is provided on the circuit layer 24. In the circuit board 2 of the present embodiment, the solder resist film SR is directly provided on the resin layer 11. Therefore, the circuit layer 24 formed by etching the metal layer 12 becomes the circuit layer of the outermost layer of the circuit substrate 2.

In the circuit substrate 2 formed in this manner, the average linear expansion coefficient of the insulating layer 211 of the core layer 21 from 25 ° C to the glass transition point is, for example, 10 to 50 ppm / ° C. Further, similarly, the average linear expansion coefficient of the insulating layer 22 from 25 ° C to the glass transition point is, for example, 10 to 50 ppm / ° C.

In the above manner, the circuit board 2 including the solder resist film SR, the layer obtained by hardening the resin layer 11, and the circuit layer 24, the insulating layer 22, and the core layer obtained by selectively removing the metal layer 12 can be obtained. twenty one.

Next, a 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 to the solder resist film SR of the circuit board 2 via the adhesive 32. Further, the semiconductor element 31 is connected to the circuit board 2 by a bonding wire W.

The bonding wire W is connected to the semiconductor element 31 and soldered to a portion (pad) of the circuit layer 24 of the circuit substrate 2.

The semiconductor device 3 is, for example, an electronic control unit or a power conversion inverter unit that is mounted on a vehicle such as a hybrid electric vehicle, a fuel cell vehicle, or an electric vehicle, and is mounted on a processor unit of a mobile terminal such as a smart phone.

When the resin layer 11 is placed in an environment where temperature changes are severe for a long period of time, the stress generated by the difference in linear expansion coefficient between the circuit board 2 and the semiconductor element 31 can be stably alleviated, so that it is used in an engine room for automobiles. It is especially effective when using a semiconductor device.

The connection reliability between the semiconductor element 31 of the semiconductor device 3 and the circuit board 2 is high.

This is because the resin layer 11 is provided on the circuit board 2.

As described above, the storage modulus E' _RT at 25 ° C of the resin layer 11 after heat curing at 190 ° C for 2 hours is 1.5 GPa or less, and the storage modulus E' _HT at 175 ° C is 0.7 GPa or less at 25 ° C. At 175 ° C, the storage modulus of the resin layer was lowered.

Thereby, the stress generated by the difference in linear expansion coefficient between the semiconductor element 31 and the circuit board 2 can be alleviated by the resin layer 11 by temperature change.

The circuit board 2 has a larger average linear expansion coefficient than the semiconductor element 31, and a large expansion and contraction occurs due to 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 or the connection portion of the bonding wire W and the pad portion of the circuit layer 24. However, since the resin layer 11 has a low storage modulus, the resin layer 11 is deformed to absorb the load applied to the bonding wire W or the connection portion of the bonding wire W and the circuit layer 24.

Therefore, for example, as the insulating layers 22 and 211 constituting the circuit board 2, even if a linear expansion coefficient is relatively high, for example, an insulating layer having an average linear expansion coefficient of 25 ppm/° C. or higher from 25 ° C to a glass transition point is also used. The connection reliability between the circuit board 2 and the semiconductor element 31 can be improved.

In addition, by setting the storage modulus E' _RT to 0.1 GPa or more and the storage modulus E' _HT to 10 MPa or more, physical polishing resistance (brushing, erasing, and the like) at the time of manufacturing the circuit board 2 can be ensured. Polished for damage resistance). That is, the polishing of the manufacturing process of the circuit board 2 can prevent the resin layer from being removed.

Further, by setting the storage modulus E' _RT to 0.1 GPa or more and the storage modulus E' _HT to 10 MPa or more, the resin layer 11 can be prevented from being soft, and the position of the semiconductor element 31 relative to the circuit substrate 2 can be prevented. Offset. Thereby, the connection reliability of the semiconductor element 31 and the circuit board 2 can be improved.

Further, by the storage modulus E _'RT is set to 0.1GPa or more, the storage modulus E' _HT is set to more than 10MPa, also in the semiconductor element 31 is mounted on the circuit board 2, to prevent the semiconductor element 31 sunk Circuit board 2 side

Further, in the present embodiment, in the circuit board 2, the resin layer 11 is disposed directly under the circuit layer 24 to which the outermost layer of the bonding wires W is connected, so that the stress relaxation effect of the resin layer 11 can be effectively exhibited.

In order to improve the connection reliability between the semiconductor element 31 and the circuit board 2, a method of applying a large amount of solder for bonding the bonding wire W to the circuit substrate 2 or a bonding portion of the bonding wire W and the circuit substrate 2 may be considered. A method of strengthening the cloth resin.

However, in the case where a large amount of solder is applied or a case where a resin is applied, the pad portion of the circuit substrate 2 must be enlarged. Therefore, it becomes difficult to achieve miniaturization 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 improved, and the circuit board 2 can be prevented from being downsized.

Further, the present invention is not limited to the above-described embodiments, and modifications, improvements, etc. within a scope that can achieve the object of the invention are included in the present invention.

For example, in the above-described embodiment, the metal layer of the resin layer is laminated on the inner layer circuit substrate on which the circuit layer 212 is formed, but the invention is not limited thereto.

For example, as shown in FIG. 5(A), on the front side of the insulating layer 211 where the circuit layer is not formed, A prepreg (insulating layer 22) is disposed on the back surface, and a metal layer 1 with a resin layer is disposed on the outer side. The resin layer 11 of the metal layer 1 with the resin layer is in contact with the insulating layer 22.

In this case, a prepreg is placed on the front surface and the back surface of the insulating layer 211 which is a core material, and a metal layer with a resin layer is laminated on the outer side thereof, and pressurized and heated in the same manner as in the above embodiment to form a laminate. .

Further, as shown in FIG. 5(B), 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 the resin layer is in contact with the insulating layer 211. In this case, after the metal layer 1 with the resin layer is placed on the front surface and the back surface of the insulating layer 211, pressure heating is performed in the same manner as in the above embodiment to form a laminated board.

In either case, the resin layer 11 is in the C stage.

Through holes are formed in the laminated plates, and the metal layer 12 is etched in a circuit layer to fill the inside of the via holes, and the circuit layers are connected to each other, thereby forming a circuit substrate.

Further, in the above embodiment, the semiconductor element and the circuit board are connected by a bonding wire, but the invention is not limited thereto. For example, the semiconductor element and the circuit substrate may be connected by solder bumps.

Example

Next, an embodiment of the present invention will be described.

(Example 1)

(Manufacture of metal layer with resin layer)

A metal layer of a resin-attached layer having a resin layer of the composition shown in Table 1 was produced. In addition, the unit of the quantity of each material shown in Table 1 is a mass part.

The details are as follows.

First, liquid epoxidized polybutadiene (manufactured by Daicel Co., Ltd., trade name: EPL-PB3600: compound represented by chemical formula (18)), 37 parts by mass, naphthalene type epoxy resin (manufactured by DIC Corporation, trade name HP4710: chemical formula) (6-3) compound) 22 parts by mass, bisphenol A type epoxy Resin (manufactured by Mitsubishi Chemical Corporation, trade name Epikote 828EL) 12 parts by mass, tetraphenol ethane novolac type epoxy resin (CAS30621-65-9, manufactured by Nanya Plastics Co., Ltd., product name NPPN431) 0.6 parts by mass, phenolic novolac 28 parts by mass of resin (manufactured by SUMITOMO BAKELITE Co., Ltd., trade name PR51714), and 2-phenyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd., 2P4MZ) 0.4 parts by mass dissolved in methyl ethyl ketone (inorganic filler material is By mixing), a resin varnish having a solid content concentration of 60% by mass was prepared. The obtained resin varnish was applied to a metal layer (manufactured by Nippon Seki Co., Ltd., trade name: YGP-18, thickness: 18 μm), and then dried at 100 ° C for 2 minutes and at 180 ° C for 4 minutes to obtain a resin layer having a thickness of 30 μm. The resin layer is in a semi-hardened state.

(Manufacture of circuit board)

Next, an inner layer circuit substrate is prepared. As the inner layer circuit board (core layer 21), the following ones are used.

‧Insulation layer 211: Halogen-free FR-4 equivalent material (manufactured by SUMITOMO BAKELITE), thickness 0.4mm

‧Circuit layer 212: copper foil thickness 18μm, L/S=120/180μm, clearance hole 1mm , 3mm , slit 2mm

A prepreg (EI-6765, manufactured by SUMITOMO BAKELITE Co., Ltd.) was placed on the front and back surfaces of the inner layer circuit board, and a metal layer with a resin layer was placed in contact with each prepreg with a resin layer. Thereafter, vacuum heat press molding was carried out for 60 seconds at a pressure of 0.5 MPa and a temperature of 100 ° C using a vacuum press type laminator apparatus. Further, heat curing was performed by a hot air dryer at a temperature of 190 ° C for 2 hours. Thereafter, copper plating is performed by a general additive method to form via holes 23 and circuit layers 24. A solder resist film SR (manufactured by Taiyo Ink Co., Ltd., PSR4000/AUS308) was formed on the surface of the circuit layer 24, whereby the circuit substrate 2 was obtained.

(Manufacture of semiconductor device)

The semiconductor element 31 is mounted on the surface of the obtained circuit board 2, and the circuit layer 24 and the semiconductor element 31 are connected by a bonding wire W. Providing a connection between the semiconductor element 31 and the circuit substrate 2 Agent 32. The wire W and the circuit layer 24 of the circuit board 2 are joined via lead-free solder.

Wire bonding is performed under the following conditions.

Wire bonding machine: Eagle60 (made by ASM)

Gold line: SGS-H, 25μm (manufactured by Sumitomo Metal Mining Co., Ltd.)

Wire bonding temperature: 130 ° C

Bonding load: 45g

Ultrasonic power: 120 (128kHz)

(Example 2)

(Manufacture of metal layer with resin layer)

A metal layer of a resin-attached layer having a resin layer of the composition shown in Table 1 was produced.

The details are as follows.

First, liquid epoxidized polybutadiene (manufactured by Daicel Co., Ltd., trade name: EPL-PB3600: compound represented by chemical formula (18)), 12 parts by mass, naphthalene type epoxy resin (manufactured by DIC Corporation, trade name HP4710: chemical formula) (6-3) compound) 35 parts by mass, bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name Epikote 828EL) 20 parts by mass, tetraphenol ethane novolac type epoxy resin (CAS30621- 65-9, manufactured by Nanya Plastics Co., Ltd., product name: NPPN431) 0.6 parts by mass, phenolic novolac resin (manufactured by SUMITOMO BAKELITE Co., Ltd., trade name PR51714) 32 parts by mass, 2-phenyl-4-methylimidazole (Shikoku Chemical Industry Co., Ltd.) The company manufactured, 2P4MZ) 0.4 parts by mass dissolved in methyl ethyl ketone (inorganic filler was mixed) to prepare a resin varnish having a solid content concentration of 60% by mass. The obtained resin varnish was applied to a metal layer (manufactured by Nippon Seki Co., Ltd., trade name: YGP-18, thickness: 18 μm), and then dried at 100 ° C for 2 minutes and at 180 ° C for 4 minutes to obtain a resin layer having a thickness of 30 μm. The resin layer is in a semi-hardened state.

The subsequent steps are the same as in the first embodiment.

(Example 3)

(Manufacture of metal layer with resin layer)

A metal layer of a resin-attached layer having a resin layer of the composition shown in Table 1 was produced.

The details are as follows.

First, liquid epoxidized polybutadiene (manufactured by Daicel Co., Ltd., trade name: EPL-PB3600: compound represented by chemical formula (18)) 33 parts by mass, naphthalene type epoxy resin (manufactured by DIC Corporation, trade name HP4710: chemical formula) (6-3) compound) 23 parts by mass, bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name Epikote 828EL) 12 parts by mass, tetraphenol ethane novolac type epoxy resin (CAS30621- 65-9, manufactured by Nanya Plastics Co., Ltd., product name: NPPN431) 0.6 parts by mass, phenolic novolac resin (manufactured by SUMITOMO BAKELITE Co., Ltd., trade name PR51714) 31 parts by mass, 2-phenyl-4-methylimidazole (Four countries chemical industry) The company manufactured, 2P4MZ) 0.4 parts by mass dissolved in methyl ethyl ketone (inorganic filler was mixed) to prepare a resin varnish having a solid content concentration of 60% by mass. The obtained resin varnish was applied to a metal layer (manufactured by Nippon Seki Co., Ltd., trade name: YGP-18, thickness: 18 μm), and then dried at 100 ° C for 2 minutes and at 180 ° C for 4 minutes to obtain a resin layer having a thickness of 30 μm. The resin layer is in a semi-hardened state.

The subsequent steps are the same as in the first embodiment.

(Example 4)

(Manufacture of metal layer with resin layer)

A metal layer of a resin-attached layer having a resin layer of the composition shown in Table 1 was produced.

The details are as follows.

First, liquid epoxidized polybutadiene (manufactured by Daicel Co., Ltd., trade name: EPL-PB3600: compound represented by chemical formula (18)), 16 parts by mass, naphthalene type epoxy resin (manufactured by DIC Corporation, trade name HP4710: chemical formula) (6-3) compound 33 parts by mass, bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name Epikote 828EL) 19 parts by mass, tetraphenol ethane novolac type epoxy resin (CAS30621- 65-9, Nanya Plastics Co., Ltd., NPPN431), 0.6 parts by mass, phenolic novolak resin (manufactured by SUMITOMO BAKELITE Co., Ltd., trade name PR51714) 31 parts by mass, 2-phenyl-4-methylimidazole (Four countries chemical industry) Made by the company, 2P4MZ) 0.4 parts by mass was dissolved in methyl ethyl ketone (the inorganic filler was mixed) to prepare a resin varnish having a solid content concentration of 60% by mass. The obtained resin varnish was applied to a metal layer (manufactured by Nippon Seki Co., Ltd., trade name: YGP-18, thickness: 18 μm), and then dried at 100 ° C for 2 minutes and at 180 ° C for 4 minutes to obtain a resin layer having a thickness of 30 μm. The resin layer is in a semi-hardened state.

The subsequent steps are the same as in the first embodiment.

(Example 5)

(Manufacture of metal layer with resin layer)

A metal layer of a resin-attached layer having a resin layer of the composition shown in Table 1 was produced.

The details are as follows.

First, liquid epoxidized polybutadiene (manufactured by Daicel Co., Ltd., trade name: EPL-PB3600: compound represented by chemical formula (18)), 6 parts by mass, naphthalene type epoxy resin (manufactured by DIC Corporation, trade name HP4710: chemical formula) (6-3) Compounds: 37 parts by mass, bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name Epikote 828EL) 22 parts by mass, tetraphenol ethane novolac type epoxy resin (CAS30621- 65-9, Nanya Plastics Co., Ltd., NPPN431) 0.6 parts by mass, phenolic novolak resin (manufactured by SUMITOMO BAKELITE Co., Ltd., trade name PR51714) 34 parts by mass, 2-phenyl-4-methylimidazole The company manufactured, 2P4MZ) 0.4 parts by mass dissolved in methyl ethyl ketone (inorganic filler was mixed) to prepare a resin varnish having a solid content concentration of 60% by mass. The obtained resin varnish was applied to a metal layer (manufactured by Nippon Seki Co., Ltd., trade name: YGP-18, thickness: 18 μm), and then dried at 100 ° C for 2 minutes and at 180 ° C for 4 minutes to obtain a resin layer having a thickness of 30 μm. The resin layer is in a semi-hardened state.

The subsequent steps are the same as in the first embodiment.

(Comparative Example 1)

(Manufacture of metal layer with resin layer)

A metal layer of a resin-attached layer having a resin layer of the composition shown in Table 1 was produced.

The details are as follows.

First, liquid epoxidized polybutadiene (manufactured by Daicel Co., Ltd., trade name: EPL-PB3600: compound represented by chemical formula (18)), 46 parts by mass, cresol novolac type epoxy resin (manufactured by DIC Corporation, trade name) N690) 13 parts by mass, bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name Epikote 828EL) 8 parts by mass, tetraphenol ethane novolac type epoxy resin (CAS30621-65-9, manufactured by Nanya Plastics Co., Ltd.) , the product name: NPPN 431), 0.4 parts by mass, phenolic novolak resin (manufactured by SUMITOMO BAKELITE Co., Ltd., trade name PR51714) 32 parts by mass, 2-phenyl-4-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd., 2P4MZ) 0.6 parts by mass It was dissolved in methyl ethyl ketone (inorganic filler was mixed) to prepare a resin varnish having a solid content concentration of 60% by mass. The obtained resin varnish was applied to a metal layer (manufactured by Nippon Seki Co., Ltd., trade name: YGP-18, thickness: 18 μm), and then dried at 100 ° C for 2 minutes and at 180 ° C for 4 minutes to obtain a resin layer having a thickness of 30 μm. The resin layer is in a semi-hardened state.

The subsequent steps are the same as in the first embodiment.

(Comparative Example 2)

(Manufacture of metal layer with resin layer)

A metal layer of a resin-attached layer having a resin layer of the composition shown in Table 1 was produced.

The details are as follows.

First, liquid epoxidized polybutadiene (manufactured by Daicel Co., Ltd., trade name: EPL-PB3600: compound represented by chemical formula (18)), 10 parts by mass, naphthalene type epoxy resin (manufactured by DIC Corporation, trade name HP4710: chemical formula) (6-3) compound) 20 parts by mass, bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name Epikote 828EL) 11 parts by mass, tetraphenol ethane novolac type epoxy resin (CAS30621- 65-9, manufactured by Nanya Plastics Co., Ltd., NPPN431) 0.6 parts by mass, phenolic novolak resin (manufactured by SUMITOMO BAKELITE Co., Ltd., trade name PR51714), 18 parts by mass, 2-phenyl-4-methylimidazole (Four countries chemical industry) 0.3 parts by mass of 2P4MZ) was dissolved in methyl ethyl ketone, and further, 40 parts by mass of an inorganic filler (manufactured by Admatechs Co., Ltd., trade name: SO25R) and 0.1 parts by mass of a coupling agent were added. borrow Thus, a resin varnish having a solid content concentration of 50% by mass was prepared. The obtained resin varnish was applied to a metal layer (manufactured by Nippon Seki Co., Ltd., trade name: YGP-18, thickness: 18 μm), and then dried at 100 ° C for 2 minutes and at 180 ° C for 4 minutes to obtain a resin layer having a thickness of 30 μm. The resin layer is in a semi-hardened state.

The subsequent steps are the same as in the first embodiment.

(Comparative Example 3)

A metal layer of a resin-attached layer having a resin layer of the composition shown in Table 1 was produced.

The details are as follows.

30 parts by mass of a hydroxyl group-containing polyamine resin (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAFLEX BPAM01), and 40 parts by mass of a methoxynaphthalene-based epoxy resin (manufactured by DIC Corporation, trade name: HP-5000) 20 parts by mass of phenolic novolac type cyanate resin (Primaset PT-30, manufactured by Lonza Japan Co., Ltd.), 2-phenyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., 2P4MZ) 0.3 parts by mass dissolved in A Further, the ethyl ketone was further added with an inorganic filler (nano-cerium oxide filler, average particle diameter: 56 nm) of 9.5 parts by mass and a coupling agent of 0.2 parts by mass. A resin varnish having a solid content concentration of 60% by mass was prepared. The obtained resin varnish was applied to a metal layer (manufactured by Nippon Seki Co., Ltd., trade name: YGP-18, thickness: 18 μm), and then dried at 100 ° C for 2 minutes and at 180 ° C for 4 minutes to obtain a resin layer having a thickness of 30 μm. The resin layer is in a semi-hardened state.

The subsequent steps are the same as in the first embodiment.

(measurement)

(storage modulus)

The resin layer of the metal layer of the resin-attached layer obtained in each of the examples and the comparative examples was peeled off 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 test piece of 8 × 20 mm. Using this test piece, the measurement was carried out by a dynamic viscoelasticity measuring apparatus in a tensile mode, a frequency of 1 Hz, a temperature increase rate of 5 ° C/min, and a temperature range of -50 ° C to 300 ° C. Further, a storage modulus E' _{RT of} 25 ° C and a storage modulus E' _{HT of} 175 ° C were obtained.

(glass transfer point)

The resin layer of the metal layer of the resin-attached layer obtained in each of the examples and the comparative examples was peeled off 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 test piece of 5 × 20 mm. The test piece was measured using a TMA/2940 manufactured by TA Instruments under the conditions of a load of 3 g and a temperature of -50 ° C to 300 ° C at a temperature increase rate of 10 ° C / min to obtain a glass transition point Tg.

(Evaluation)

For each of the examples and the comparative examples, ten semiconductor devices were prepared and subjected to a heat cycle test. The heat cycle test was carried out for 30,000 times at -40 ° C, 7 minutes to +125 ° C, and 7 minutes as one cycle. The solder joint portion between the bonding wire and the circuit board after the heat cycle test was observed with a microscope, and the crack was generated.

The results are shown in Table 1.

◎ indicates that 10 of the semiconductor devices are not cracked, and ○ indicates that among the 10 semiconductor devices, 6 to 9 are not cracked, and × indicates that 10 to 5 of the semiconductor devices are not cracked.

In Examples 1 to 5, the occurrence of cracks was suppressed, and the connection reliability between the semiconductor element of the semiconductor device and the circuit board was good. In particular, in Examples 1 to 3 and Example 5, the difference between the storage modulus E' _{RT at} 25 ° C and the storage modulus E' _HT at 175 ° C is 1 GPa or less, which is very small, and the glass transition point is also 120 ° C or more. Therefore, good results are obtained.

On the other hand, in Comparative Example 1, it is considered that the storage modulus E' _{RT at} 25 ° C and the storage modulus E' _{HT at} 175 ° C are small, and the resin layer is very soft, so that the semiconductor element is liable to occur in the thermal cycle test. The position of the circuit board is shifted, and cracks are generated.

Further, in Comparative Examples 2 and 3, it is considered that the storage modulus E' _{RT at} 25 ° C and the storage modulus E' _{HT at} 175 ° C are extremely large, so that the stress relaxation effect due to the resin layer cannot be obtained, and cracking occurs. .

The present application claims priority on the basis of Japanese Patent Application No. 2012-266008, filed on Dec.

1‧‧‧Metal layer with resin layer

11‧‧‧ resin layer

12‧‧‧metal layer

Claims (8)

A metal layer with a resin layer applied to a metal layer of a resin layer for a circuit board of a circuit board, wherein the resin layer is thermosetting, and the resin layer is thermally cured at 190 ° C for 2 hours. The storage modulus E' _RT of the layer at 25 ° C is 0.1 GPa or more and 1.5 GPa or less, and the storage modulus E' _HT of the resin layer at 175 ° C after the resin layer is thermally cured at 190 ° C for 2 hours is 10 MPa or more and 0.7. GPa below. The metal layer of the resin layer of claim 1, wherein the difference between the storage modulus E' _RT and the storage modulus E' _HT is 1 GPa or less. The metal layer of the resin layer of claim 1 or 2, wherein the resin layer has a glass transition point of 120 ° C or more after heat curing at 190 ° C for 2 hours. The metal layer of the resin layer of claim 1, wherein the resin layer comprises a thermosetting resin and an inorganic filler. A metal layer with a resin layer as in the first aspect of the patent application, wherein the resin layer has a thickness of 30 μm or less. A laminate for a circuit board, comprising: a metal layer with a resin layer obtained by curing the resin layer of the metal layer of the resin layer of any one of claims 1 to 5; An insulating resin layer on the resin layer side of the metal layer of the resin layer. A circuit board comprising a layer obtained by curing the resin layer of a metal layer of a resin layer according to any one of claims 1 to 5, and a metal layer selectively removing the resin layer. The circuit layer formed by the metal layer is disposed on the circuit layer formed on the circuit board and disposed on the outermost layer. A semiconductor device comprising the circuit substrate of claim 7 and The semiconductor element provided on the circuit board, and the circuit layer of the semiconductor element and the outermost layer of the circuit board are connected by a bonding wire.