WO2020017524A1 - Copper foil processing method, copper foil, laminate, copper-clad laminated plate, printed wiring board, and module corresponding to high-speed communication - Google Patents

Abstract

Provided is a copper foil processing method by which, regardless of the type of resin composition or the type of resin of a resin layer to be laminated on a conductive layer, peeling off of the resin layer is unlikely to occur even after a reflow step. Further provided are a copper foil obtained by performing the copper foil processing method, and a laminate using the copper foil, a copper-clad laminated plate, a printed wiring board, and a module suitable for high-speed communication. Specifically, provided is a copper foil processing method including: a step (1) for forming a tin layer or a tin alloy layer on the surface of a copper foil; a step (2) for converting, to a tin oxide, tin present on the surface of the tin layer or the tin alloy layer; and a step (3) for performing a coupling process on the tin oxide.

Description

Copper foil processing method, copper foil, laminate, copper-clad laminate, printed wiring board, and high-speed communication compatible module

The present invention relates to a method for treating a copper foil, a copper foil, a laminate, a copper-clad laminate, a printed wiring board, and a module for high-speed communication.

With the trend of miniaturization and high performance of electronic devices in recent years, higher wiring density and higher integration have been developed in printed wiring boards, and with this, laminated boards for printed wiring boards have There is an increasing demand for improved reliability by improving heat resistance. In addition, with the remarkable improvement in information communication volume and communication speed in network infrastructure devices and large-sized computers, semiconductor packages mounted on these electronic devices need to be compatible with high frequencies, and substrates with low transmission loss are required. I have.

In order to reduce the transmission loss, it is effective that the surface of the conductive layer has few irregularities, that is, the surface roughness of the conductive layer is small. However, if the surface roughness of the conductive layer is small, the resin laminated thereon may be used. However, there is a problem that the adhesion between the transmission loss is insufficient and the low transmission loss and the adhesion are in a trade-off relationship.
In order to solve this problem, in recent years, a "flat bond process" has been used in which the surface roughness of the conductive layer is kept small and the adhesion to the resin laminated thereon is sufficient (Patent Reference 1). In the flat bond treatment, a tin layer or a tin alloy layer having high adhesion to the conductive layer is formed on the conductive layer, and a coupling agent layer is formed by performing a coupling treatment to roughen the surface of the conductive layer. This is a process that can increase the adhesion to the resin layer without changing the state.

JP 2016-072306 A

However, when the present inventors further studied, after performing a flat bond treatment on the conductive layer, a resin layer is formed thereon, and then, in the laminate produced by press molding, cream It has been found that the resin layer may peel off after a “reflow process” in which the solder is melted and the mounted components are soldered. Further study revealed that the problem would occur with a high probability when using a specific resin or resin composition.However, heat resistance, low coefficient of thermal expansion, and low dielectric constant required printed wiring boards. In fact, it may be necessary to select such a resin depending on the properties to be obtained.

Therefore, an object of the present invention is to provide a method for treating a copper foil, which makes it difficult for the resin layer to peel off even after passing through a reflow step, regardless of the type of the resin or the resin composition of the resin layer laminated on the conductive layer. Is to provide. Further, an object of the present invention is to provide a copper foil obtained by performing the copper foil processing method, and to provide a laminate using the copper foil, a copper-clad laminate, a printed wiring board, and a high-speed communication compatible module. To provide.

The present inventors have conducted intensive studies in order to achieve the above object, and as a result, after forming a tin layer or a tin alloy layer in a flat bond process, and before performing a coupling process, the tin layer Alternatively, the present inventors have found that the problem can be solved by converting tin present on the surface of the tin alloy layer to tin oxide, and have completed the present invention.

That is, the present invention relates to the following [1] to [14].
[1] Step (1) of forming a tin layer or a tin alloy layer on the surface of a copper foil,
Converting tin existing on the surface of the tin layer or tin alloy layer into tin oxide (2),
A step (3) of performing a coupling treatment on the tin oxide;
A method for treating a copper foil.
[2] The method for treating a copper foil according to [1], wherein the tin alloy layer is an alloy layer containing tin and nickel.
[3] The method for treating a copper foil according to the above [1] or [2], wherein in the step (2), the tin is converted into tin oxide by heat treatment or air oxidation.
[4] The method for treating a copper foil according to the above [3], wherein the temperature of the heat treatment is 35 to 200 ° C.
[5] The method for treating a copper foil according to any one of the above [1] to [4], wherein in the step (1), the copper foil is formed with a circuit.
[6] The above [1] to [1], wherein the surface roughness (Rz) of the surface of the copper foil on the tin layer or tin alloy layer side after the step (1) is 0.2 to 2.0 μm. The method for treating a copper foil according to any one of [5].
[7] A copper foil obtained by subjecting the copper foil to the method for treating a copper foil according to any one of the above [1] to [6].
[8] A tin layer or a tin alloy layer on a copper foil, a tin oxide film on a surface of the tin layer or the tin alloy layer opposite to the copper foil, and a coupling on the tin oxide film A laminate having an agent layer.
[9] The laminate according to the above [8], wherein the tin layer or the tin alloy layer has a thickness of 0.01 to 1.0 μm.
[10] The laminate according to the above [8] or [9], further comprising an acidic resin layer having a pH of 3.0 to 5.0 or a prepreg containing the acidic resin layer on the coupling agent layer.
[11] The method according to any one of [8] to [10], wherein the surface roughness (Rz) of the surface of the copper foil on the tin layer or tin alloy layer side is 0.2 to 2.0 μm. Laminate.
[12] A copper-clad laminate having a copper foil on at least one surface of the laminate according to any one of [8] to [11].
[13] A printed wiring board obtained by performing circuit processing on the copper-clad laminate according to the above [12].
[14] A high-speed communication-compatible module manufactured using the printed wiring board according to the above [13].

According to the present invention, there is provided a method for treating a copper foil, which makes it difficult for the resin layer to peel even after a reflow step, regardless of the type of the resin or the resin composition of the resin layer laminated on the conductive layer. can do. Furthermore, it is possible to provide a copper foil obtained by performing the method for treating the copper foil, and to provide a laminate, a copper-clad laminate, a printed wiring board, and a high-speed communication compatible module using the copper foil. it can.

It is a schematic diagram for explaining the presumed mechanism where the effect of the present invention appears when the processing method of the copper foil of the present invention is adopted. It is the schematic for demonstrating the estimation mechanism which a resin layer peels when the conventional copper foil processing method is employ | adopted.

In the numerical ranges described in this specification, the upper limit or the lower limit of the numerical range may be replaced with the value shown in the embodiment. In addition, the lower limit and the upper limit of the numerical range are arbitrarily combined with the lower limit and the upper limit of the other numerical ranges, respectively.
An embodiment in which the items described in this specification are arbitrarily combined is also included in the present invention.
Further, in the present specification, the “solid content” refers to a non-volatile content excluding a volatile substance such as a solvent, and indicates a component that remains without volatilization when the resin composition is dried, and is a liquid at room temperature. , Syrupy and waxy ones. Here, room temperature refers to 25 ° C. in this specification.
In the present specification, the “resin component” is a component used in the production of a resin or a resin, excluding an inorganic filler, and specifically, among components contained in a resin composition described below, an inorganic filler It is a component excluding materials.

[Treatment method of copper foil]
The processing method of the copper foil of the present invention,
Forming a tin layer or a tin alloy layer on the surface of the copper foil (1),
Converting tin existing on the surface of the tin layer or tin alloy layer into tin oxide (2),
A step (3) of performing a coupling treatment on the tin oxide;
This is a method for treating a copper foil.
According to the method for treating a copper foil of the present invention, regardless of the type of the resin (or the type of the resin composition) of the resin layer to be laminated on the copper foil, the resin layer is less likely to be separated even after the reflow step. Become. In particular, the effect is exhibited through the above step (2). In general, a flat bond process is performed by combining the step of forming a tin layer or a tin alloy layer on the surface of a copper foil [the step (1)] and the step of performing a coupling treatment [the step (3)]. It may be called a process.
Hereinafter, each step will be described in detail.

(Step (1))
Step (1) is a step of forming a tin layer or a tin alloy layer on the surface of the copper foil. In the present invention, the copper foil may be formed with a circuit, and is preferably formed with a circuit. In the present invention, even when a copper foil is formed on a circuit, it may be simply referred to as a copper foil. In such a case, “copper foil” can be read as “circuit”. When a copper foil is formed on a circuit, a tin layer or a tin alloy layer is formed not only on the surface of the copper foil but also between circuits.
The tin layer or the tin alloy layer has a high affinity for the copper foil. Therefore, the adhesion between the copper foil and the tin layer or the tin alloy layer can be ensured without roughening the surface of the copper foil. Therefore, the surface roughness of the copper foil is kept small. For example, the surface roughness (Rz) of the surface of the copper foil on the tin layer or tin alloy layer side can be 0.2 to 2.0 μm. , 0.5 to 2.0 μm, or 1.0 to 1.8 μm.
Here, in this specification, the “surface roughness” of the copper foil is a ten-point average surface roughness (Rz), which is a value measured according to JIS B0601 (1994).

The tin layer or the tin alloy layer may be a tin layer or a tin alloy layer usually formed in a so-called flat bond process. For example, a tin layer or a tin alloy layer can be formed by performing a tin-based treatment on the surface of a copper foil using a “Flat Bond” series of Mec Corporation. Examples of the tin-based treatment include substitution tin plating, immersion in a treatment solution containing at least one selected from the group consisting of a tin salt, an organic acid, an inorganic acid, a reducing agent, and the like.
The tin layer or the tin alloy layer formed on the surface of the copper foil may be either, but is preferably a tin alloy layer from the viewpoint of suppressing the ionization and diffusion of tin into the copper foil. The tin alloy layer is preferably an alloy layer containing tin and nickel, and more preferably an alloy layer containing tin, copper and nickel.

The thickness of the tin layer or the tin alloy layer is not particularly limited, but is usually preferably 0.01 to 1.0 μm, more preferably 0.03 to 0.7 μm, and still more preferably 0.05 to 0.5 μm. And particularly preferably 0.05 to 0.3 μm.

(Step (2))
The step (2) is a step of converting tin existing on the surface of the tin layer or the tin alloy layer into tin oxide. The tin oxide is not particularly limited, but is preferably at least one selected from the group consisting of tin (II) oxide [SnO] and tin (IV) oxide [SnO ₂ ].

As a method of converting tin existing on the surface of the tin layer or the tin alloy layer to tin oxide, a known method capable of converting metal tin to tin oxide can be used, and is not particularly limited. For example, (a) a method of heat-treating the surface of the tin layer or the tin alloy layer, and (b) a method of oxidizing air by leaving the tin layer or the tin alloy layer at room temperature. Among them, the method (a) is preferable from the viewpoint of sufficiently converting tin to tin oxide in a short time.
In the method (a), the heating temperature is not particularly limited, but is preferably a temperature that promotes oxidation of the surface of the tin layer or the tin alloy layer, for example, preferably 35 to 200 ° C. , More preferably 35 to 160 ° C, further preferably 60 to 140 ° C, particularly preferably 80 to 135 ° C, and most preferably 100 to 135 ° C. When the heating temperature is in this range, the effect of suppressing the separation of the resin layer after passing through the reflow step is large.
The heating time is not particularly limited, but from the viewpoint of sufficiently oxidizing the surface of the tin layer or the tin alloy layer, preferably 5 seconds to 60 minutes, more preferably 10 seconds to 40 minutes, and still more preferably 1 minute. -40 minutes, particularly preferably 5 minutes to 35 minutes.
The heat treatment may be performed once, but may be performed twice or more as necessary.
In the method (a), the heating means is not particularly limited, and for example, a heater, a warm bath, or the like can be used.

Whether tin existing on the surface of the tin layer or the tin alloy layer could be converted to tin oxide was determined by analyzing the composition of the surface of the tin layer or the tin alloy layer by X-ray photoelectron spectroscopy (XPS). It can be recognized by confirming its existence. The X-ray photoelectron spectroscopy (XPS) may use Al-Kα radiation as an X-ray source and measure at a detection angle of 45 °, and there is no particular limitation on the XPS measuring apparatus, but it is described in Examples. What is necessary is just to measure with an apparatus of.
The mechanism by which the effect of the present invention is exhibited by the step (2) will be described with reference to FIG. When the tin oxide film 3 is formed on the surface of the tin layer or the tin alloy layer 2 on the copper foil 1 in the step (2) (see FIG. 1A), the tin oxide film 3 and the step ( The coupling agent layer 4 is sufficiently formed due to high affinity with the coupling agent used in the coupling treatment performed in 3), and the pH is adjusted to 3.0 to 5 as shown in FIG. It is presumed that the oxidation effect 6 by the acidic resin layer 5 of 0.0 was suppressed, and as a result, as shown in FIG. 1C, the peeling did not occur even after the reflow treatment, leading to the effect of the present invention.
On the other hand, if the step (3) is performed without passing through the step (2) (see FIG. 2), as shown in FIG. 2A, the tin layer on the copper foil 1 or the tin alloy layer 2 is formed. The formation of the coupling agent layer 4 is not always sufficient. When the acidic resin layer 5 having a pH of 3.0 to 5.0 is provided on the coupling agent layer 4, as shown in FIG. In addition, tin ions (Sn ⁺ ) are formed from the tin layer or the tin alloy layer 2 by the oxidizing action 6 of the acidic resin layer 5, and the tin ions migrate to the acidic resin layer 5 as shown in FIG. As shown in c), it is presumed that there is a portion 7 in which the adhesion between the tin layer or the tin alloy layer 2 and the acidic resin layer 5 is reduced, and this causes peeling.

(Step (3))
In this step, the tin oxide (tin oxide film) formed in the step (2) is subjected to a coupling treatment. The coupling treatment forms a coupling agent layer. As the coupling agent used in the coupling treatment, a coupling agent used in a known flat bond treatment step can be used. The coupling agent layer has high adhesion to the tin oxide film and also has excellent adhesion to the resin layer.
The coupling agent is not particularly limited, and examples thereof include a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent. Among these, a silane coupling agent is preferable, and examples of the silane coupling agent include an aminosilane-based coupling agent, an epoxysilane-based coupling agent, and a styrene-silane-based coupling agent.
The coupling treatment can be performed by dipping in a coupling agent, showering using the coupling agent, or the like.

The present invention also provides a copper foil obtained by subjecting a copper foil to the method for treating a copper foil of the present invention. As described above, the copper foil may be formed with a circuit, and is preferably formed with a circuit.

[Laminate]
The present invention has a tin layer or a tin alloy layer on a copper foil, a tin oxide film on a surface of the tin layer or the tin alloy layer opposite to the copper foil, and a cup on the tin oxide film. A laminate having a ring agent layer is also provided. The copper foil, tin layer, tin alloy layer, tin oxide film, and coupling agent layer are as described above. The laminate of the present invention can be manufactured by treating a copper foil by the above-described method for treating a copper foil of the present invention.
The laminate of the present invention may have a resin layer (may be a prepreg) on the coupling agent layer. In particular, the resin layer may be an acidic resin layer having a pH of 3.0 to 5.0. This is advantageous in that In the laminate of the present invention, even if the resin layer on the coupling agent layer is an acidic resin layer having a pH of 3.0 to 5.0, the resin layer hardly peels off after the reflow step. Here, the pH of the resin layer is a value obtained by measuring an extract obtained by storing the substrate at 130 ° C. for 200 hours with a pH meter, and more specifically a value measured according to the method described in Examples. .
The resin layer can be manufactured using a resin film formed from a resin composition or a prepreg containing the resin composition.

<Resin composition>
As the resin composition contained in the resin film and the prepreg, a thermosetting resin composition is preferable. The thermosetting resin composition is not particularly limited as long as it contains a thermosetting resin. Hereinafter, “resin composition” can be read as “thermosetting resin composition”.

(Thermosetting resin)
As the thermosetting resin, a known thermosetting resin used as an insulating material for a printed wiring board can be used. For example, polyphenylene ether derivatives, epoxy resins, cyanate resins, isocyanate resins, bisallylnadiimide resins, benzoxazine resins, allyl resins, dicyclopentadiene resins, silicone resins, triazine resins, polymaleimide compounds and modified maleimide compounds [(1) Addition reaction product of polymaleimide compound and monoamine compound, (2) addition reaction product of polymaleimide compound and diamine compound (polymer), (3) addition reaction product of polymaleimide compound with monoamine compound and diamine compound (polymerization) Material) etc.].
In particular, examples in which the resin composition becomes an acidic resin composition having a pH of 3.0 to 5.0 are not particularly limited, but are selected from the group consisting of the polymaleimide compound and the modified maleimide compound. A case where an organic phosphorus-based compound described below is contained as a curing accelerator together with at least one kind is exemplified.
One thermosetting resin may be used alone, or two or more thermosetting resins may be used in combination. For example, an embodiment in which the polyphenylene ether derivative is used in combination with at least one selected from the group consisting of the polymaleimide compound and the modified maleimide compound is exemplified. Furthermore, an embodiment in which the polyphenylene ether derivative is used in combination with the isocyanate resin, an embodiment in which the polyphenylene ether derivative is used in combination with the epoxy resin, and the like are also included.
In any case, the modified maleimide compound is preferably an addition reaction product (polymer) of a polymaleimide compound and a diamine compound.

(Other components)
As components that can be contained in the resin composition, in addition to the thermosetting resin, a thermoplastic resin, a thermoplastic elastomer, an inorganic filler, a copolymer resin, a curing accelerator, an organic filler, a flame retardant, an ultraviolet absorber , An antioxidant, a photopolymerization initiator, a fluorescent brightener, an adhesion improver and the like, and may contain at least one selected from the group consisting of these.

(Polyphenylene ether derivative)
As the polyphenylene ether derivative, a polyphenylene ether derivative having at least one N-substituted maleimide structure-containing group is preferable. Resin composition having excellent high-frequency characteristics, high adhesiveness to copper foil, high glass transition temperature, low coefficient of thermal expansion, and high flame retardancy because the polyphenylene ether derivative has at least one group containing an N-substituted maleimide structure It tends to be a thing. Here, the coefficient of thermal expansion referred to in this specification is a value also called a coefficient of linear expansion. The N-substituted maleimide structure-containing group is not particularly limited as long as it contains an N-substituted maleimide group.

From the same viewpoint as described above, the polyphenylene ether derivative preferably has at least one N-substituted maleimide structure-containing group and a structural unit represented by the following general formula (I).

(In the formula, R ¹ is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. X is an integer of 0 to 4.)

Examples of the aliphatic hydrocarbon group represented by R ¹ in the general formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and n -A pentyl group and the like. The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogen atom is preferably a fluorine atom from the viewpoint of being halogen-free.
Among them, R ¹ is preferably an aliphatic hydrocarbon group having 1 to 5 carbon atoms.

x is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 2. When x is 1 or 2, R ¹ may be substituted at the ortho position on the benzene ring (however, based on the substitution position of the oxygen atom). When x is 2 or more, a plurality of R ¹ may be the same or different.

Specifically, the structural unit represented by the general formula (I) is preferably a structural unit represented by the following general formula (I ′).

The N-substituted maleimide structure-containing group contained in the polyphenylene ether derivative includes nitrogen atoms of two maleimide groups from the viewpoint of high-frequency characteristics, adhesion to a copper foil, heat resistance, glass transition temperature, coefficient of thermal expansion, and flame retardancy. A bismaleimide structure in which they are bonded via an organic group (however, a structure derived from the structure is also included. Here, the structure derived from the structure means that a carbon-carbon double bond of the maleimide group is A functional group (e.g., a structure that has reacted with an amino group)), and is preferably a group represented by the following general formula (Z). The polyphenylene ether derivative having a group represented by the following general formula (Z) is obtained, for example, by reacting a polyphenylene ether (1) with an aminophenol compound (2) to obtain a polyphenylene ether compound having a primary amino group at a molecular terminal. Thus, it can be easily produced by reacting this with the bismaleimide compound (3).

(In the formula, each R ² is independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Y is an integer of 0 to 4. A ¹ is an organic group, which is preferably described later.) It is a group represented by the general formula (II), (III), (IV) or (V).)

The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ² are the same as described for R ¹ .

y is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0. If y is an integer of 2 or more, plural R ² together may be different even in the same.

The groups represented by the general formulas (II), (III), (IV) or (V) as preferred organic groups represented by A ¹ are as follows.

(In the formula, R ³ is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. P is an integer of 0 to 4.)
The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ³ are the same as described for R ¹ .

p is an integer of 0 to 4, and is preferably an integer of 0 to 2, more preferably 0 or 1, and further preferably 0 from the viewpoint of availability. When p is an integer of 2 or more, a plurality of R ³ may be the same or different.

(In the formula, R ⁴ and R ⁵ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ² is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms. A group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, a single bond or a group represented by the following general formula (III-1), wherein q and r are each independently an integer of 0 to 4. is there.)

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ⁴ and R ⁵ include the same as those in the case of R ¹ . The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and further preferably an ethyl group.

Examples of the alkylene group having 1 to 5 carbon atoms represented by A ² include a methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group and the like. Is mentioned. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoints of high-frequency characteristics, adhesion to a copper foil, heat resistance, glass transition temperature, coefficient of thermal expansion, and flame retardancy, and a methylene group. Is more preferable.

The alkylidene group having 2 to 5 carbon atoms which A ² represents, for example, ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group, and the like. Among these, an isopropylidene group is preferred from the viewpoints of high-frequency characteristics, adhesiveness to copper foil, heat resistance, glass transition temperature, coefficient of thermal expansion, and flame retardancy.
A ² is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms among the above options.

q and r are each independently an integer of 0 to 4, and from the viewpoint of availability, each is preferably an integer of 0 to 2, and more preferably 0 or 2. When q or r is an integer of 2 or more, a plurality of R ⁴ or R ⁵ may be the same or different.

Incidentally, the group represented by the general formula represented by A ² (III-1) are as follows.

(Wherein, R ⁶ and R ⁷ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. A ³ is an alkylene group having 1 to 5 carbon atoms, an isopropylidene group, an ether group, A sulfide group, a sulfonyl group, a carbonyloxy group, a keto group, or a single bond. S and t are each independently an integer of 0 to 4.)

The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ⁶ and R ⁷ are described in the same manner as in the case of R ⁴ and R ⁵ .

As the alkylene group having 1 to 5 carbon atoms represented by A ³ , the same alkylene group having 1 to 5 carbon atoms represented by A ² can be mentioned.
A ³ is preferably an alkylidene group having 2 to 5 carbon atoms among the above options.

s and t are each an integer of 0 to 4, and from the viewpoint of availability, each is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. . When s or t is an integer of 2 or more, a plurality of R ⁶ or R ⁷ may be the same or different.

(In the formula, n is an integer of 0 to 10.)

Δn is preferably 0 to 5, more preferably 0 to 3, from the viewpoint of availability.

(In the formula, R ⁸ and R ⁹ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. U is an integer of 1 to 8.)

The aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R ⁸ and R ⁹ are the same as those described for R ¹ .
u is an integer of 1 to 8, preferably 1 to 3, and more preferably 1.

The A ¹ in the group represented by the general formula (Z), the high frequency characteristics, adhesion to a copper foil, heat resistance, glass transition temperature, in view of thermal expansion and flame retardancy, any of the following formulas Is preferably a group represented by

The A ¹ in the group represented by the general formula (Z), the high frequency characteristics, adhesion to a copper foil, heat resistance, glass transition temperature, in view of thermal expansion and flame retardancy, any of the following formulas Is more preferably a group represented by

The polyphenylene ether derivative is preferably a polyphenylene ether derivative represented by the following general formula (Z ′).

(In the formula, A ¹ , R ¹ , R ² , x and y are as defined above. M is an integer of 1 or more.)

M is preferably an integer of 1 to 300, more preferably an integer of 10 to 300, further preferably an integer of 30 to 200, and particularly preferably an integer of 50 to 150.

The polyphenylene ether derivative is preferably a polyphenylene ether derivative represented by any of the following formulas (Z′-1) to (Z′-4).

(In the formula, m is the same as m in the general formula (Z ′), and the preferred range is also the same.)

From the viewpoint that the raw material is inexpensive, a polyphenylene ether derivative represented by the above formula (Z'-1) is preferable, and from the viewpoint of excellent dielectric properties and low water absorption, the above formula (Z'- The polyphenylene ether derivative represented by 2) is preferable, and from the viewpoint of excellent adhesiveness to copper foil and mechanical properties (elongation, breaking strength, etc.), the above formula (Z′-3) or the above formula (Z ′) It is preferably a polyphenylene ether derivative represented by '-4). Therefore, the polyphenylene ether derivative represented by any of the above formulas (Z'-1) to (Z'-4) may be used alone or in combination of two or more in accordance with the desired properties. You may.

The number average molecular weight of the polyphenylene ether derivative is preferably from 4,000 to 14,000, more preferably from 4,500 to 12,000, and still more preferably from 7,000 to 12,000. , 7,000 to 10,000. When the number average molecular weight is 4,000 or more, a better glass transition temperature tends to be obtained in the resin composition. If the number average molecular weight is 14,000 or less, the moldability of the resin composition tends to be good.
In the present specification, the number average molecular weight is a value converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC), and more specifically, the measurement of the number average molecular weight described in Examples. It is a value obtained by the method.

(Modified maleimide compound)
Examples of the modified maleimide compound include (1) an addition reaction product of a polymaleimide compound and a monoamine compound, (2) an addition reaction product (polymer) of a polymaleimide compound and a diamine compound, and (3) a polymaleimide compound and a monoamine compound. An addition reaction product (polymer) of a diamine compound with a diamine compound is preferable. Among these, an addition reaction product of the (2) polymaleimide compound and a diamine compound is preferable from the viewpoint of heat resistance and reliability.
Examples of the addition reaction product of the polymaleimide compound and the diamine compound include a maleimide compound (b1) having at least two N-substituted maleimide groups in one molecule, and at least two primary amino groups in one molecule. An addition reaction product with the amine compound (b2) is preferred.

(Maleimide compound (b1) having at least two N-substituted maleimide groups in one molecule)
The maleimide compound (b1) having at least two N-substituted maleimide groups in one molecule (hereinafter also referred to as “component (b1)”) has at least two N-substituted maleimide groups in one molecule. The structure is not particularly limited as long as it is a structure, but a maleimide compound having two N-substituted maleimide groups in one molecule is preferable, and a compound represented by the following general formula (b1-1) is more preferable.

(In the formula, X ^B1 is a group represented by the following general formula (b1-2), (b1-3), (b1-4) or (b1-5).)

(In the formula, R ^B1 is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms. P1 is an integer of 0 to 4.)

(Wherein, R ^B2 is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms. X ^B2 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group, A carbonyloxy group, a keto group, a single bond or a group represented by the following general formula (b1-3 ′). Q1 is independently an integer of 0 to 4.)

(Wherein, R ^B3 is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms. X ^B3 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group. , A carbonyloxy group, a keto group or a single bond. R1 is each independently an integer of 0 to 4.)

(In the formula, n1 is an integer of 1 to 10.)

(In the formula, R ^B4 is each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. U1 is an integer of 1 to 8.)

In the general formula (b1-2), examples of the aliphatic hydrocarbon group represented by R ^B1 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and a An alkyl group having 1 to 5 carbon atoms such as a pentyl group.

In the general formula (b1-3), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^B2 include the same as those in the case of R ^B1 .
The alkylene group having a carbon number of 1 to 5 X ^B2 represents, methylene group, 1,2-dimethylene group, a 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group and the like Can be
The alkylidene group having 2 to 5 carbon atoms which X ^B2 represents, ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group, and the like.
X ^B2 is preferably an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms, among the above options.

In the formula (b1-3 ′), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^B3 include the same as those in the case of R ^B2 .
As the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X ^{B3, the same as} the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X ^B2 can be mentioned. Can be
The X ^B3, Among the alternatives is preferably alkylidene group having 2 to 5 carbon atoms.

In the general formula (b1-4), n1 is an integer of 1 to 10, but is preferably 0 to 5 and more preferably 0 to 3 from the viewpoint of availability.
In the general formula (b1-5), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^B4 include the same as those in the case of R ^{B1 in} the general formula (b1-2).

As the component (b1), N, N′-ethylenebismaleimide, N, N′-hexamethylenebismaleimide, N, N ′-(1,3-phenylene) bismaleimide, N, N ′-[1,3 -(2-methylphenylene)] bismaleimide, N, N '-[1,3- (4-methylphenylene)] bismaleimide, N, N'-(1,4-phenylene) bismaleimide, bis (4- Maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide, bis (4-maleimidophenyl) ether, Bis (4-maleimidophenyl) ketone, bis (4-maleimidocyclohexyl) methane, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis (male Imidomethyl) cyclohexane, 1,4-bis (maleimidomethyl) benzene, 1,3-bis (4-maleimidophenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) benzene ) Phenyl] methane, bis [4- (4-maleimidophenoxy) phenyl] methane, 1,1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) ) Phenyl] ethane, 1,2-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (4-maleimidophenoxy) phenyl] ethane, 2,2-bis [4- ( 3-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] p Bread, 2,2-bis [4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] butane, 4,4'-bis (3-maleimidophenoxy) Biphenyl, 4,4′-bis (4-maleimidophenoxy) phenyl] ketone, bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (4-maleimidophenoxy) phenyl] ketone, bis [4- (3 -Maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] ether and the like. As the component (b1), one type may be used alone, or two or more types may be used in combination.
Among these, a maleimide compound having a phenoxy group is preferable from the viewpoint of excellent solubility in a solvent, and bis (4-maleimidophenyl) methane, 2,2- Bis [4- (4-maleimidophenoxy) phenyl] propane is preferred.

(Amine compound (b2) having at least two primary amino groups in one molecule)
The amine compound (b2) having at least two primary amino groups in one molecule (hereinafter also referred to as “component (b2)”) is preferably an amine compound having two primary amino groups in one molecule. And a compound represented by the following general formula (b2-1) is more preferable.

(In the formula, Y ^B1 is a group represented by the following general formula (b2-2), (b2-3) or (b2-4).)

^{(Wherein, R B5} each independently, .P2 an aliphatic hydrocarbon group having 1 to 5 carbon atoms is an integer of 0-4.)

(Wherein, R ^B6 is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Y ^B2 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group. , A carbonyloxy group, a keto group, a single bond, a group represented by the following general formula (b2-3 ′) or a group represented by the following general formula (b2-3 ″). , 0 to 4).

(Wherein, R ^B7 is each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Y ^B3 is an alkylene group having 1 to 5 carbon atoms, an alkylidene group having 2 to 5 carbon atoms, an ether group. , Carbonyloxy, keto, or a single bond. S1 is each independently an integer of 0 to 4.)

( ^Wherein Y ^B4 and Y ^B6 are each independently an alkylene group having 1 to 5 carbon atoms or an alkylidene group having 2 to 5 carbon atoms. Y ^B5 is an aromatic hydrocarbon having 6 to 12 ring carbon atoms. It is a hydrogen group.)

(Wherein, R ^B8 is each independently an alkyl group having 1 to 5 carbon atoms, a phenyl group or a substituted phenyl group. R ^B9 is each independently a divalent organic group. M2 is 1 It is an integer of １００100.)

In the general formula (b2-2), examples of the aliphatic hydrocarbon group represented by R ^B5 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a t-butyl group, and a An alkyl group having 1 to 5 carbon atoms such as a pentyl group.

In the general formula (b2-3), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^B6 include the same as those in the case of R ^B5 .
Examples of the alkylene group having 1 to 5 carbon atoms represented by Y ^B2 include a methylene group, 1,2-dimethylene group, 1,3-trimethylene group, 1,4-tetramethylene group, 1,5-pentamethylene group and the like. Can be
The alkylidene group having 2 to 5 carbon atoms which Y ^B2 represented, ethylidene group, propylidene group, isopropylidene group, butylidene group, isobutylidene group, pentylidene group, isopentylidene group, and the like.

In the formula (b2-3 ′), examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^B7 include the same as those in the case of R ^B6 .
In the formula (b2-3 ′), examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by Y ^B3 include an alkylene group having 1 to 5 carbon atoms represented by Y ^{B2 and} The same as the 2 to 5 alkylidene groups can be mentioned.
In the general formula (b2-3 ″), examples of the alkylene group having 1 to 5 carbon atoms represented by Y ^B4 and Y ^B6 and the alkylidene group having 2 to 5 carbon atoms include alkylene groups having 1 to 5 carbon atoms represented by Y ^B2. And the same as the alkylidene group having 2 to 5 carbon atoms. Among them, an alkylidene group having 2 to 5 carbon atoms is preferable, and an isopropylidene group is more preferable. Y ^B4 and Y ^B6 may be the same or different, but are preferably the same.
In formula (b2-3 ^''), the aromatic hydrocarbon group having ring carbon atoms 6-12 represented by ^{Y B5,} 1,3-phenylene group, a phenylene group such as 1,4-phenylene group; A naphthylene group; a biphenylylene group and the like. Among these, a phenylene group is preferred.

In the formula (b2-4), the alkyl group having 1 to 5 carbon atoms represented by R ^B8 is more preferably an alkyl group having 1 to 3 carbon atoms. ^Examples of the alkyl group represented by ^RB8 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. Groups are preferred.
Examples of the substituent in the substituted phenyl group represented by ^RB8 include an alkyl group, an alkenyl group, and an alkynyl group. Among them, the alkyl group is preferable. Examples of the alkyl group include the same as the alkyl group represented by ^RB8 .
^Examples of the divalent organic group represented by RB9 include an alkylene group, an alkylidene group, an alkenylene group, an alkynylene group, an arylene group, —O—, and a divalent linking group obtained by combining these. Among these, an alkylene group and an arylene group are preferable. Examples of the alkylene group include an alkylene group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, and a propylene group. Examples of the arylene group include an arylene group having 6 to 12 ring carbon atoms such as a phenylene group and a naphthylene group.
m2 is an integer of 1 to 100, preferably an integer of 2 to 50, more preferably an integer of 3 to 40, still more preferably an integer of 5 to 30, and further preferably an integer of 7 to 30; It may be an integer of 30 or an integer of 15 to 30.

As the component (b2), a modified siloxane having an amino group at a terminal, diaminobenzidine, diaminodiphenylmethane, 3,3′-diethyl-4,4′-diaminodiphenylmethane, diaminodiphenylether, 3,3′-dimethoxy-4,4 '-Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 1,3'-bis (4-aminophenoxy) benzene, 2,2'-bis [4- (4-aminophenoxy) phenyl ] Propane, 4,4'-bis (4-aminophenoxy) biphenyl, 1,4'-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4 ' -Diamino-3,3'-biphenyldiol, 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bi Aniline, 4,4 '- [1,4-phenylene bis (1-methylethylidene)] bisaniline, and the like. As the component (b2), one type may be used alone, or two or more types may be used in combination.

Among these, from the viewpoint of obtaining high elasticity and high heat resistance, 3,3′-diethyl-4,4′-diaminodiphenylmethane, 4,4 ′-[1,3-phenylenebis (1-methylethylidene) Bisaniline, 4,4 '-[1,4-phenylenebis (1-methylethylidene)] bisaniline and 2,2'-bis [4- (4-aminophenoxy) phenyl] propane are preferred.
In addition, from the viewpoint of low thermal expansion, a modified siloxane having an amino group at a terminal is preferable. As the modified siloxane having an amino group at the terminal, a commercially available product may be used. Examples of the commercially available product include “X-22-161A” (functional group equivalent: 800 g / mol) and “X- 22-161B "(functional group equivalent: 1,500 g / mol) (above, manufactured by Shin-Etsu Chemical Co., Ltd.)," BY16-853U "(functional group equivalent: 460 g / mol) (above, manufactured by Dow Corning Toray), "XF42-C5379" (functional group equivalent: 750 g / mol) (all manufactured by Momentive Performance Materials Japan GK) and the like.

Further, the component (b2) contains a modified siloxane having an amino group at a terminal and an amine compound other than the modified siloxane having an amino group at a terminal from the viewpoint of achieving low thermal expansion, high elasticity, and high heat resistance. It is also preferable to do so.
When a modified siloxane having an amino group at the end and an amine compound other than the modified siloxane having an amino group at the end are used in combination as the component (b2), the mass ratio [modified siloxane having an amino group at the end / modified siloxane at the end] The amine compound other than the modified siloxane having an amino group] is preferably 3/97 to 90/10, more preferably 10/90 to 80/20, and still more preferably 20/80 to 70/30.

変 性 The modified maleimide compound which is an addition reaction product of the component (b1) and the component (b2) has, for example, a structural unit represented by the following general formula (B-1).

^{(Wherein, X B1} is the same as ^{X B1} in the formula ^{(b1-1), Y B1} is the same as ^{Y B1} in the formula (b2-1).)

(Cyanate resin)
Although the cyanate resin is not particularly limited, for example, 2,2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ethane, bis (3,5-dimethyl-4-cyclohexane) Anatophenyl) methane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, α, α′-bis (4-cyanatophenyl) -m- Examples include diisopropylbenzene, a cyanate compound of a phenol-added dicyclopentadiene polymer, a phenol novolak type cyanate compound, and a cresol novolak type cyanate compound. One type of cyanate resin may be used alone, or two or more types may be used in combination. Among these, it is preferable to use 2,2-bis (4-cyanatophenyl) propane from the viewpoint of the production cost and the total balance of the high frequency characteristics and other characteristics.

When a cyanate resin is used, a curing agent for the cyanate resin, a curing assistant, and the like can be used in combination, if necessary. These are not particularly restricted but include, for example, monophenol compounds, polyphenol compounds, amine compounds, alcohol compounds, acid anhydrides, carboxylic acid compounds and the like. These may be used alone or in combination of two or more. The amounts of the curing agent and the curing aid are not particularly limited, and can be appropriately adjusted depending on the purpose. Among these, it is preferable to use a monophenol compound from the viewpoints of high-frequency characteristics, heat resistance, moisture absorption resistance and storage stability.

In the case of using the monophenol compound, it is preferable to adopt a method of preliminarily reacting with a cyanate resin and using it as a phenol-modified cyanate prepolymer from the viewpoint of solubility in an organic solvent. The monophenol compound to be used in combination may be blended in a prescribed amount when pre-polymerized, or may be blended separately before and after pre-polymerization. Can be adopted.

(Epoxy resin)
The epoxy resin is preferably an epoxy resin having two or more epoxy groups. Here, the epoxy resin is classified into a glycidyl ether type epoxy resin, a glycidylamine type epoxy resin, a glycidyl ester type epoxy resin, and the like. Among them, a glycidyl ether type epoxy resin may be selected.

Epoxy resins are classified into various epoxy resins according to the difference in the main skeleton. Among the above types of epoxy resins, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin and other bisphenol type epoxy resins. Epoxy resin; alicyclic epoxy resin; aliphatic chain epoxy resin; phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin and other novolak type epoxy resins; phenol aralkyl Epoxy resin; stilbene epoxy resin; dicyclopentadiene epoxy resin; naphthalene skeleton such as naphthol novolak epoxy resin and naphthol aralkyl epoxy resin It is classified into dicyclopentadiene type epoxy resin; type epoxy resins; biphenyl type epoxy resins; biphenyl aralkyl type epoxy resins; xylylene-type epoxy resins; dihydroanthracene type epoxy resin.

Epoxy resin may be used alone or in combination of two or more. Among these, from the viewpoint of high-frequency characteristics, heat resistance, glass transition temperature, coefficient of thermal expansion, flame retardancy, and the like, a naphthalene skeleton-containing epoxy resin, a biphenylaralkyl-type epoxy resin is preferable, and a naphthalene skeleton-containing epoxy resin is more preferable. And a naphthol novolak type epoxy resin.

When an epoxy resin is used, a curing agent for the epoxy resin, a curing aid, and the like can be used in combination, if necessary. Although these are not particularly limited, for example, polyamine compounds such as diethylenetriamine, triethylenetetramine, diaminodiphenylmethane, m-phenylenediamine, dicyandiamide; bisphenol A, phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, phenol Polyphenol compounds such as aralkyl resins; acid anhydrides such as phthalic anhydride and pyromellitic anhydride; carboxylic acid compounds; and active ester compounds. These may be used alone or in combination of two or more. The amount used is not particularly limited, and can be appropriately adjusted depending on the purpose.

(Inorganic filler)
Examples of the inorganic filler include silica, alumina, titanium oxide, mica, barium titanate, strontium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, calcium carbonate silicon nitride, boron nitride, talc, silicon carbide, Quartz powder, short glass fiber, fine glass powder, hollow glass and the like can be used. Preferred examples of the glass include E glass, T glass, and D glass. As the inorganic filler, one type may be used alone, or two or more types may be used in combination.
Among these, silica is preferred from the viewpoint of dielectric properties, heat resistance and low thermal expansion. Examples of the silica include, for example, precipitated silica having a high water content produced by a wet method and dry-process silica which is produced by a dry method and hardly contains bound water, and the like. , Crushed silica, fumed silica, fused spherical silica and the like. Among these, fused spherical silica is preferred from the viewpoints of low thermal expansion and fluidity when filled in a resin.

(4) The average particle diameter of the inorganic filler is preferably 0.1 to 10 μm, more preferably 0.3 to 8 μm. When the average particle diameter is 0.1 μm or more, there is a tendency that the fluidity at the time of highly filling the resin can be kept good, and when the average particle diameter is 10 μm or less, the mixing probability of coarse particles is reduced, and coarse particles are caused. Tends to suppress the occurrence of defects. Here, the average particle diameter is a particle diameter at a point corresponding to a volume of 50% when a cumulative frequency distribution curve based on the particle diameter is determined with the total volume of the particles being 100%. Can be measured by a particle size distribution measuring device or the like.

The inorganic filler may be surface-treated with a coupling agent. The method of surface treatment with the coupling agent may be a method of performing a dry or wet surface treatment on the inorganic filler before being blended into the resin composition, and the surface-untreated inorganic filler may be treated with other components. And then adding a silane coupling agent to the composition after mixing to form a composition, that is, a so-called integral blending method. Examples of the coupling agent include a silane coupling agent, a titanate coupling agent, and a silicone oligomer.

(4) When the resin composition contains an inorganic filler, the content is preferably from 10 to 300 parts by mass, more preferably from 50 to 250 parts by mass, per 100 parts by mass of the resin component in the resin composition. When the content of the inorganic filler is within the above range, the moldability and the low thermal expansion property tend to be good.

When the resin composition contains an inorganic filler, it is preferable to improve the dispersibility of the inorganic filler by performing a treatment with a dispersing machine such as a three-roll mill, a bead mill, or a nanomizer, if necessary.

(Curing accelerator)
The resin composition may contain a curing accelerator from the viewpoint of promoting the curing reaction.
Examples of the curing accelerator include organic phosphorus compounds such as triphenylphosphine, triphenylphosphonium, tetraphenylphosphonium tetra-p-tolylborate, and triphenylphosphine-triphenylborane; 2-methylimidazole, 2-ethyl-4-methyl Imidazole, 1-benzyl-2-methylimidazole, 2-undecylimidazole, isocyanate mask imidazole (addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole), 2,4-diamino-6- [2 '-Methylimidazolyl- (1')]-ethyl-s-triazine, isocyanuric acid adducts and the like; imidazoles and derivatives thereof; secondary amines, tertiary amines, quaternary ammonium salts and the like. Nitrogen compounds; dicumyl peroxide 2,5-dimethyl-2,5-bis (t-butylperoxy) -3-hexyne, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, bis (1-phenyl-1) Organic peroxides such as -methylethyl) peroxide, diisopropylbenzene hydroperoxide, α, α'-bis (t-butylperoxy) diisopropylbenzene; zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate And the like. As the curing accelerator, one type may be used alone, or two or more types may be used in combination.
When the resin composition contains a curing accelerator, the content is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 13 parts by mass, based on 100 parts by mass of the resin component in the resin composition. It is more preferably from 2 to 13 parts by mass.

(Organic fillers, flame retardants, ultraviolet absorbers, antioxidants, photopolymerization initiators, optical brighteners, adhesion improvers)
Examples of the organic filler include a resin filler made of polyethylene, polypropylene resin and the like, a resin filler having a core-shell structure, and the like.
Examples of the flame retardant include aromatic phosphoric ester compounds, phosphazene compounds, phosphinic esters, metal salts of phosphinic acid compounds, red phosphorus, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide And flame retardants such as melamine sulfate and melamine polyphosphate; and inorganic flame retardants such as antimony trioxide.
Examples of the ultraviolet absorber include a benzotriazole-based ultraviolet absorber.
Examples of the antioxidant include a hindered phenol antioxidant and a hindered amine antioxidant.
Examples of the photopolymerization initiator include benzophenones, benzylketals, and thioxanthone-based photopolymerization initiators.
Examples of the fluorescent whitening agent include a fluorescent whitening agent of a stilbene derivative.
Examples of the adhesion improver include a urea compound such as urea silane, and the coupling agent.

(Prepreg)
The prepreg is obtained by impregnating a fiber base material with the resin composition.
The prepreg can be produced by impregnating the fiber base material with the resin composition of the present invention and semi-curing (B-stage) by heating or the like.
As the fiber base material, well-known ones used for various laminated boards for electric insulating materials can be used. Examples of the material include inorganic fibers such as E glass, S glass, low dielectric glass, and Q glass; low dielectric glass organic fibers such as polyimide, polyester, and tetrafluoroethylene; and mixtures thereof.

These fiber base materials have, for example, a shape such as a woven fabric, a nonwoven fabric, a roving, a chopped strand mat, and a surfacing mat. Thus, one kind may be used alone, or two or more kinds of materials and shapes may be combined. The thickness of the fiber base material can be, for example, about 0.03 to 0.5 mm. These fiber base materials are preferably surface-treated with a silane coupling agent or the like or mechanically subjected to fiber opening treatment, from the viewpoint of heat resistance, moisture resistance, workability, and the like.

The prepreg is usually impregnated with the fiber base material so that the amount of the resin composition adhering to the fiber base material (content of the resin composition in the prepreg) is 20 to 90% by mass. It can be obtained by heating and drying at a temperature of 200 ° C. for 1 to 30 minutes and semi-curing (B stage).

[Copper clad laminate]
The copper-clad laminate of the present invention is obtained by laminating and forming a laminate of the present invention with a configuration in which a copper foil is disposed via the resin layer or the prepreg.
As the molding conditions, the molding conditions for the laminated board for electric insulating material and the multilayer board can be applied. For example, using a multi-stage press, a multi-stage vacuum press, continuous molding, an autoclave molding machine, or the like, molding can be performed at a temperature of 100 to 250 ° C., a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours.

[Printed wiring board]
The printed wiring board of the present invention is obtained by processing a circuit on the copper-clad laminate of the present invention. The copper foil of the copper-clad laminate may be subjected to wiring processing by an ordinary etching method, a plurality of laminated boards subjected to wiring processing via a prepreg may be laminated, and hot pressing may be performed to form a multilayer at once. Thereafter, a multilayer printed wiring board can be manufactured through formation of through holes or blind via holes by drilling or laser processing, and formation of interlayer wiring by plating or conductive paste.

[High-speed communication compatible module]
The high-speed communication compatible module of the present invention is a high-speed communication compatible module manufactured using the printed wiring board of the present invention.
The high-speed communication-compatible module of the present invention is, for example, a communication module or the like in which a semiconductor chip or the like is mounted on the printed wiring board of the present invention. It is suitable for applications where the amount of information communication and the speed are large.

Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.

[Production of polyphenylene ether derivative]
A polyphenylene ether derivative was produced according to the following procedure and the blending amount in Table 1.

(Production Example A-1: Production of polyphenylene ether derivative (A-1))
Toluene, polyphenylene ether having a number average molecular weight of about 16,000, and p-aminophenol were charged into a 2 L-capacity glass flask capable of heating and cooling equipped with a thermometer, a reflux condenser, and a stirrer. And dissolved with stirring.
After visual confirmation of dissolution, t-butyl peroxyisopropyl monocarbonate and manganese naphthenate were added and reacted at a solution temperature of 90 ° C. for 4 hours. After cooling to 70 ° C., a primary amino group was added to the molecular terminal. A polyphenylene ether compound (a) having the following formula: was obtained.
When a small amount of the reaction solution was taken out and measured by gel permeation chromatography (GPC), the peak derived from p-aminophenol disappeared, and the number average molecular weight of the polyphenylene ether compound (a) was about 9, It was 200. Also, a small amount of the reaction solution was dropped into a methanol / benzene mixed solvent (mixing mass ratio: 1/1), reprecipitated, and the purified solid (reaction product) was subjected to FT-IR measurement. The appearance of a peak derived from a primary amino group at around 400 cm ^-1 was confirmed.

Here, the number average molecular weight was converted from a calibration curve using standard polystyrene by gel permeation chromatography (GPC). The calibration curve is standard polystyrene: TSKstandard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, [Product Name] was used to approximate by a cubic equation. The measurement conditions of GPC are shown below.
<Apparatus>
Pump: L-6200 type [manufactured by Hitachi High-Technologies Corporation]
Detector: L-3300 type RI [manufactured by Hitachi High-Technologies Corporation]
Column oven: L-655A-52 [manufactured by Hitachi High-Technologies Corporation]
Column: guard column; TSK Guardcolumn HHR-L + column; TSKgel G4000HHR + TSKgel G2000HHR [all manufactured by Tosoh Corporation, trade name]
Column size: 6.0 × 40 mm (guard column), 7.8 × 300 mm (column)
Eluent: tetrahydrofuran Sample concentration: 30 mg / 5 mL
Injection volume: 20 μL
Flow rate: 1.00 mL / min Measurement temperature: 40 ° C

Next, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide and propylene glycol monomethyl ether were added to the reaction solution, and the temperature of the solution was increased with stirring. The reaction was carried out for 4 hours while keeping the temperature at ° C. Thereafter, the mixture was cooled and filtered through a 200 mesh filter to produce a polyphenylene ether derivative [referred to as polyphenylene ether derivative (A-1)].

A small amount of the reaction solution thus obtained was taken out, reprecipitated in the same manner as described above, and the purified solid was subjected to FT-IR measurement. The disappearance of the peak derived from the primary amino group at around 3,400 cm ⁻¹ , The appearance of a peak derived from the carbonyl group of maleimide at 700 to 1,730 cm ^-1 was confirmed. GPC of the solid (under the same conditions as above) was measured to find that the number average molecular weight was about 9,400.

(Production Examples A-2 to A-3: Production of Polyphenylene Ether Derivatives (A-2) to (A-3))
Polyphenylene ether derivatives (A-2) to (A-3) were produced in the same manner as in Production Example A-1, except that the raw materials and the amounts added in Production Example A-1 were changed as shown in Table 1. did. Table 1 shows the number average molecular weights of the polyphenylene ether derivatives (A-2) to (A-3).

Abbreviations of each material in Table 1 are as follows.
[1] Polyphenylene ether (1)
-PPO640: polyphenylene ether, number average molecular weight = about 16,000, trade name (manufactured by SABIC Innovative Plastics)
[2] Aminophenol compound (2)
-P-Aminophenol [3] bismaleimide compound (3)
3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebismaleimide ・ 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane ・ 1,6-bismaleimide- ( 2,2,4-trimethyl) hexane [4] reaction catalyst, t-butyl peroxyisopropyl monocarbonate, manganese naphthenate [5] organic solvent, toluene, propylene glycol monomethyl ether

[Production of modified maleimide compounds (B-1) to (B-3) and phenol-modified cyanate prepolymer (C-1)]
Modified maleimide compounds (B-1) to (B-3), which are thermosetting resins, and a phenol-modified cyanate prepolymer (C-1) were produced according to the following procedure and the blending amounts shown in Table 2.

[Production Example B-1: Production of Modified Maleimide Compound (B-1)]
A 2-L (2- (4-maleimidophenoxy) phenyl) propane, 2,2-bis (2-bis (4-maleimidophenoxy) phenyl) propane 4- (4-Aminophenoxy) phenyl) propane and propylene glycol monomethyl ether are added, and the mixture is reacted for 3 hours while stirring while keeping the liquid temperature at 120 ° C., and then cooled and filtered through a 200 mesh filter. Thus, a modified maleimide compound (B-1) was produced.

[Production Examples B-2 to B-3: Production of Modified Maleimide Compounds (B-2) to (B-3)]
The modified maleimide compounds (B-2) to (B-3) were prepared in the same manner as in Production Example B-1, except that the raw materials and the amounts thereof were changed as shown in Table 2 in Production Example B-1. Manufactured.

[Production Example C-1: Production of phenol-modified cyanate prepolymer (C-1)]
Toluene, 2,2-bis (4-cyanatophenyl) propane and p- (α-cumyl) phenol were placed in a heatable and coolable 1 L glass flask equipped with a thermometer, a reflux condenser, and a stirrer. Was added and manganese naphthenate was added as a reaction catalyst with stirring while keeping the liquid temperature at 110 ° C., and the mixture was reacted for 3 hours. Thereafter, the mixture was cooled and filtered through a 200 mesh filter to produce a phenol-modified cyanate prepolymer (C-1).

The symbol of each material in Table 2 is as follows.
(1) Polymaleimide compound, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane (2) Aromatic diamine compound, 2,2-bis (4- (4-aminophenoxy) phenyl) propane / 4,4 '-[1,4-phenylenebis (1-methylethylidene)] bisaniline / 4,4'-[ 1,3-phenylenebis (1-methylethylidene)] bisaniline (3) cyanate resin / BADCy: Primaset (registered trademark) BADCy, 2,2-bis (4-cyanatophenyl) propane (manufactured by Lonza)
(4) Monophenol compound, p- (α-cumyl) phenol (5) Reaction catalyst, manganese naphthenate (6) Organic solvent, toluene, propylene glycol monomethyl ether

[Examples 1 to 21, Comparative Examples 1 to 21]
(Preparation of resin composition)
The components shown in Tables 3 to 6 are stirred and mixed while heating at room temperature or at 50 to 80 ° C. according to the blending amounts (unit: parts by mass) shown in Tables 3 to 6 to obtain a solid content concentration of 55 to 60% by mass. Was prepared.
Here, as the compounding amount of the inorganic filler, the density of the resin composition (excluding the inorganic filler) is usually 1.20 to 1.25 g / cm ³ , and the density of the inorganic filler used is 2. Since it is 2 to 3.01 g / cm ³ , when 109 parts by mass of the inorganic filler is mixed with 156 parts by mass of the resin composition (excluding the inorganic filler), the amount is about 21 to 27% by volume.
It should be noted that the raw materials and intermediate products used in the above production examples are extremely small or inactivated, and can be ignored even if they remain in the resin composition.
(Manufacture of prepreg)
Each resin composition prepared as described above was applied to a 0.1 mm thick glass cloth (E glass, manufactured by Nitto Boseki Co., Ltd.), and then heated and dried at 160 ° C. for 7 minutes to obtain a resin content. (Resin content) A prepreg of about 54% by mass was produced.

(Treatment of Copper Foil in Examples 1 to 21)
35 μm thick low-profile copper foil “FV-WS” [trade name, M surface (mat surface) surface roughness (Rz): 1.5 μm, Furukawa Electric Co., Ltd.] S surface (shiny surface) Then, a tin-based treatment, which is the first step of the flat bond treatment, was performed [Step (1)] to form a tin alloy layer having a thickness of 0.05 to 0.1 μm.
Thereafter, the copper foil on which the tin alloy layer was formed was subjected to a heat treatment at 120 ° C. for 20 minutes using a heater [step (2)].
Further, the formed tin alloy layer was subjected to a coupling process as a second step of the flat bond process [step (3)]. A stack of six prepregs is placed between two copper foils that have been treated in this way, and heated and pressed under the conditions of a temperature of 230 ° C., a pressure of 3.9 MPa, and a time of 180 minutes. Thus, a double-sided copper-clad laminate was produced. This double-sided copper-clad laminate is referred to as “normal double-sided copper-clad laminate”.
In addition, the operation of passing the thus obtained normal double-sided copper-clad laminate through a constant temperature bath over 300 seconds so that the substrate temperature reached a maximum of 260 ° C. was performed six times. The copper-clad laminate after the treatment is referred to as “double-sided copper-clad laminate after six 260 ° C. reflow treatments”.
Each measurement and evaluation were performed using the double-sided copper-clad laminate obtained as described above according to the methods described below. The results are shown in Tables 3 and 4.

(Treatment of copper foil in Comparative Examples 1 to 21)
A double-sided copper-clad laminate was produced in the same manner as in Examples 1 to 21 except that step (2) was not performed. Then, the obtained double-sided copper-clad laminate is passed through a thermostat bath for 300 seconds so that the substrate temperature becomes 260 ° C. at the maximum, six times, and the double-sided copper-clad laminate after the reflow treatment at 260 ° C. is performed six times. Produced.
Each measurement and evaluation were performed using the double-sided copper-clad laminate obtained as described above according to the methods described below. The results are shown in Tables 5 and 6.

[Evaluation measurement method]
(1) Analysis of pH of Resin Composition Using a test piece of 40 × 30 mm size obtained by etching copper foil on both sides of a normal double-sided copper-clad laminate prepared in each example, using Teflon (registered trademark) together with 50 ml of ultrapure water ) Put in container A. On the other hand, another Teflon container B containing only 50 ml of ultrapure water was also prepared.
After each Teflon container A and B was covered with a Teflon lid and the Teflon container was sealed, these Teflon containers A and B were stored in dedicated stainless steel containers. In that state, it was stored in a dryer set at 130 ° C. for 200 hours. The pH of each liquid was measured by using a liquid heat treated with a test piece and ultrapure water as an extract, and a liquid heat treated with only ultrapure water as a control liquid. The pH of the control solution was 7. Tables 3 to 6 show the pH of the extract.

(2) Measurement of peel strength Using a normal double-sided copper-clad laminate prepared in each example or a double-sided copper-clad laminate subjected to 260 ° C. reflow six times treatment, JIS C6481 (1996) “5.7 Peel strength The peel strength was measured in accordance with "Sasa".

(3) Measurement of tin adhesion amount on peeled surface after peeling copper foil (2) Scanning electron microscope / energy dispersive X-ray spectroscopy of the surface of prepreg after peeling copper foil by measuring peel strength described above (2) Observed by a method (SEM / EDX), the amount of tin adhering to the surface of the prepreg after peeling off the copper foil (unit: mass%) was measured. When the amount of tin adhesion is large, it is considered that tin in the tin alloy layer has migrated to the resin composition in the prepreg, and it can be said that the resin layer is in a state where peeling of the resin layer easily occurs.

(4) Measurement of element abundance ratio on tin alloy layer surface A 1 cm square sample was cut out from the center of the double-sided copper-clad laminate obtained in Example 1 after the reflow treatment at 260 ° C. six times, and subjected to X-ray photoelectron spectroscopy (XPS). ) Was used to perform elemental quantitative analysis of the conductor surface under the following measurement conditions. Table 7 shows the results.
(XPS measurement conditions)
Equipment: VersaProbe2 (made by ULVAC-PHI)
X-ray source: Al-Kα ray Detection angle: 45 °

The abbreviations of the respective materials in Tables 3 to 6 are as follows.
(Thermosetting resin)
(1) Polyphenylene ether derivative A-1: The polyphenylene ether derivative (A-1) obtained in Production Example A-1 was added to the table by appropriately removing the organic solvent or adding toluene and propylene glycol monomethyl ether. The solid content concentration described.
A-2: The polyphenylene ether derivative (A-2) obtained in Production Example A-2 was subjected to removal of an organic solvent or addition of toluene and propylene glycol monomethyl ether as appropriate to obtain a solid content concentration shown in the table. And what.
A-3: The polyphenylene ether derivative (A-3) obtained in Production Example A-3 was appropriately subjected to removal of an organic solvent or addition of toluene and propylene glycol monomethyl ether to obtain a solid content concentration shown in the table. And what.
(2) Modified maleimide compound · B-1: The modified maleimide compound (B-1) obtained in Production Example B-1 is described in the table by appropriately removing the organic solvent or adding propylene glycol monomethyl ether. Solids concentration.
B-2: The modified maleimide compound (B-2) obtained in Production Example B-2 was adjusted to a solid content concentration shown in the table by appropriately removing the organic solvent or adding propylene glycol monomethyl ether. thing.
B-3: The modified maleimide compound (B-3) obtained in Production Example B-3 was adjusted to a solid concentration shown in the table by appropriately removing the organic solvent or adding propylene glycol monomethyl ether. thing.
(3) Cyanate resin C-1: The phenol-modified cyanate prepolymer (C-1) obtained in Production Example C-1 was appropriately removed by removing an organic solvent or adding toluene to obtain a solid described in the table. What is a partial concentration.
(4) Epoxy resin / NC-7000L: naphthol novolak type epoxy resin, trade name (manufactured by Nippon Kayaku Co., Ltd.)

(5) Hardening accelerator <organic oxide>
・ Α, α'-bis (t-butylperoxy) diisopropylbenzene ・ bis (1-phenyl-1-methylethyl) peroxide ・ diisopropylbenzene hydroperoxide <imidazole curing agent>
G-809L: isocyanate mask imidazole (addition reaction product of hexamethylene diisocyanate resin and 2-ethyl-4-methylimidazole), trade name (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
2-methylimidazole 2-ethyl-4-methylimidazole 1-benzyl-2-methylimidazole 2-undecylimidazole 2MA-OK: 2,4-diamino-6- [2'-methylimidazolyl- ( 1 ′)]-Ethyl-s-triazine isocyanuric acid adduct, trade name (manufactured by Shikoku Chemicals Co., Ltd.)
<Phosphorus curing accelerator>
・ Tetraphenylphosphonium tetra-p-tolylborate ・ Triphenylphosphine-triphenylborane (6) Inorganic filler (D)
Spherical fused silica, average particle size: 0.5 μm, density 2.2 g / cm ³
(7) Flame retardant (E)
OP-930: aluminum dialkyl phosphinate, metal salt of disubstituted phosphinic acid, phosphorus content: 23.5% by mass, trade name (manufactured by Clariant)
Cyclic organic phosphorus compound: 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, phosphorus content: 9.6% by mass

Tables 3 to 6 show that the laminates according to Examples 1 to 21 can significantly suppress the decrease in the peel strength after the reflow treatment and the tin adhesion amount on the peeled surface as compared with Comparative Examples 1 to 21. Significantly less. As described above, according to the present invention, even when a prepreg containing a resin composition having a high acidity is laminated on a copper foil, concern about a decrease in peel strength after a reflow treatment has been solved. This is because, as shown in Table 7, the tin oxide film having a high affinity for the coupling agent is formed on the tin alloy layer by the step (2) in the present invention, and the coupling agent layer is sufficiently formed on the film. It is presumed that the resin composition was less affected by the acidity of the resin composition.

銅 The copper foil, copper-clad laminate, and printed wiring board obtained by using the copper foil processing method of the present invention can be suitably used for electronic parts such as multilayer printed wiring boards and high-speed communication compatible modules.

Reference Signs List 1 Copper foil 2 Tin or tin alloy layer 3 Tin oxide film 4 Coupling agent layer 5 Acidic resin layer at pH 3.0 to 5.0 6 Oxidation action by acidic resin layer at pH 3.0 to 5.0 7 Adhesion decreases Part

Claims (14)

1. Forming a tin layer or a tin alloy layer on the surface of the copper foil (1),
   Converting tin existing on the surface of the tin layer or tin alloy layer into tin oxide (2),
   A step (3) of performing a coupling treatment on the tin oxide;
   A method for treating a copper foil.
2. The method for treating a copper foil according to claim 1, wherein the tin alloy layer is an alloy layer containing tin and nickel.
3. 処理 The copper foil treatment method according to claim 1 or 2, wherein in the step (2), the tin is converted into tin oxide by heat treatment or air oxidation.
4. 方法 The method for treating a copper foil according to claim 3, wherein the temperature of the heat treatment is 35 to 200 ° C.
5. (5) The method for treating a copper foil according to any one of the above (1) to (4), wherein in the step (1), the copper foil is formed with a circuit.
6. 6. The surface roughness (Rz) of the surface of the copper foil on the side of the tin layer or the tin alloy layer after the step (1) is 0.2 to 2.0 μm. 2. The method for treating a copper foil according to claim 1.
7. 銅 A copper foil obtained by subjecting the copper foil to the method for treating a copper foil according to any one of claims 1 to 6.
8. Having a tin layer or a tin alloy layer on the copper foil, having a tin oxide film on the surface of the tin layer or the tin alloy layer opposite to the copper foil, and forming a coupling agent layer on the tin oxide film. Having a laminate.
9. The laminate according to claim 8, wherein the thickness of the tin layer or the tin alloy layer is 0.01 to 1.0 μm.
10. 10. The laminate according to claim 8 or 9, further comprising an acidic resin layer having a pH of 3.0 to 5.0 or a prepreg containing the acidic resin layer on the coupling agent layer.
11. The laminate according to any one of claims 8 to 10, wherein the surface roughness (Rz) of the surface of the copper foil on the tin layer or tin alloy layer side is 0.2 to 2.0 μm.
12. A copper-clad laminate having a copper foil on at least one surface of the laminate according to any one of claims 8 to 11.
13. A printed wiring board obtained by processing a circuit on the copper-clad laminate according to claim 12.
14. A high-speed communication-compatible module manufactured using the printed wiring board according to claim 13.

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