TW201938658A - Prepreg, layered plate, multilayer printed wiring board, semiconductor package, and resin composition, and method of manufacturing prepreg, layered plate, and multilayer printed wiring board - Google Patents

Abstract

Provided are a prepreg, a layered plate, a multilayer printed wiring board, and a semiconductor package which have high adhesion to conductors, excellent heat resistance, high glass transition temperatures, low thermal expansion coefficients, and fire resistance, and are capable of stably exhibiting excellent high frequency properties (dielectric characteristics at high frequency zones). Also provided is a resin composition which is capable of providing the prepreg. Further provided is a method of manufacturing the prepreg, the layered plate, and the multilayer printed wiring board. Specifically, the prepreg comprises a resin composition and a sheet-like fiber reinforced substrate, wherein the amount of outgassing when heated at a temperature of 163 DEG C for 15 minutes is less than 0.7 mass% based on the total prepreg.

Description

Prepreg, laminated board, multilayer printed wiring board, semiconductor package and resin composition, and manufacturing method of prepreg, laminated board, and multilayer printed wiring board

The invention relates to a prepreg, a laminated board, a multilayer printed wiring board, a semiconductor package and a resin composition, and a method for manufacturing a prepreg, a laminated board, and a multilayer printed wiring board.

High-speed and large-capacity signals used in mobile communication equipment and network infrastructure equipment represented by mobile phones, and large-scale computers are being developed year by year. This network infrastructure is the base of mobile communication equipment Devices, servers, routers, etc. Along with this, printed circuit boards mounted in such electronic devices also need to be able to cope with high frequency, so a substrate material is required which has excellent dielectric characteristics (low dielectric constant) in a high frequency region that can reduce transmission loss. (Electric coefficient and low dielectric loss tangent, hereinafter also referred to as high-frequency characteristics). In recent years, as applications for processing such high-frequency signals, in addition to the above-mentioned electronic devices, they are also being used in the field of ITS (Intelligent Transport Systems) (automotive, transportation system related fields) and indoor short-range communication. Development of practical and practical plans for emerging systems that handle high-frequency wireless signals, so it can be predicted that for printed circuit boards assembled in such machines, low transmission loss substrate materials will be further required in the future.

In addition, from the perspective of environmental problems in recent years, the construction of electronic components by lead-free soldering and the flame retardancy by halogen-free materials have been required. Therefore, printed circuit boards also need to have The printed circuit board has higher heat resistance and flame resistance.

Conventionally, for a printed wiring board requiring low transmission loss, a polyphenylene ether (PPE) resin has been used as a heat-resistant thermoplastic polymer excellent in high-frequency characteristics. For example, a method is proposed in which polyphenylene ether is used in combination with a thermosetting resin. Specifically, it has been disclosed that a resin composition containing polyphenylene ether and an epoxy resin (for example, refer to Patent Document 1); and a resin containing a polyphenylene ether and a thermosetting resin having a low dielectric constant cyanate resin. A resin composition (for example, refer to Patent Document 2) and the like.

However, the resin compositions described in the aforementioned Patent Documents 1 to 2 are still insufficiently comprehensive in terms of high-frequency characteristics, adhesion to conductors, low thermal expansion coefficient, and flame retardancy in the GHz region, or may be caused by Polyphenylene ether has low compatibility with a thermosetting resin and may have reduced heat resistance.

In order to solve such a problem, the present inventors have also proposed a resin composition which uses polyphenylene ether resin and polybutadiene resin as a substrate and performs a half-stage (stage A) in the production of a resin composition containing an organic solvent. By forming a semi-interpenetrating network, it is possible to improve compatibility, heat resistance, low thermal expansion coefficient, adhesion to a conductor, and the like (for example, refer to Patent Document 3). However, in addition to the high frequency of substrate materials for printed wiring boards in recent years, from the standpoint of high density, high reliability, and environmental suitability, it is still necessary to continue to develop high adhesion with conductors, Low thermal expansion coefficient, high glass transition temperature, high flame resistance, etc.

In addition, for printed circuit board substrate materials used in network-related equipment applications such as servers and routers, high-density and high-layering are required, and high reflow heat resistance and reliable perforation are required. Sex. Further, as a high-frequency characteristic, excellent dielectric characteristics in a higher frequency region are required, and in general, although the substrate material shows a tendency that the dielectric loss tangent is higher at higher frequencies, it is necessary to increase the frequency in the 10 GHz region. The above exhibits excellent dielectric characteristics, instead of the previous dielectric characteristic values at 1 to 5 GHz.

In order to solve such a problem, the present inventors have proposed a resin composition which is compatible by blending a polyphenylene ether derivative having a specific molecular structure, a specific thermosetting resin, and a styrene-based thermoplastic elastomer. It is good and can exhibit high frequency characteristics, high heat resistance, high adhesion to a conductor, low thermal expansion characteristics, high flame resistance, and the like (see Patent Document 4).
[Prior technical literature]
(Patent Literature)

Patent Document 1: Japanese Patent Application Laid-Open No. 58-069046.
Patent Document 2: Japanese Patent Publication No. 61-018937.
Patent Document 3: Japanese Patent Application Laid-Open No. 2008-95061.
Patent Document 4: International Publication No. 2016/175326.

[Problems to be solved by the invention]
However, as a result of diligent research, the present inventors found that even if the conventional resin composition is used, the results may still be lower than the expected high-frequency characteristics, so the development of a resin composition that can perform stable and Excellent high frequency characteristics.
In view of the above situation, the problem to be solved by the present invention is to provide a prepreg, a laminated board, a multilayer printed wiring board, and a semiconductor package. The prepreg has high adhesion to a conductor, excellent heat resistance, High glass transition temperature, low thermal expansion coefficient and flame resistance, and capable of showing stable and excellent high-frequency characteristics (dielectric characteristics in a high-frequency region); and providing a resin composition capable of providing the prepreg And, a method for manufacturing a prepreg, a laminated board, and a multilayer printed wiring board is further provided.
[Technical means to solve the problem]

As a result of diligent research in order to solve the above problems, the present inventors have found the following facts to complete the present invention: In a resin composition containing a polyphenylene ether derivative having a specific molecular structure and an organic solvent, the concentration of the solid content is set If it is a specific value, it will have high adhesion to the conductor, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient, and flame resistance, and it can exhibit stable and excellent high-frequency characteristics.

That is, the present invention relates to the following techniques [1] to [19].
[1] A prepreg comprising a resin composition and a sheet-like fiber reinforced base material, and
The amount of exhaust gas generated when the prepreg was heated at a temperature of 163 ° C. for 15 minutes was less than 0.7% by mass based on the entire prepreg.
[2] The prepreg according to the above [1], wherein the resin composition contains a polyphenylene ether derivative (A), and the polyphenylene ether derivative (A) has an N-substituted maleimide Structural group.
[3] The prepreg according to the above [2], wherein the group containing the N-substituted maleimide structure is a group containing a bismaleimide structure, and the bismaleimide In the amine structure, the nitrogen atoms of the two maleimidine groups are bonded to each other via an organic group.
[4] The resin composition according to the above [2] or [3], wherein the group containing the N-substituted maleimide structure is a group represented by the following general formula (Z):

In the general formula (Z), R ^{2 is} each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, y is an integer of 0 to 4, and A ¹ is represented by the following general formulae (II), (III), (IV) or (V);

In the general formula (II), R ^{3 is} each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and p is an integer of 0 to 4;

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

In the general formula (III-1), R ⁶ and R ⁷ are each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and A ³ is an alkylene group, isopropylidene group, or ether having 1 to 5 carbon atoms. Group, thioether group, sulfofluorenyl group, carbonyloxy group, keto group or single bond, and s and t are each independently an integer of 0 to 4;

In the general formula (IV), n is an integer from 0 to 10;

In the general formula (V), R ⁸ and R ⁹ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and u is an integer of 1 to 8.
[5] The prepreg according to any one of the above [1] to [4], wherein the resin composition further comprises a hardening accelerator (B), the hardening accelerator (B) is selected from organic compounds At least one of the group consisting of an oxide, an imidazole-based hardening accelerator, and a phosphorus-based hardening accelerator.
[6] The prepreg according to any one of the above [1] to [5], wherein the resin composition further comprises a thermosetting resin (C), the thermosetting resin (C) being selected from the group consisting of At least one selected from the group consisting of an epoxy resin, a cyanate resin, and a maleimide compound.
[7] The prepreg according to the above [6], wherein the maleimide compound in the thermosetting resin (C) is selected from the group consisting of the maleimide compound (a) and the following At least one member of the group consisting of an amino bismaleimide compound (c) represented by the general formula (VI), the maleimide compound (a) having at least two N-substituted maleates醯 imine structure of the group,

In the general formula (VI), A ^{4 has} the same definition as A ¹ in the general formula (Z) described in the above [4], and A ⁵ is a group represented by the following general formula (VII):

In the general formula (VII), R ¹⁷ and R ¹⁸ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom, and A ⁸ is one having 1 to 5 carbon atoms. An alkylene group, an alkylene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfofluorenyl group, a carbonyloxy group, a keto group, a fluorenyl group, a single bond or the following general formula (VII-1) A group represented by (VII-2), q 'and r' are each independently an integer of 0 to 4;

In the general formula (VII-1), R ¹⁹ and R ²⁰ are each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and A ⁹ is an alkylene group, an isopropylidene group, or an intermediate group having 1 to 5 carbon atoms. Benzene isopropylidene or p-phenylene isopropylidene, ether group, thioether group, sulfofluorenyl group, carbonyloxy group, keto group or single bond, s 'and t' are each independently an integer of 0 to 4 ;

In the general formula (VII-2), R ²¹ is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and A ¹⁰ and A ¹¹ are each independently an alkylene group, isopropylidene group, or ether having 1 to 5 carbon atoms. Group, thioether group, sulfofluorenyl group, carbonyloxy group, keto group, or single bond, and w is an integer of 0 to 4.
[8] A laminated board comprising the prepreg and the metal foil according to any one of [1] to [7] above.
[9] A multilayer printed wiring board comprising the prepreg according to any one of the above [1] to [7] or the laminated board according to the above [8].
[10] A semiconductor package obtained by assembling a semiconductor element to the multilayer printed wiring board described in [9] above.
[11] A resin composition containing a polyphenylene ether derivative (A) and an organic solvent, the polyphenylene ether derivative (A) having a group containing an N-substituted maleimide structure, and the resin The solid content concentration of the composition was 50.5 mass% or more.
[12] The resin composition according to the above [11], wherein the polyphenylene ether derivative (A) having a group containing an N-substituted maleimide structure has a general formula (I) Represented structural unit:

In the general formula (I), each of R ^{1 is} independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and x is an integer of 0 to 4.
[13] The resin composition according to the above [11] or [12], wherein the group containing the N-substituted maleimide structure is a group represented by the following general formula (Z):

In the general formula (Z), R ^{2 is} each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, y is an integer of 0 to 4, and A ¹ is represented by the following general formulae (II), (III), (IV) or (V);

In the general formula (II), R ^{3 is} each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and p is an integer of 0 to 4;

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

In the general formula (III-1), R ⁶ and R ⁷ are each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and A ³ is an alkylene group, isopropylidene group, or ether having 1 to 5 carbon atoms. Group, thioether group, sulfofluorenyl group, carbonyloxy group, keto group or single bond, and s and t are each independently an integer of 0 to 4;

In the general formula (IV), n is an integer from 0 to 10;

In the general formula (V), R ⁸ and R ⁹ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and u is an integer of 1 to 8.
[14] The resin composition according to any one of the above [11] to [13], wherein the resin composition further comprises a hardening accelerator (B), the hardening accelerator (B) being selected from organic solvents At least one of the group consisting of an oxide, an imidazole-based hardening accelerator, and a phosphorus-based hardening accelerator.
[15] The resin composition according to any one of the above [11] to [14], wherein the resin composition further comprises a thermosetting resin (C), the thermosetting resin (C) being selected from the group consisting of At least one selected from the group consisting of an epoxy resin, a cyanate resin, and a maleimide compound.
[16] The resin composition according to the above [15], wherein the maleimide compound in the thermosetting resin (C) is selected from the group consisting of a maleimide compound (a) and At least one member of the group consisting of an amino bismaleimide compound (c) represented by the general formula (VI), the maleimide compound (a) having at least two N-substituted maleates醯 imine structure of the group,

In the general formula (VI), A ^{4 has} the same definition as A ¹ in the general formula (Z) described in the above [13], and A ⁵ is a group represented by the following general formula (VII):

In the general formula (VII), R ¹⁷ and R ¹⁸ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom, and A ⁸ is one having 1 to 5 carbon atoms. An alkylene group, an alkylene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfofluorenyl group, a carbonyloxy group, a keto group, a fluorenyl group, a single bond or the following general formula (VII-1) A group represented by (VII-2), q 'and r' are each independently an integer of 0 to 4;

In the general formula (VII-1), R ¹⁹ and R ²⁰ are each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and A ⁹ is an alkylene group, an isopropylidene group, or an intermediate group having 1 to 5 carbon atoms. Benzene isopropylidene or p-phenylene isopropylidene, ether group, thioether group, sulfofluorenyl group, carbonyloxy group, keto group or single bond, s 'and t' are each independently an integer of 0 to 4 ;

In the general formula (VII-2), R ²¹ is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and A ¹⁰ and A ¹¹ are each independently an alkylene group, isopropylidene group, or ether having 1 to 5 carbon atoms. Group, thioether group, sulfofluorenyl group, carbonyloxy group, keto group, or single bond, and w is an integer of 0 to 4.
[17] A method for producing a prepreg, comprising impregnating or coating a resin composition on a sheet-like fiber-reinforced base material and drying the resin composition to produce a prepreg, and the method includes exhausting the prepreg The treatment step (X) in which the amount satisfies the following conditions, and the conditions for the exhaust amount are:
The amount of exhaust gas generated when the prepreg was heated at a temperature of 163 ° C. for 15 minutes was less than 0.7% by mass based on the entire prepreg.
[18] A method for manufacturing a laminated board, which comprises manufacturing a laminated board by laminating a prepreg and a metal foil, and heating and pressing by a pressing method. The prepreg is as described in the above [17] It is obtained by a method for manufacturing a prepreg.
[19] A method for manufacturing a multilayer printed wiring board, which comprises manufacturing a multilayer printed wiring board by performing circuit formation processing and multilayer adhesion processing on a prepreg or a laminated board, the prepreg being manufactured by the above [17] It is obtained by the manufacturing method of the prepreg mentioned above, and this laminated board is obtained by the manufacturing method of the laminated board as described in said [18].
[Effect of the invention]

According to the present invention, it is possible to provide a prepreg, a laminated board, a multilayer printed wiring board, and a semiconductor package. The prepreg has high adhesion to a conductor, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient, and difficulty. Combustibility, and can exhibit stable and excellent high-frequency characteristics (dielectric characteristics in the high-frequency region). Furthermore, it is possible to provide a resin composition capable of providing the prepreg. Therefore, this resin composition, a prepreg, and a laminated board can be suitably used for electronic component applications, such as a multilayer printed wiring board and a semiconductor package.
Furthermore, by the manufacturing method of the multilayer printed wiring board using the manufacturing method of the prepreg of this invention, or the manufacturing method of a laminated board, it is possible to manufacture a multilayer printed wiring board which consists of a laminated board, and this laminated board It has high adhesion to the conductor, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient and flame resistance, and excellent high-frequency characteristics (dielectric characteristics in the high-frequency region).

Hereinafter, embodiments of the present invention will be described in detail. In addition, in this specification, a numerical range from X to Y may be expressed as "X to Y" (X and Y are real numbers). For example, a description such as "0.1 to 2" indicates a numerical range of 0.1 or more and 2 or less, and the numerical range includes 0.1, 0.34, 1.03, 2 and the like.
In the numerical range described in this specification, the upper limit value or lower limit value of the numerical range may be replaced with the value shown in the embodiment. The lower limit value and the upper limit value of the numerical range may be arbitrarily combined with the lower limit value or the upper limit value of the other numerical ranges.
It is also included in the scope of the present invention that an arbitrary combination of the matters described in this specification is included.

[Prepreg]
The present invention provides a prepreg comprising a resin composition and a sheet-like fiber-reinforced base material. When the prepreg is heated at a temperature of 163 ° C for 15 minutes (hereinafter, sometimes referred to as "exhaust volume" The amount of exhaust gas generated during the heat treatment for investigation ") was less than 0.7% by mass based on the entire prepreg (specifically, less than 0.70% by mass). The exhaust amount is preferably 0.69 mass% or less, more preferably 0.67 mass% or less, still more preferably 0.65 mass% or less, and particularly preferably 0.63 mass% or less, and most preferably, based on the entire prepreg as a reference. 0.61 mass% or less. The lower limit of the exhaust gas amount is not particularly limited, but it is usually 0.1 mass% or more, may be 0.3 mass% or more, may be 0.4 mass% or more, and may be 0.45 mass% or more.
Furthermore, in the present invention, the prepreg is not made completely hardened (C-staged), that is, it is made semi-hardened (B-staged).
The inventors have determined through research that in order to obtain a laminated board having the following characteristics, it is important to suppress the exhaust gas volume of the prepreg to within the aforementioned specific value, and have completed the present invention. The characteristics are as follows: Those with high adhesion, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient, and good flame resistance, and have excellent high-frequency characteristics.

As one of the methods for reducing the exhaust amount of the prepreg of the present invention, (a) a method of adjusting the solid content concentration of the resin composition of the present invention to 50.5% by mass or more, and (b) a method of manufacturing a preform It is preferable to use at least one selected from the group consisting of the methods for adjusting the drying conditions during the immersion.
Furthermore, in the present invention, the aforementioned exhaust gas volume is a mass change rate, which is a mass and exhaust gas volume of a prepreg before heating treatment (hereinafter, sometimes simply referred to as a prepreg before heating treatment) based on the exhaust gas volume investigation. The gas volume survey is obtained by using the mass of the heat-treated prepreg (hereinafter sometimes referred to as the heat-treated prepreg), and the mass change rate can be calculated by the following formula:
Exhaust volume (% by mass) = {(mass of prepreg before heat treatment-mass of prepreg after heat treatment) / mass of prepreg before heat treatment} × 100
The component of the exhaust gas is not particularly limited, and it is considered that it contains at least one selected from the group consisting of raw materials mixed with each component, and each component is composed of an organic solvent and a resin contained in a resin composition Thing.

(Manufacturing method of prepreg)
As a method for producing a prepreg according to the present invention, for example, a method for producing a prepreg, in which a resin composition is impregnated or coated on a sheet-like fiber-reinforced substrate and dried to produce a prepreg, and The manufacturing method includes a disposing step (X) of satisfying a condition that an exhaust amount of the prepreg body satisfies the condition of "exhaust gas generated when the prepreg body is heated at a temperature of 163 ° C for 15 minutes. The amount is less than 0.7% by mass based on the entire prepreg. " The exhaust amount is the same as that described above.
As this step (X), the exhaust amount of the prepreg is not particularly limited as long as it is within the aforementioned range, and examples include: (a) a step of adjusting the solid content concentration of the resin composition of the present invention to 50.5 mass% or more [Hereinafter, sometimes referred to as (a) step], (b) A step of adjusting the drying conditions during the production of the prepreg [hereinafter, sometimes referred to as (b) step], and the like.
The solid content concentration of the resin composition in the step (a) will be described later. In the aforementioned step (b), from the viewpoint of operating in such a manner that the resin in the resin composition is not decomposed, staying in the B-stage without forming the C-stage, and reducing the amount of exhaust gas, Preferably, for example, the following drying conditions are used: The temperature is preferably 80 to 200 ° C, more preferably 100 to 180 ° C, and still more preferably 120 to 170 ° C. The heat drying is preferably 1 to 30 minutes, and more preferably 5 to 25 minutes, more preferably 10 to 20 minutes.
The amount of the resin composition used is preferably such that the solid content derived from the resin composition in the dried prepreg becomes 30 to 90% by mass (the residual portion corresponds to the content of the sheet-like fiber-reinforced substrate). To make adjustments. When the solid content derived from the resin composition in the dried prepreg is set within the above range to form a laminated board, there is a tendency that a better moldability can be obtained.

As the sheet-like fiber-reinforcing base material of the prepreg, a known material used in a laminated board for various electric insulation materials can be used. Examples of the material of the sheet-like fiber reinforcing substrate include inorganic fiber such as E glass fiber, D glass fiber, S glass fiber, and Q glass fiber; organic fibers such as polyimide, polyester, and tetrafluoroethylene; the And other fiber mixtures. The sheet-like fiber-reinforcing substrate may have a shape such as a woven fabric, a non-woven fabric, a roving, a chopped strand mat, or a surfacing mat. The thickness of the sheet-like fiber-reinforced substrate is not particularly limited, and for example, those having a thickness of 0.02 to 0.5 mm can be used. Further, from the viewpoints of impregnation of the resin composition, heat resistance when forming a laminated board, moisture absorption resistance, and processability, those obtained by surface treatment with a coupling agent or the like can be suitably used, and mechanical properties can be applied. Open fiber processing.
The resin composition contained in the prepreg will be described later.

As a method of impregnating or coating a resin composition on a sheet-like reinforcing substrate, a solvent method can be adopted.
The solvent method is a method in which an organic solvent is contained in a resin composition, and a sheet-like fiber-reinforced base material is impregnated in the obtained resin composition, so that the resin composition is impregnated in the sheet-like fiber-reinforced base material, It was then allowed to dry.

[Resin composition]
The resin composition contained in the prepreg of the present invention is not particularly limited, and a known resin composition used for an insulating resin layer or the like of a printed wiring board can be used. Among them, from the viewpoints of high adhesion to the conductor, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient, flame resistance, and high-frequency characteristics, it is preferably a resin composition containing a polyphenylene ether derivative (A) [hereinafter, may be simply referred to as a polyphenylene ether derivative (A) or (A) component], the polyphenylene ether derivative (A) has a group containing an N-substituted maleimide structure .
One aspect of a preferable resin composition is that it can be made into a high-adhesion to a conductor, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient, and flame resistance, and obtain excellent high-frequency characteristics. Is a resin composition containing a polyphenylene ether derivative (A) and an organic solvent, the polyphenylene ether derivative (A) having a group containing an N-substituted maleimide structure, and the resin The solid content concentration of the composition was 50.5 mass% or more. The solid content concentration referred to herein is a solid content concentration that also includes an inorganic filler when the resin composition of the present invention contains an inorganic filler (D) described later.
By setting the solid content of the resin composition to 50.5 mass% or more, compared with the case where the solid content is less than 50.5 mass%, there is a tendency that stable and high-frequency characteristics can be obtained. When a resin composition is impregnated or coated with a sheet-like fiber-reinforced substrate to produce a prepreg, the resin composition is difficult to handle if the fluidity of the resin composition is low, so in general, it is unlikely to increase the solid content. concentration. Therefore, the solid content concentration is often adjusted to less than 50.5 mass%. However, if a resin composition containing a polyphenylene ether derivative (A) is deliberately attempted to increase the solid content concentration to the above range, it is observed that the reduction of the organic solvent remaining in the laminate may reduce the high-frequency characteristics. Related to the reduction.

(Polyphenylene ether derivative (A))
The polyphenylene ether derivative (A) is not particularly limited as long as it is a polyphenylene ether derivative having a group containing an N-substituted maleimide structure. The number of the N-substituted maleimide structure-containing groups may be at least one.

In particular, by having a polyphenylene ether derivative (A) having a group containing an N-substituted maleimide structure, it can become an excellent high-frequency characteristic, high adhesion to a conductor, high glass transition temperature, Resin composition with low thermal expansion coefficient and high flame resistance. Here, the thermal expansion coefficient referred to in the present invention is a value also called a linear expansion coefficient. The group containing an N-substituted maleimide structure is not particularly limited as long as it contains an N-substituted maleimide.

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

In the general formula (I), each of R ^{1 is} independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and x is an integer of 0 to 4.

Examples of the aliphatic hydrocarbon group represented by R ¹ in the general formula (I) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, and n-pentyl. Base etc. 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. As the halogen element, from the viewpoint of making it halogen-free (reducing the content of chlorine atom, bromine atom, and iodine atom), a fluorine atom is preferred.
Among the above, 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. Furthermore, when x is 1 or 2, R ¹ may be substituted at the ortho position on the benzene ring (however, it is based on the substitution position of the oxygen atom). When x is 2 or more, a plurality of R ¹ may be the same as or different from each other.

As a structural unit represented by the said general formula (I), the structural unit represented by the following general formula (I ') is specifically preferable.

As a group containing a polyphenylene ether derivative (A), which contains an N-substituted maleimide structure, it has high frequency characteristics, adhesion to conductors, heat resistance, glass transition temperature, thermal expansion coefficient, and flame retardancy. From the viewpoint, it is preferable to include a bismaleimide structure (which also includes a structure derived from the structure. Here, the so-called structure derived from the structure is that the maleimide group has Carbon-carbon double bond with a functional group (amino group, etc.) and the structure formed by the reaction of etc.), the nitrogen atoms of the two maleimide groups in the double maleimide structure are organic The base is bonded. More preferred is a group represented by the following general formula (Z).

In the general formula (Z), R ^{2 is} each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, y is an integer of 0 to 4, and A ¹ is represented by the following general formulae (II), (III), (IV) or (V).

The description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and a halogen atom represented by R ² is the same as in the case of R ¹ .

y is an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0. When y is an integer of 2 or more, the plural R ² may be the same as or different from each other.

The group represented by A ^{1 and} represented by the following general formula (II), (III), (IV), or (V) is as follows.

In the general formula (II), each of R ^{3 is} independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and p is an integer of 0 to 4.
The description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and a halogen atom represented by R ³ is the same as in the case of R ¹ .

p is an integer of 0 to 4, and from the viewpoint of easiness of acquisition, it is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. When p is an integer of 2 or more, the plural R ³ may be the same as or different from each other.

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

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and halogen atoms represented by R ⁴ and R ⁵ are 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 and an ethyl group, and still more 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-ethylene, 1,3-propyl, and 1,4-butylene. , 1,5-pentyl and so on. The alkylene group is preferably an alkylene group having 1 to 3 carbon atoms from the viewpoint of high-frequency characteristics, adhesion to a conductor, heat resistance, glass transition temperature, thermal expansion coefficient, and flame retardancy. Is a methylenyl group.

Examples of the alkylene group having 2 to 5 carbon atoms represented by A ² include ethylene, propylene, isopropylidene, butylene, isobutylene, pentylene, and isopentylene. Among these, from the viewpoints of high-frequency characteristics, adhesiveness to a conductor, heat resistance, glass transition temperature, thermal expansion coefficient, and flame retardancy, isopropylidene is preferred.
Among the above, A ² is preferably an alkylene group having 1 to 5 carbon atoms and an alkylene group having 2 to 5 carbon atoms.

q and r are each independently an integer of 0 to 4, and from the viewpoint of easiness of acquisition, it 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 as or different from each other.

The group represented by general formula (III-1) represented by A ² is as follows.

In the general formula (III-1), R ⁶ and R ⁷ are each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and A ³ is an alkylene group, isopropylidene group, or ether having 1 to 5 carbon atoms. Group, thioether group, sulfofluorenyl group, carbonyloxy group, keto group, or single bond, and s and t are each independently an integer of 0 to 4.

The descriptions of the aliphatic hydrocarbon groups having 1 to 5 carbon atoms and halogen atoms represented by R ⁶ and R ⁷ are the same as those of R ⁴ and R ⁵ .

Examples of the alkylene group having 1 to 5 carbon atoms represented by A ^{3 are the} same as the alkylene group having 1 to 5 carbon atoms represented by A ² .
Among the above, A ³ is preferably an alkylene group having 2 to 5 carbon atoms.

s and t are integers of 0 to 4, and from the viewpoint of easiness of acquisition, they are preferably integers 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 as or different from each other.

In General Formula (IV), n is an integer of 0-10.

From the viewpoint of availability, 0 to 5 is preferred, and 0 to 3 is more preferred.

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

The description of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and a halogen atom represented by R ⁸ and R ⁹ is the same as in the case of R ¹ .
u is an integer of 1 to 8, preferably an integer of 1 to 3, and more preferably 1.

As A ¹ in the group represented by the general formula (Z), from the viewpoint of high-frequency characteristics, adhesion to a conductor, heat resistance, glass transition temperature, thermal expansion coefficient, and flame retardancy, the following are preferred: A group represented by any one of the formulae.

As A ¹ in the group represented by the general formula (Z), from the viewpoints of high-frequency characteristics, adhesion to a conductor, heat resistance, glass transition temperature, thermal expansion coefficient, and flame retardancy, the following are more preferable: A group represented by any one of the formulae.

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

In the general formula (A '), A ¹ , R ¹ , R ² , x, and y have the same meanings as defined above, and 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, still more preferably an integer of 30 to 200, and particularly preferably an integer of 50 to 150.

The polyphenylene ether derivative (A) is preferably a polyphenylene ether derivative represented by any one of the following formulae (A'-1) to (A'-4).

In the formula, m is the same as m in the aforementioned general formula (A '), and the preferred range is also the same.

From the viewpoint of cheap raw materials, the polyphenylene ether derivative of the above formula (A'-1) is preferable, and from the viewpoint of excellent dielectric properties and low water absorption, the above formula (A ' -2) The polyphenylene ether derivative is preferably the above-mentioned formula (A'-3) or the above-mentioned formula (A) from the viewpoint of excellent adhesion to a conductor and mechanical properties (tensile strength, breaking strength, etc.). '-4) Polyphenylene ether derivative. Therefore, it is possible to use one of the polyphenylene ether derivatives represented by any one of the above-mentioned formulae (A'-1) to (A'-4) alone, or to use two or more kinds in combination, in accordance with the characteristics intended.

The number average molecular weight of the polyphenylene ether derivative (A) of the present invention is preferably from 4000 to 14,000, more preferably from 5,000 to 12,000, even more preferably from 7,000 to 12,000, and particularly preferably from 7,000 to 10,000. The number average molecular weight of the polyphenylene ether derivative (A) may be 4,000 to 8,000, or 4,000 to 6,500. As long as the number average molecular weight is 4,000 or more, the resin composition of the present invention, a prepreg and a laminated board using the resin composition tend to obtain a better glass transition temperature. In addition, as long as the number average molecular weight is 14,000 or less, when the resin composition of the present invention is used in a laminated board, there is a tendency that a better moldability can be obtained.
In the present specification, the number average molecular weight is a value obtained by gel permeation chromatography (GPC) conversion from a calibration curve using standard polystyrene. More specifically, The value obtained by the above-mentioned method of measuring the number average molecular weight.

The content of the (A) component in the resin composition of the present invention is not particularly limited, and from the viewpoint of high-frequency characteristics and the like, it is preferably 1% by mass or more, more preferably 1 to 50% by mass relative to the resin composition. %, More preferably 1 to 25% by mass, and particularly preferably 1 to 10% by mass.

(Manufacturing method of polyphenylene ether derivative (A))
The polyphenylene ether derivative (A) can be obtained, for example, by the following production method.
First, it is known to make an amine phenol compound [hereinafter, referred to as an amine phenol compound (VIII)] and a polyphenylene ether having a number average molecular weight of 15,000 to 25,000 in an organic solvent. Redistribution reaction, it is possible to produce a polyphenylene ether compound (A '') having a primary amine group while reducing the molecular weight of polyphenylene ether (hereinafter, also simply referred to as a polyphenylene ether compound (A '')) Then, the polyphenylene ether compound (A '') and a bismaleimide compound represented by the general formula (IX) [hereinafter, referred to as a maleimide compound (IX) ] By performing the Michael addition reaction, a polyphenylene ether derivative (A) can be produced.

In the general formula (VIII), R ² and y are the aforementioned general formula (Z) in R ² and y are the same.

In the general formula (IX), A ¹ is the same as A ¹ in the general formula (Z).

Examples of the amine phenol compound (VIII) include ortho-amine phenol, m-amine phenol, and p-amine phenol. Among these, from the viewpoints of the reaction yield at the time of producing the polyphenylene ether compound (A '') and the heat resistance when the resin composition, the prepreg and the laminated board are produced, m-aminophenol, Para-aminophenol is more preferably para-aminophenol.

The molecular weight of the polyphenylene ether compound (A '') can be controlled by the amount of the amine phenol compound (VIII) used. The more the amount of the amine phenol compound (VIII) used, the more the obtained polyphenylene ether compound (A '' ), The more the molecular weight can be reduced. That is, in order to make the number-molecular weight of the polyphenylene ether derivative (A) finally manufactured into an appropriate range, the amount of the amine-phenol compound (VIII) used may be adjusted.

The blending amount of the amine phenol compound (VIII) is not particularly limited. For example, as long as the number average molecular weight of the polyphenylene ether that reacts with the amine phenol compound (VIII) is 15,000 to 25,000, 100 parts by mass of the polyphenylene ether. By using within the range of 0.5 to 6 parts by mass, a polyphenylene ether derivative (A) having a number average molecular weight of 4000 to 14000 can be obtained.

The organic solvent used in the production step of the polyphenylene ether compound (A '') is not particularly limited, and examples thereof include methanol, ethanol, butanol, butylcellulose, ethylene glycol monomethyl ether, and propylene glycol monomethyl. Alcohol solvents such as ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; aromatic hydrocarbons such as toluene, xylene, mesitylene; methoxyethyl acetate Esters, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate, etc .; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl Nitrogen-containing compounds such as 2-pyrrolidone and the like. These components may be used individually by 1 type, and may use 2 or more types together. Among these, toluene, xylene, and mesitylene are preferred from the viewpoint of solubility.

In addition, in the production step of the polyphenylene ether compound (A ''), a reaction catalyst can be used as necessary. As the reaction catalyst, a reaction catalyst used in a known redistribution reaction can be applied. For example, from the viewpoint of obtaining a polyphenylene ether compound (A '') having a good number reproducibility and a stable number average molecular weight, an organic peroxide such as tertiary butyl isopropylperoxide and the like can be used in combination with A metal salt of a carboxylic acid such as manganese naphthenate. The amount of the reaction catalyst used is not particularly limited. For example, from the viewpoints of the reaction rate when producing the polyphenylene ether compound (A ") and the inhibition of gelation, organic matter can be converted to 100 parts by mass of the aforementioned polyphenylene ether that reacts with the amine phenol compound (VIII). The peroxide is set to 0.5 to 5 parts by mass, and the carboxylic acid metal salt is set to 0.05 to 0.5 parts by mass.

A specific amount of the aforementioned amine-phenol compound (VIII), the aforementioned number-average molecular weight polyphenylene ether of 15,000-25,000, an organic solvent, and a required reaction catalyst are poured into the reactor, and the reaction is performed while heating, holding, and stirring. In this way, a polyphenylene ether compound (A '') can be obtained. For the reaction temperature and reaction time in this step, conventional reaction conditions at the time of a redistribution reaction can be applied.
From the viewpoint of operability and inhibition of gelation, and from the viewpoint of controlling the molecular weight of the polyphenylene ether compound (A ") for obtaining the desired number average molecular weight (A) component, for example, The reaction is performed under the conditions of a reaction temperature of 70 to 110 ° C and a reaction time of 1 to 8 hours.

The solution of the polyphenylene ether compound (A '') prepared as described above can be directly and continuously supplied to the production step of the polyphenylene ether derivative (A) in the next step. At this time, the solution of the polyphenylene ether compound (A '') may be cooled or adjusted to the reaction temperature in the next step. The solution may be concentrated as necessary to remove a part of the organic solvent as described later, or it may be diluted by adding an organic solvent.

Examples of the bismaleimide imine compound (IX) used in the production of the polyphenylene ether derivative (A) include bis (4-maleimidephenyl) methane and polyphenylmethane maleate. Hydrazone, bis (4-maleimidephenyl) ether, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide , 4-methyl-1,3-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis (4- (4-maleimide phenoxy) phenyl ) Propane, bis (4-maleiminoiminophenyl) fluorene, bis (4-maleiminoiminophenyl) sulfide, bis (4-maleiminophenyl) ketone, bis (4- (4-maleimidoiminophenoxy) phenyl) fluorene, 4,4'-bis (3-maleimidoiminophenoxy) biphenyl, 1,6-bismaleimidoimino- (2,2,4-trimethyl) hexane and the like. These compounds may be used individually by 1 type, and may use 2 or more types together.

Among these, bis (4-maleiminophenyl) methane and 3,3'-dimethyl-5,5 are preferred from the viewpoint of high reactivity and higher heat resistance. '-Diethyl-4,4'-diphenylmethane bismaleimide, 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane.

From the viewpoint that a polyphenylene ether derivative containing a polyphenylene ether derivative represented by the aforementioned formula (A'-1) can be obtained and the price is inexpensive, bis (4-maleiminophenylene) is preferred. ) Methane.
From the viewpoint that a polyphenylene ether derivative containing a polyphenylene ether derivative represented by the aforementioned formula (A'-2) can be obtained and has excellent dielectric properties and low water absorption, 3,3'- Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide.
A polyphenylene ether derivative containing a polyphenylene ether derivative represented by the aforementioned formula (A'-3) or (A'-4) can be obtained, and has high adhesion and mechanical properties (tensile, breaking strength) to the conductor From the viewpoint of being excellent, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, 1,6-bismaleimidoimino- (2 , 2,4-trimethyl) hexane.

The use amount of the bismaleimide compound (IX) is determined based on the use amount of the amine phenol compound (VIII). That is, the equivalent ratio (Tb1 / Ta1) of the -NH ₂ group equivalent (Ta1) of the amine phenol compound (VIII) to the maleimide group equivalent (Tb1) of the bismaleimide compound (IX) may be It is set in the range of 2 to 6, and it can also be adjusted in the range of 2 to 4. By using the bismaleimide imine compound (IX) within the range of the above-mentioned equivalent ratio, the resin composition, the prepreg, and the laminate of the present invention tend to obtain more excellent heat resistance and high Glass transition temperature and high flame resistance.

In the Michael addition reaction in the production of the polyphenylene ether derivative (A), a reaction catalyst can be used as necessary. The reaction catalyst that can be used is not particularly limited, and examples thereof include acid catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine, and tributylamine; and imidazoles such as methylimidazole and phenylimidazole. Compounds; phosphorus catalysts such as triphenylphosphine. These components may be used individually by 1 type, and may use 2 or more types together. The amount of the reaction catalyst is not particularly limited. For example, it is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the polyphenylene ether compound (A '').

A specific amount of the above-mentioned bismaleimide compound (IX) and a reaction catalyst according to need are poured into a solution of a polyphenylene ether compound (A ''), and a polyphenylene oxide is obtained by performing a Michael addition reaction. Ether derivative (A). This step is preferably performed while heating, holding, and stirring. As reaction conditions, from the viewpoint of operability and inhibition of gelation, for example, the reaction temperature is preferably 50 to 160 ° C and the reaction time is 1 to 10 Within hours. In this step, the reaction concentration (solid content concentration) and solution viscosity can be adjusted by adding or concentrating an organic solvent as described above. As the additional organic solvent, the organic solvents exemplified in the production steps of the polyphenylene ether compound (A '') can be applied, and these components may be used alone or in combination of two or more. Among these, from the viewpoint of solubility, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N, N-dimethylformamide, and N, N- Dimethylacetamide, toluene.

The reaction concentration (solid content concentration) in the production steps of the polyphenylene ether derivative (A) and the polyphenylene ether compound (A ″) is not particularly limited. For example, in any of the production steps It is preferably 10 to 60% by mass, and more preferably 20 to 50% by mass. As long as the reaction concentration is 10% by mass or more, the reaction rate does not become too slow, and it tends to become more advantageous in terms of manufacturing costs. In addition, if the reaction concentration is 60% by mass or less, there is a tendency to obtain better solubility. In addition, when the viscosity of the solution is low, the stirring efficiency is good, and gelation tends to be less likely to occur.

In addition, after the production of the polyphenylene ether derivative (A), from the viewpoint of operability at the time of taking out from the reactor, and the addition of various thermosetting resins and the like to the polyphenylene ether derivative (A), the invention was made. When using the resin composition (for example, the viscosity of the solution and the concentration of the solution suitable for the production of prepregs), some or all of the organic solvents in the solution can be appropriately removed and concentrated, and organic solvents can be added to dilution. The organic solvent used for the addition is not particularly limited, and one or more kinds of the organic solvents can be applied.

By the formation of the polyphenylene ether compound (A '') and the polyphenylene ether derivative (A) obtained in the aforementioned manufacturing steps, a small amount of samples can be taken out after the respective steps are completed, and GPC measurement and IR Spectroscopy).
First, from the GPC measurement, the molecular weight of the polyphenylene ether compound (A ") is reduced compared to the polyphenylene ether of the raw material, and the peak of the amine phenol compound (VIII) of the raw material disappears. Furthermore, from the IR measurement, It can be seen that the appearance of the primary amine group of 3300 to 3500 cm ^-1 can confirm that the desired polyphenylene ether compound (A '') has been produced. In addition, after further purification of the polyphenylene ether derivative (A) by reprecipitation, from the IR measurement, it was confirmed that the peak of the primary amine group at 3300 to 3500 cm ^-1 disappeared and the malea at 1700 to 1730 cm ^-1 was confirmed. The appearance of the peak of the carbonyl group of the sulfonimine can confirm that the desired polyphenylene ether derivative (A) has been produced.

Compared with a resin composition containing a polyphenylene ether compound (A '') and a component (C) described later, the resin composition of the present invention has adhesion to a conductor, a coefficient of thermal expansion, flame retardancy, and processability. (Drilling, cutting) tends to be more excellent.

(Organic solvents)
The resin composition of the present invention preferably contains an organic solvent to adjust the solid content concentration from the viewpoint of dielectric characteristics, the viewpoint that processing is easy to perform, and the viewpoint that it becomes easy to manufacture a prepreg described later. Within the aforementioned range.
From the viewpoint of high-frequency characteristics, the content of the organic solvent in the resin composition of the present invention is preferably adjusted so that the solid content concentration becomes 50.5% by mass or more. The solid content concentration of the resin composition is preferably 50.5 to 90% by mass, more preferably 51.0 to 80% by mass, still more preferably 53.0 to 80% by mass, even more preferably 55.0 to 80% by mass, and particularly preferably 55.0. It is 75% by mass, and most preferably 55.0 to 70.0% by mass. By using a resin composition having a solid content concentration within the above range, stable and excellent high-frequency characteristics can be expressed, and good high-frequency characteristics can be further improved. In addition, the handleability of the prepreg becomes easy, and further, the impregnation property to the substrate and the appearance of the prepared prepreg are good, and it becomes easy to produce a prepreg having a desired thickness. Propensity. On the other hand, if the solid content concentration is less than 50.5% by mass, the organic solvent in the resin composition may remain slightly, so the high-frequency characteristics may be slightly reduced. In order to meet the strong demand for high-frequency characteristics in recent years, it is important to suppress the degradation of the high-frequency characteristics.

Examples of the organic solvent include alcohol-based solvents such as ethanol, propanol, butanol, methylcellulose, butylcellulose, and propylene glycol monomethyl ether; acetone, methyl ethyl ketone, and methyl isopropyl alcohol. Ketone solvents such as butyl ketone and cyclohexanone; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene, mesitylene; dimethylformamide, dimethylacetamide, N -A solvent containing a nitrogen atom such as methylpyrrolidone; a solvent containing a sulfur atom such as dimethylarsinide; an ester solvent such as γ-butyrolactone. These components may be used individually by 1 type, and may mix and use 2 or more types. Among these, from the viewpoint of solubility, alcohol-based solvents, ketone-based solvents, and aromatic solvents are preferred, and aromatic solvents are more preferred. More specifically, propylene glycol monomethyl ether and toluene are preferable.

(Hardening accelerator (B))
The resin composition of the present invention preferably contains a hardening accelerator (B) in addition to the component (A), and is selected from the group consisting of an organic peroxide, an imidazole-based hardening accelerator, and a phosphorus-based hardening accelerator. At least one of the groups (hereinafter, may be simply referred to as a hardening accelerator (B) or (B) component). By containing (B) component, heat resistance etc. can be improved further.

The organic peroxide is not particularly limited, and examples thereof include methyl ethyl ketone peroxide, methyl ethyl acetate, ethyl acetone peroxide, and 1,1-bis (tertiary butyl peroxide). Cyclohexane, 2,2-bis (tertiary butyl peroxide) butane, tertiary butyl hydroperoxide, dicumyl hydroperoxide, 2,5-dihydroperoxy-2,5-di Methylhexane, 2,5-dimethyl-2,5-bis (tertiary butyl peroxide) hexyne, acetamidine peroxide, octyl peroxide, dodecyl peroxide, benzamidine peroxide , M-toluene peroxide, diisopropyl peroxide dicarbonate, tertiary butyl isopropyl peroxide monocarbonate, 1,1-di (tertiary hexyl peroxide) cyclohexane, tertiary elongation of benzoic acid Butyl ester, n-butyl-4,4-di (tert-butyl peroxide), p-menthane hydroperoxide, dicumyl hydroperoxide, -1,1,3,3 hydroperoxide -Tetramethylbutyl ester, cumene hydroperoxide, di (2-tert-butyl isopropyl peroxide) benzene, dicumyl peroxide, dicumyl hydroperoxide, 2,5-di Methyl-2,5-di (tertiary-butyl peroxide) hexane, tertiary-butyl isopropyl peroxide, di-tertiary peroxide Group, di-tertiary butyl peroxide, bis (1-phenyl-1-methylethyl) peroxide, α, α'-bis (tertiary butyl peroxide) dicumyl, and the like.

From the viewpoint of further improving the heat resistance, it is preferable that the organic peroxide contains at least one selected from the group consisting of the following organic peroxides: tert-butyl isopropyl monocarbonate Esters, 1,1-bis (tertiary hexyl peroxide) cyclohexane, bis (1-phenyl-1-methylethyl) peroxide, dicumyl hydroperoxide, and α, α'-bis ( Tributyl) dicumyl peroxide.

From the standpoint of storage stability and coatability, the organic peroxide is preferably one having a half-life temperature of 140 ° C. or higher and more preferably 160 ° C. or higher. The one-minute half-life temperature can be obtained by preparing a 0.1 mol / L organic peroxide solution in a solvent that is inactive to free radicals such as benzene, and making it in a glass container replaced with nitrogen. Pyrolysis was performed to measure the temperature at which the amount of active oxygen became half at one minute.

Examples of the imidazole-based hardening accelerator include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1 -Benzyl-2-methylimidazole, 2-heptadecylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline , 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethylimidazoline, 2-isopropylimidazole Phthaloline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline and the like.

From the viewpoint of storage stability of the resin composition, the imidazole-based hardening accelerator is preferably a masking imidazole masked by a masking agent. Examples of the masking agent include acrylonitrile, phenylene diisocyanate, toluidine isocyanate, naphthyl diisocyanate, methylene bisphenyl isocyanate, Melamine acrylic acid, hexyl diisocyanate, etc.

Examples of the phosphorus-based hardening accelerator include morphine, piperidine, pyrrolidine, dimethylamine, diethylamine, dicyclohexylamine, N-alkylarylamine, piperazine, diallylamine, and thiazoline , Amines such as thiomorpholine; dimethyl Tertiary amines such as amines, 2- (dimethylaminomethyl) phenol, 2,4,6-ginseno (diaminomethyl) phenol; tetrabutylammonium iodide, tetrabutylammonium bromide, Tetrabutylammonium chloride, tetrabutylammonium fluoride, chloride Quaternary ammonium salts such as benzalconium chloride, benzylbis (2-hydroxyethyl) ethylammonium chloride, decyl (2-hydroxyethyl) methylammonium chloride, and the like.

(B) A component may be used individually by 1 type, and may use 2 or more types together.

The content ratio of the (B) component is not particularly limited, and is, for example, 100 parts by mass with respect to the (A) component of the present invention (where the (C) component described later is the total of the (A) component and the (C) component) 100 parts by mass), preferably 0.01 to 25 parts by mass, and more preferably 0.01 to 20 parts by mass. If (B) component is used in such a range, it will become easy to obtain more favorable heat resistance and storage stability.

(Thermosetting resin (C))
The resin composition of the present invention may include, as component (C), a thermosetting resin selected from the group consisting of an epoxy resin, a cyanate resin, and a maleimide compound. 1 species. The maleimide compound does not include the polyphenylene ether derivative (A).

The epoxy resin is preferably an epoxy resin having two or more epoxy groups. Here, the epoxy resin can be classified into an epoxy-epoxy-type epoxy resin, an epoxy-amine-type epoxy resin, and an epoxy-epoxy resin. Among these, epoxy-epoxy type epoxy resin can be selected.

Epoxy resins can be classified into various epoxy resins based on different main skeletons. Among the above-mentioned different types of epoxy resins, they can be further classified into: bisphenol A epoxy resin, bisphenol F epoxy resin, Bisphenol epoxy resin such as bisphenol S epoxy resin; alicyclic epoxy resin; aliphatic chain epoxy resin; phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol Novolac epoxy resins such as A novolac epoxy resin, bisphenol F novolac epoxy resin, etc .; phenol arane epoxy resin; styrenic epoxy resin; dicyclopentadiene epoxy resin Naphthalene skeleton type epoxy resins such as naphthol novolac epoxy resin and naphthol arane epoxy resin; biphenyl epoxy resin; biphenylarane epoxy resin; xylene epoxy resin ; Dihydroanthracene type epoxy resin; Dicyclopentadiene type epoxy resin and the like.

An epoxy resin may be used individually by 1 type, and may use 2 or more types together. Among these, from the viewpoints of high-frequency characteristics, heat resistance, glass transition temperature, thermal expansion coefficient, flame retardancy, and the like, a naphthalene skeleton-type epoxy resin and a biphenylarane-type epoxy resin are preferred.

When an epoxy resin is used as the component (C), a curing agent, a curing aid, and the like of the epoxy resin can be used in combination as necessary. These components are not particularly limited, and examples thereof include polyamine compounds such as diethylenetriamine, triethylenetetramine, diaminediphenylmethane, m-phenylenediamine, and dicyandiamine; bisphenol A and phenol novolac Polyphenol compounds such as resins, cresol novolac resins, bisphenol A novolac resins, phenol arane resins; acid anhydrides such as phthalic anhydride, pyromite anhydride; carboxylic acid compounds; active ester compounds, and the like. These components may be used individually by 1 type, and may use 2 or more types together. The amount used is not particularly limited and can be appropriately adjusted depending on the purpose. Among these, from the viewpoints of heat resistance, glass transition temperature, thermal expansion coefficient, storage stability, and insulation reliability, polyhydric phenol compounds and active ester compounds are preferably used.

The cyanate resin is not particularly limited, and examples thereof include 2,2-bis (4-cyanoxybenzene) propane, bis (4-cyanoxybenzene) ethane, and bis (3,5-dimethyl-4- Cyanobenzene) methane, 2,2-bis (4-cyanobenzene) -1,1,1,3,3,3-hexafluoropropane, α, α'-bis (4-cyanobenzene) m-bis Cumene, cyanate compound of phenol addition dicyclopentadiene polymer, phenol novolac type cyanate compound, cresol novolac type cyanate compound, and the like. The cyanate resin may be used alone or in combination of two or more. Among these, 2,2-bis (4-cyanooxybenzene) propane is preferably used from the viewpoint of production cost and the viewpoint of a comprehensive balance of high-frequency characteristics and other characteristics.

When a cyanate resin is used as the component (C), a hardener, a hardening aid, and the like of the cyanate resin can be used in combination as necessary. These components are not particularly limited, and examples thereof include monophenol compounds, polyphenol compounds, amine compounds, alcohol compounds, acid anhydrides, and carboxylic acid compounds. These components may be used individually by 1 type, and may use 2 or more types together. The use amount of the hardener and the hardening assistant is not particularly limited, and can be appropriately adjusted according to the purpose. Among these, a monophenol compound is preferably used from the viewpoint of high-frequency characteristics, heat resistance, moisture absorption resistance, and storage stability.

When a monophenol compound is used, it is preferable to use a method of preparing a phenol-modified cyanate prepolymer by performing a pre-reaction from the viewpoint of solubility in an organic solvent. The monophenol compound used in combination can be formulated with all of a predetermined amount during prepolymerization, or a predetermined amount can be prepared in batches before and after prepolymerization, but from the standpoint of storage stability, Method for batch deployment.

The maleimide compound is not particularly limited, and may contain, for example, a compound selected from the maleimide compound (a) [hereinafter, sometimes referred to as (a) component] and a compound represented by the following general formula (VI) At least one member of the group consisting of an amino bismaleimide compound (c) [hereinafter, sometimes referred to as (c) component], the maleimide compound (a) having at least two compounds N-substituted maleimide group. From the viewpoints of solubility in an organic solvent, high-frequency characteristics, adhesion to a conductor, and moldability of a prepreg, as the maleimide imine compound, an aminobismaleimide is preferred. Imine compound (c).

The amine bismaleimide compound (c) can be obtained by, for example, (a) component and an aromatic diamine compound (b) having two primary amine groups [hereinafter, sometimes referred to as (b) component] It is obtained by performing a Michael addition reaction in an organic solvent.

In the general formula (VI), A ^{4 has} the same definition as A ¹ in the aforementioned general formula (Z), and A ⁵ is a group represented by the following general formula (VII).

In the general formula (VII), R ¹⁷ and R ¹⁸ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom, and A ⁸ is one having 1 to 5 carbon atoms. An alkylene group, an alkylene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfofluorenyl group, a carbonyloxy group, a keto group, a fluorenyl group, a single bond or the following general formula (VII-1) or The group represented by (VII-2), q 'and r' are each independently an integer of 0-4.

In the general formula (VII-1), R ¹⁹ and R ²⁰ are each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and A ⁹ is an alkylene group, an isopropylidene group, or an intermediate group having 1 to 5 carbon atoms. Benzene isopropylidene or p-phenylene isopropylidene, ether group, thioether group, sulfofluorenyl group, carbonyloxy group, keto group, or single bond, and s 'and t' are each independently an integer of 0 to 4 .

In the general formula (VII-2), R ²¹ is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and A ¹⁰ and A ¹¹ are each independently an alkylene group, isopropylidene group, or ether having 1 to 5 carbon atoms. Group, thioether group, sulfofluorenyl group, carbonyloxy group, keto group, or single bond, and w is an integer of 0 to 4.

As an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom represented by R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ^{21 in the} general formula (VII), (VII-1) or (VII-2), Examples thereof are the same as those of R ¹ in the general formula (I). The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.

The alkylene group having 1 to 5 carbon atoms and the alkylene group having 2 to 5 carbon atoms represented by A ⁸ and A ⁹ in the general formula (VII) or (VII-1) and the general formula (VII-2) The description of the alkylene group having 1 to 5 carbon atoms represented by A ¹⁰ and A ^{11 in the} above is the same as in the case of A ² in the general formula (III).

q 'and r' are each independently an integer of 0 to 4, and from the viewpoint of easiness of acquisition, it is preferably an integer of 0 to 2, and more preferably 0 or 2. s 'and t' are each independently an integer of 0 to 4. From the standpoint of easiness of acquisition, it is preferably an integer of 0 to 2, more preferably both of 0 or 1, and even more preferably both 0. w is an integer of 0 to 4, and from the viewpoint of easiness of acquisition, an integer of 0 to 2 is preferred, and 0 is more preferred.

Although it does not specifically limit as said (a) component, For example, the same thing as the said bismaleimide compound (IX) can be used. Examples of the component (a) include bis (4-maleimidephenyl) methane, polyphenylmethanemaleimide, bis (4-maleimidephenyl) ether, and bis (4 -Maleimide phenyl) fluorene, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1 , 3-phenylene bismaleimide, m-phenylene bismaleimide, 2,2-bis (4- (4-maleimide phenoxy) phenyl) propane, bis (4- Maleimide phenyl) sulfide, bis (4-maleimide phenyl) ketone, bis (4- (4-maleimide phenoxy) phenyl) fluorene, 4,4 ' -Bis (3-maleimidophenoxy) biphenyl, 1,6-bismaleimidoimino- (2,2,4-trimethyl) hexane and the like. (a) A component may be used individually by 1 type, and may use 2 or more types together based on the objective and a use. In addition, as the component (a), a bismaleimide compound is preferred. From the viewpoint of being inexpensive, bis (4-maleimidephenyl) methane is more preferred. From the viewpoint of excellent characteristics and low water absorption, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide is preferred. From the viewpoint that the conductor is excellent in high adhesion and mechanical properties (tensile strength, breaking strength, etc.), 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane is preferred. .

As described above, the amine maleimide compound (c) can be obtained by subjecting the aforementioned (a) component to an aromatic diamine compound (b) having two primary amine groups in a Michael addition reaction in an organic solvent. obtain.

The component (b) is not particularly limited. From the viewpoints of high solubility in organic solvents, high reaction rate during synthesis, and improved heat resistance, 4,4'-diamine diphenylmethane can be cited. , 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2-bis (4 -(4-aminophenoxy) phenyl) propane, 4,4 '-[1,3-phenylenebis (1-methylethylene)] bisaniline, 4,4'-[1,4 -Phenylene bis (1-methylethylene)] bisaniline and the like.
From the viewpoints of excellent solubility, reaction rate, and heat resistance and being inexpensive, 4,4'-diaminediphenylmethane and 4,4'-diamino-3,3'-dimethyl are preferred. Diphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane. Moreover, from the viewpoint of being excellent in solubility, reaction rate, and heat resistance and exhibiting high adhesion to a conductor, 2,2-bis (4- (4-aminophenoxy) phenyl) is preferred Propane, 4,4 '-[1,3-phenylenebis (1-methylethylene)] bisaniline, 4,4'-[1,4-phenylenebis (1-methylethylene) ] Diphenylamine. Furthermore, from the viewpoints of excellent solubility, reaction rate, heat resistance, and adhesiveness to the conductor, and high-frequency characteristics and moisture absorption resistance, it is preferable to select 4,4 '-[1,3-benzidine (1-methylethylene)] bisaniline, 4,4 '-[1,4-phenylenebis (1-methylethylene)] bisaniline.
These components may be used individually by 1 type, and may use 2 or more types together according to the objective, use, etc.

The organic solvent used in the production of the aforementioned aminobismaleimide imine compound (c) is not particularly limited, and for example, the organic solvent exemplified in the production step of the polyphenylene ether compound (A '') can be applied. These organic solvents may be used individually by 1 type, and may use 2 or more types together. Among these, from the viewpoint of solubility, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether, N, N-dimethylformamide, and N, N- Dimethylacetamide.

The amount of component (a) and component (b) used in the production of the component (c) is preferably -NH ₂ group equivalent (Ta2) of component (b) and the maleimidine group of component (a). The equivalent ratio (Tb2 / Ta2) of the equivalent (Tb2) is in the range of 1 to 10, and more preferably in the range of 2 to 10. By using the component (a) and the component (b) within the above range, the resin composition, the prepreg, and the laminated board of the present invention can obtain excellent high-frequency characteristics, high adhesion to a conductor, and excellent Heat resistance, high glass transition temperature and high flame resistance.

The reaction catalyst may not be used in the Michael addition reaction in the production of the aforementioned amine maleimide compound (c) component, but it can still be used as required. The reaction catalyst is not particularly limited, and a reaction catalyst capable of being used in the Michael addition reaction when producing the polyphenylene ether derivative (A) can be used. The preparation amount of the reaction catalyst is also the same as described above, and is not particularly limited.

When a maleimide compound is used as the component (C), a curing agent, a cross-linking agent, a curing aid, and the like of the maleimide compound can be used in combination. These components are not particularly limited, and examples thereof include vinyl compounds such as styrene monomer, divinylbenzene, and divinyl biphenyl; (meth) acrylate compounds; triallyl tricyanate, and isocyanurate Allyl compounds such as triallyl acid; polyamine compounds such as diamine diphenylmethane; and the like. These components may be used individually by 1 type, and may use 2 or more types together. The amount of these components used is also not particularly limited, and can be appropriately adjusted depending on the purpose. Among these, ethylene compounds and polyamine compounds can be used from the viewpoints of high-frequency characteristics, heat resistance, and the like.

Pour a specific amount of the above-mentioned components (a), (b), organic solvents, and reaction catalysts as needed in the reactor, heat, keep warm, stir, and allow the Michael addition reaction to proceed to obtain amino horses. Lyximine compound (c). The reaction conditions such as the reaction temperature and the reaction time in this step can be applied to, for example, the reaction conditions at the time of the Michael addition reaction at the time of producing the polyphenylene ether derivative (A).

The reaction concentration (solid content concentration) is not particularly limited, but is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass. When the reaction concentration is 10% by mass or more, the reaction speed does not become too slow, but it tends to become more advantageous in terms of manufacturing costs. When the reaction concentration is 90% by mass or less, there is a tendency to obtain better solubility. In addition, the lower the viscosity of the solution is, the better the stirring efficiency is, and the gelation is reduced. In addition, after the amine maleimide compound (c) is produced, it is possible to remove (concentrate) part or all of the organic solvent or add additional organic solvents depending on the purpose, as in the case of producing the polyphenylene ether derivative (A). Organic solvents for dilution.

(Content ratio of (A) component and (C) component)
When the resin composition of the present invention contains the component (C), the content ratio [(A) / (C)] of the component (A) to the component (C) is not particularly limited. Based on the mass ratio, It is preferably 5/95 to 80/20, more preferably 5/95 to 75/25, still more preferably 5/95 to 70/30, even more preferably 5/95 to 50/50, and particularly preferably 10 / 90 ～ 50/50. With respect to the total of the (A) component and the (C) component, as long as the content ratio of the (A) component is 5% by mass or more, more excellent high-frequency characteristics and low hygroscopicity tend to be obtained. Moreover, if it is 80 mass% or less, there exists a tendency for more excellent heat resistance, more excellent moldability, and more excellent processability.

The thermosetting resin composition of the present invention can optionally use an inorganic filler (D) (hereinafter, sometimes referred to as (D) component), a flame retardant (E) (hereinafter, sometimes referred to as ( E) ingredients). By including these components, various characteristics at the time of forming a laminated board can be further improved. For example, by arbitrarily containing a suitable inorganic filler in the curable resin composition of the present invention, low thermal expansion characteristics, high elastic modulus properties, heat resistance, flame resistance, and the like can be improved. In addition, by containing a suitable flame retardant, high flame resistance can be imparted while suppressing reduction in high-frequency characteristics, heat resistance, adhesion to the conductor, and glass transition temperature.

(Inorganic Filler (D))
The (D) component used in the thermosetting resin composition of the present invention is not particularly limited, and examples thereof include silicon dioxide, aluminum oxide, titanium oxide, mica, beryllite, barium titanate, and potassium titanate. Clay, talc, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, calcined clay, etc. , Aluminum borate, silicon carbide, etc. These components may be used individually by 1 type, and may use 2 or more types together. The shape and particle diameter of the inorganic filler are not particularly limited. For example, those having a particle diameter of 0.01 to 20 μm, and preferably those having a particle diameter of 0.1 to 10 μm can be suitably used. Here, the particle diameter means an average particle diameter, and is a particle diameter corresponding to a point of 50% by volume when a cumulative particle size distribution curve derived from the particle diameter is obtained by setting the total volume of the particles to 100%. It can be measured by a particle size distribution measuring device or the like using a laser diffraction scattering method.

When the (D) component is used, the amount used is not particularly limited, but for example, the content ratio of the (D) component in the thermosetting resin composition containing the (D) component is preferably 3 to 65% by volume, more preferably It is 5 to 60% by volume, and more preferably 10 to 60% by volume. When the content ratio of the (D) component in the entire thermosetting resin composition is within the above range, good curability, moldability, and chemical resistance can be obtained. When the component (D) is used, a coupling agent is preferably used in combination for the purpose of improving the dispersibility of the component (D) and the adhesion between the component (D) and the organic component in the resin composition. The coupling agent is not particularly limited, and various silane coupling agents and titanate coupling agents can be used, for example. These components may be used individually by 1 type, and may use 2 or more types together. The amount of the coupling agent used is not particularly limited, but it is preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 3 parts by mass based on 100 parts by mass of the (D) component used. As long as it is within this range, degradation of various characteristics can be reduced, and the characteristics produced by using the (D) component can be effectively exhibited. When a couplant is used, it is preferred to use a surface-treated organic filling material rather than an integral blending treatment. The surface-treated organic filling material is dried in advance and directly using the couplant. The organic filler is surface-treated by a wet method. The overall blending treatment method is to add the (D) component to the resin composition and then add a coupling agent. By using this method, the characteristics of the aforementioned (D) component can be more effectively expressed.

When the component (D) is used in the present invention, in order to improve the dispersibility of the component (D) to the thermosetting resin composition, it is more preferable to disperse the component (D) in an organic solvent in advance as necessary. Use the slurry. The organic solvent used when slurrying the (D) component is not particularly limited, and the organic solvent exemplified in the above-mentioned production process of the polyphenylene ether derivative (A ') can be applied. These components may be used individually by 1 type, and may use 2 or more types together. Among these, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are preferred from the viewpoint of dispersibility. The concentration of the non-volatile components in the slurry is not particularly limited. For example, from the viewpoint of the precipitability and dispersibility of the inorganic filler, it is preferably set in the range of 50 to 80% by mass, more preferably 60 to 80 quality%.

(Flame retardant (E))
The resin composition of the present invention may contain a flame retardant (E).
Examples of the (E) component include a phosphorus-based flame retardant, a metal hydrate, and a halogen-based flame retardant.
(E) From the viewpoint of environmental problems, it is preferably at least one selected from the group consisting of a phosphorus-based flame retardant and a metal hydrate, and more preferably a combination of a phosphorus-based flame retardant and a metal hydrate. . The flame retardant (E) may be used alone or in combination of two or more.

<Phosphorus flame retardant>
The phosphorus-based flame retardant is not particularly limited as long as it is used as a flame retardant, and it may be an inorganic phosphorus-based flame retardant and an organic-based phosphorus-based flame retardant. Agents are also preferred. Furthermore, from the viewpoint of environmental problems, those who do not contain a halogen atom can be selected. From the viewpoint of high-frequency characteristics, adhesiveness to a conductor, glass transition temperature, thermal expansion coefficient, and flame retardancy, an organic phosphorus flame retarder is preferred.

Examples of the inorganic phosphorus-based flame retardant include red phosphorus; ammonium phosphate, ammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium polyphosphate, and the like; inorganic nitrogen-containing phosphides such as ammonium phosphate; phosphoric acid; Phosphine oxide, etc.

Examples of the organic phosphorus-based flame retardant include an aromatic phosphate, a phosphonic acid diester having a monofunctional group substituted, a phosphonate having a bifunctional group substituted, and a bifunctional group having a bifunctional group substituted. Metal salts of phosphonic acids, organic nitrogen-containing phosphides, cyclic organic phosphides, and the like. Among these, an aromatic phosphate compound and a metal salt of phosphonic acid in which a bifunctional group is substituted can be selected. Here, the metal salt is preferably any of a lithium salt, a sodium salt, a potassium salt, a calcium salt, a magnesium salt, an aluminum salt, a titanium salt, and a zinc salt, and more preferably an aluminum salt.
Among the organic phosphorus-based flame retardants, an aromatic phosphate can be selected.

Examples of the aromatic phosphate include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tolyl diphenyl phosphate, tolyl di-2,6-xylyl phosphate, Resorcinol bis (diphenyl phosphate), 1,3-phenylene bis (di-2,6-xylyl phosphate), bisphenol A-bis (diphenyl phosphate), 1,3-phenylene Bis (diphenyl phosphate), etc.

Examples of the phosphonic acid diester in which the monofunctional group is substituted include phenylphosphonic acid divinyl ester, phenylphosphonic acid diallyl ester, phenylphosphonic acid bis (1-butene ester), and the like.
Examples of the phosphonate having a bifunctional group substituted include phenyl diphenylphosphonate, methyl diphenylphosphonate, and the like.
Examples of the metal salt of a phosphonic acid substituted with a bifunctional group include a metal salt of a dialkylphosphonic acid, a metal salt of a diallylphosphonic acid, a metal salt of a divinylphosphonic acid, and a diaryl group. Metal salts of phosphonic acid, etc. The metal salt is preferably any of a lithium salt, a sodium salt, a potassium salt, a calcium salt, a magnesium salt, an aluminum salt, a titanium salt, and a zinc salt, and more preferably an aluminum salt.

Examples of the organic nitrogen-containing phosphide include phosphazene compounds such as bis (2-allylphenoxy) phosphinozene and xylylphosphazene; melamine phosphate; melamine pyrophosphate; Melamine polyphosphate; Melamine polyphosphate, etc.

Examples of the cyclic organic phosphide include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxybenzene) -9,10-di Hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide and the like.

Among these, at least one selected from the group consisting of an aromatic phosphate, a metal salt of a phosphonic acid substituted with a bifunctional group, and a cyclic organic phosphide is preferred, and more preferably selected from the group consisting of At least one of the group consisting of a metal salt of a phosphonic acid and a cyclic organic phosphide substituted by a bifunctional group, and more preferably a metal salt and a ring of a phosphonic acid substituted by a bifunctional group Organic phosphorus compounds are used in combination. In particular, as the metal salt of a phosphonic acid substituted with a bifunctional group, a metal salt of a dialkylphosphonic acid is preferred, and an aluminum salt of a dialkylphosphonic acid is more preferred. The cyclic organic phosphide is preferably 10- (2,5-dihydroxybenzene) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

In addition, when a metal salt of a phosphonic acid substituted with a bifunctional group and a cyclic organic phosphide are used in combination, the metal salt of the phosphonic acid substituted with a bifunctional group is contained in the cyclic organic phosphide. The ratio [metal salt of phosphonic acid / cyclic organic phosphide substituted with 2 functional groups] is preferably 0.6 to 2.5, more preferably 0.9 to 2, and even more preferably 1 to 2 in terms of mass ratio. It is more preferably 1.2 to 2.

The aromatic phosphate is preferably an aromatic phosphate represented by the following general formula (E-1) or (E-2), and a metal salt of a phosphonic acid obtained by substituting the above-mentioned two functional groups. A metal salt of phosphonic acid, which is substituted by a bifunctional group represented by the following general formula (E-3), is preferred.

In the general formulae, R ^E1 to R ^E5 are each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, e and f are each independently an integer of 0 to 5, and g, h, and i are each independently An integer from 0 to 4.
R ^E6 and R ^E7 are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and M is a lithium atom, a sodium atom, a potassium atom, a calcium atom, a magnesium atom, an aluminum atom, and titanium Atom and zinc atom, m1 is an integer of 1 to 4.

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and halogen atoms represented by R ^E1 to R ^E5 are the same as those in the case of R ¹ in the general formula (I).

e and f are preferably integers of 0 to 2, and more preferably 2. g, h, and i are preferably integers of 0 to 2, more preferably 0 or 1, and even more preferably 0.

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R ^E6 and R ^E7 are the same as those in the case of R ¹ in the general formula (I). The aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably an ethyl group.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms represented by R ^E6 and R ^E7 include a phenyl group, a naphthyl group, a biphenyl group, and an anthryl group. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms.

m1 represents the valence of the metal ion, that is, it varies within the range of 1 to 4 depending on the type of M.
As M, an aluminum atom is preferred. Furthermore, when M is an aluminum atom, m1 is 3.

<Metal hydrate>
Examples of the metal hydrate include hydrates of aluminum hydroxide and hydrates of magnesium hydroxide. These components may be used individually by 1 type, and may use 2 or more types together. This metal hydrate can be classified as an inorganic filler, but when it is a material capable of imparting flame resistance, it is classified as a flame retardant.

<Halogen flame retardants>
Examples of the halogen-based flame retardant include a chlorine-based flame retardant and a bromine-based flame retardant. Examples of the chlorine-based flame retardant include chlorinated paraffin. Examples of the bromine-based flame retardant include brominated epoxy resins such as brominated bisphenol A epoxy resin and brominated phenol novolac epoxy resin; hexabromobenzene, pentabromotoluene, and ethylenebis ( Pentabromobenzene), ethylenedi (tetrabromophthalimide), 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexamethylene Bromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene, 2,4,6-ginsane (tribromophenoxy) -1,3,5- Bromine-added flame retardants such as triazabenzene (herein, "additive" means that bromine is not introduced into the polymer in a chemically bonded form, that is, is blended. ); Tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, pentabromobenzyl acrylate, brominated styrene, etc. Unsaturated double bond-containing brominated reactive flame retardants (herein, the "reactive type" means that bromine is introduced into the polymer in a chemically bonded form), etc. . These components may be used individually by 1 type, and may use 2 or more types together.

(Content ratio of (E) component)
When the phosphorus-based flame retardant is contained in the resin composition of the present invention, the content ratio of the phosphorus-based flame retardant in the resin composition of the present invention is not particularly limited. For example, in terms of solid content, the resin composition (except for The content of the phosphorus atom in the total of components other than the aforementioned (D) component) is preferably 0.2 to 5% by mass, and more preferably 0.3 to 3% by mass. When the content of the phosphorus atom is 0.2% by mass or more, it tends to obtain better flame retardancy. In addition, when the content of the phosphorus atom is 5 mass% or less, it tends to obtain better moldability, high adhesion to the conductor, excellent heat resistance, and high glass transition temperature.

On the other hand, when the halogen-based flame retardant is contained in the resin composition of the present invention, from the viewpoint of environmental problems and chemical resistance, it is 100 parts by mass with respect to the total of (A) component and (C) component ( Among them, when the component (C) is not used, it is 100 parts by mass of the component (A)), and its content is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.

When the resin composition of the present invention contains a flame retardant other than a phosphorus-based flame retardant and a halogen-based flame retardant, it is not particularly limited, but it is based on 100 masses of the total of (A) component and (C) component. Parts (wherein (C) component is 100 parts by mass when component (C) is not used), preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and still more preferably 1 to 10 parts by mass It is more preferably 1 to 6 parts by mass.

(Flame-retardant additive)
The resin composition of the present invention can contain a flame retardant additive. As the flame retardant aid, for example, an inorganic flame retardant aid such as antimony trioxide or zinc molybdate can be used.

When the resin composition of the present invention is made to contain a flame retardant additive, the content ratio is not particularly limited, but it is relative to 100 parts by mass of the total of the (A) component and the (C) component (wherein the (C) component is not used) In this case, it is 100 parts by mass of the component (A)), preferably 0.1 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass. If a flame retardant additive is used within such a range, it will tend to obtain more favorable chemical resistance.

The resin composition of the present invention can be appropriately selected to contain a coupling agent, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like, as necessary. These components may be used individually by 1 type, and may use 2 or more types together. Moreover, the usage-amount of these components is not specifically limited.
In addition, although it does not specifically limit, as an aspect of the resin composition of this invention, the aspect which does not contain a thermoplastic elastomer substantially is mentioned. Here, the term "substantially not contained" includes the following cases: 0 parts by mass, that is, it is not contained at all; or, to the extent that it is not substantially contained (for example, when it is a thermoplastic elastomer, it is 1 part by mass or less and 0.5 part by mass) Servings). Examples of the thermoplastic elastomer include styrene-based elastomers, olefin-based elastomers, amine-based elastomers, polyester-based elastomers, polyamide-based elastomers, acrylic-based elastomers, silicone-based elastomers, and Derivatives of these elastomers, etc.

(Manufacturing method of resin composition)
A resin composition can be manufactured by mixing the said (A) component and (B) component, (C) component, other components, an organic solvent, etc. which are contained as needed by a conventional method. At this time, it can be dissolved or dispersed while stirring. Conditions such as the order of mixing, temperature and time during mixing and stirring are not particularly limited and can be arbitrarily set.
As described above, when the resin composition of the present invention is produced, by adjusting the solid content concentration of the resin composition within the aforementioned range, there is a tendency that it is particularly easy to obtain a laminated board excellent in high-frequency characteristics. Therefore, in the method for producing a resin composition, it is preferable to have a "solid content concentration adjustment step which adjusts the solid content concentration of the resin composition to 50.5 mass% or more, and this resin composition contains a polyphenylene ether derivative ( A) and an organic solvent. The polyphenylene ether derivative (A) has a group containing an N-substituted maleimide structure. " The resin composition used in this solid content concentration adjustment step is the same as the description of the aforementioned resin composition.

(Physical properties or characteristics)
When a laminated board is produced from the resin composition of the present invention, the glass transition temperature of the hardened product of the resin composition at this time is not particularly limited, but from good heat resistance and reliability of through-hole connection, and when manufacturing electronic components, etc. From the viewpoint of excellent processability, the glass transition temperature of the resin composition after curing is preferably 150 ° C or higher, more preferably 160 ° C or higher, even more preferably 170 ° C or higher, particularly preferably 180 ° C or higher. Preferably, it is above 200 ° C. There is no particular upper limit to the glass transition temperature. For example, it is preferably 1000 ° C or lower, more preferably 500 ° C or lower, and even more preferably 300 ° C or lower.

When a laminated board is produced from the resin composition of the present invention, the thermal expansion coefficient (Z direction, Tg or less) of the cured product of the resin composition at this time is not particularly limited, but from the viewpoint of suppressing the warpage of the laminated board It is preferably 57 ppm / ° C or lower, more preferably 50 ppm / ° C or lower, even more preferably 45 ppm / ° C or lower, and particularly preferably 40 ppm / ° C or lower. There is no particular lower limit of the thermal expansion coefficient, and it is, for example, 25 ppm / ° C or more.
The glass transition temperature and the coefficient of thermal expansion are values measured in accordance with the IPC standard as described in the examples.

When a laminated board is produced from the resin composition of the present invention, the dielectric constant and dielectric loss tangent of the hardened product of the resin composition at this time are not particularly limited, but it is preferable from the viewpoint of being suitable for use in a high frequency band. The dielectric constant is smaller at 10 GHz. Specifically, it is preferably 3.85 or less, more preferably 3.70 or less, and even more preferably 3.60 or less. There is no particular lower limit of the dielectric constant, and it is, for example, 0.5 or more, 1.0 or more, 3.0 or more, or 3.4 or more.

Also, the dielectric loss tangent at 10 GHz is preferably small. Specifically, it is preferably 0.007 or less, more preferably 0.006 or less, and still more preferably 0.0055 or less. The lower limit of the dielectric loss tangent is not particularly limited. Although it is preferably as small as possible, it may be 0.0001 or more, 0.0020 or more, or 0.0040 or more.
In addition, the dielectric constant and the dielectric loss tangent are values measured by the cavity resonator method as in the embodiment.
In this way, the resin composition, prepreg, laminated board, and multilayer printed wiring board of the present invention can be suitably used in electronic equipment for processing high-frequency signals of 1 GHz or more, and can be particularly suitable for processing high-frequency signals of 10 GHz or more. Or electronic devices with high frequency signals above 30GHz.

[Laminated boards, multilayer printed wiring boards, and manufacturing methods thereof]
The laminated board of the present invention is a laminated board comprising the prepreg of the present invention and a metal foil. The laminated board of the present invention can be produced, for example, by laminating a prepreg obtained by the aforementioned method for producing a prepreg of the present invention and a metal foil, and heating and pressing by a pressing method. hardening. More specifically, it can be manufactured by arranging a metal plate on one or both sides of one prepreg of the present invention, or by stacking two or more prepregs of the present invention. A metal foil is arranged on one or both sides of the prepreg, and then heated and pressed to form the prepreg.

The metal used as the metal foil is not particularly limited as long as it can be used for electrical insulation materials, but from the viewpoint of conductivity, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, Iron, titanium, chromium, or an alloy containing at least one of these metal elements is more preferably copper or aluminum, and even more preferably copper.

The conditions for the heating and press forming are not particularly limited, and for example, they can be performed within a range of a temperature of 100 to 300 ° C, a pressure of 0.2 to 10 MPa, and a heating time of 0.1 to 5 hours. In addition, as the heating and press forming, a method of maintaining a vacuum state using a vacuum press or the like for 0.5 to 5 hours can be adopted.

The multilayer printed wiring board of the present invention is a multilayer printed wiring board comprising the prepreg or the laminated board of the present invention. That is, the multilayer printed wiring board of the present invention can be produced by subjecting the prepreg or the laminate of the present invention to heat and pressure molding. The conditions for the heat and pressure molding are not particularly limited, and the same conditions as those described above can be adopted. The multilayer printed wiring board of the present invention can be produced, for example, by performing circuit formation processing and multilayer adhesion processing on a prepreg or a laminated board, and the prepreg is obtained by using the prepreg manufacturing method of the present invention. This laminated board is obtained by the manufacturing method of the laminated board of this invention mentioned above. As a method for forming a circuit, a conventional method may be mentioned, that is, a method for performing a circuit forming process by perforation processing, metal plating processing, etching of a metal foil, or the like.

[Semiconductor package]
The present invention also provides a semiconductor package comprising the aforementioned printed wiring board. More specifically, the semiconductor package is formed by assembling semiconductor components on the aforementioned printed wiring board. The semiconductor package of this embodiment can be manufactured by mounting a semiconductor element such as a semiconductor wafer, a memory on a specific position of the printed wiring board, and sealing the semiconductor element with a sealing resin or the like.

As mentioned above, although suitable embodiment of this invention was described, these embodiment is only an illustration for demonstrating this invention, and the range of this invention is not limited to these embodiment.
The present invention can be implemented in various aspects different from the embodiments described above without departing from the spirit thereof.
[Example]

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

[Manufacture of polyphenylene ether derivative (A)]
The polyphenylene ether derivative (A) was produced according to the following steps and the blended amount in Table 1.

(Production example A-1: Production of polyphenylene ether derivative (A-1))
To a 2-liter glass flask, pour toluene, polyphenylene ether, and p-aminophenol having a number average molecular weight of about 16,000, and dissolve while stirring at 90 ° C. The flask container includes a thermometer, a reflux cooling tube, and stirring. Device, and can be heated and cooled.
After visually confirming that it was dissolved, tertiary butyl isocarbonate monocarbonate and manganese naphthenate were added, reacted at a solution temperature of 90 ° C for 4 hours, and then cooled to 70 ° C to obtain a compound having a primary amine group at the molecular end. Polyphenylene ether compound (A '').
A small amount of this reaction solution was taken out and measured by gel permeation chromatography (GPC). It was confirmed that the peak derived from p-aminophenol disappeared, and the number average molecular weight of the polyphenylene ether compound (A '') was about 9,200. In addition, a small amount of the reaction solution taken out was dropped into a methanol / benzene mixed solvent (mixing mass ratio: 1/1), and a solid component (reaction product) purified by reprecipitation was subjected to FT-IR (Fourier transform). (Infrared spectrum) measurement, and it was confirmed that a peak derived from a primary amine group appeared at about 3400 cm ^-1 .

Here, the number average molecular weight is calculated by gel permeation chromatography (GPC) and a calibration curve using standard polystyrene. Calibration curve using standard polystyrene TSK standard POLYSTYRENE (Type: A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [东 曹 ( (TOSOH) Co., Ltd., trade name] and approximate using cubic equations. The conditions of GPC are shown below.
[Device]
Pump: L-6200 [manufactured by Hitachi Advanced Technology Co., Ltd.].
Detector: L-3300 RI [Made by Hitachi Advanced Technology Co., Ltd.].
Column oven: L-655A-52 [Made by Hitachi Advanced Technology Co., Ltd.].
[Tubing]
Protection column: TSK Guardcolumn HHR-L + column TSK gel G4000HHR + TSK gel G2000HHR (all manufactured by Tosoh Corporation, trade name).
Column size: 6.0 × 40mm (protective tube string), 7.8 × 300mm (tube column).
Eluent: tetrahydrofuran.
Sample concentration: 30mg / 5mL.
Injection volume: 20 μL.
Flow: 1.00mL / min.
Measurement temperature: 40 ° C.

Next, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide (BMI-5100 (trade name), Yamato (Manufactured by Chemical Industry Co., Ltd.) and propylene glycol monomethyl ether, the temperature of the liquid was raised while stirring, and reacted while maintaining the temperature at 120 ° C for 4 hours, and then cooled and filtered using a # 200 mesh (mesh), Thus, a polyphenylene ether derivative (A-1) was prepared.

A small amount of this reaction solution was taken out and reprecipitated in the same manner as described above. FT-IR measurement was performed on the purified solid component. It was confirmed that the peak derived from the primary amine group at about 3400 cm ^-1 disappeared, and that the peak was at 1700 to 1730 cm. A peak of a carbonyl group derived from maleimide appears around ^-1 . When the GPC of the solid content was measured (same conditions as described above), 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))
Production Example A-1 was performed in the same manner as in Production Example A-1 except that the respective raw materials and blending amounts were changed as shown in Table 1, to produce polyphenylene ether derivatives (A-2) to (A-3). ). Table 1 shows the number average molecular weights of the polyphenylene ether derivatives (A-2) to (A-3).

[Table 1]
Table 1 (A) Production of ingredients
‧The unit of blending quantity is mass

The abbreviations of the materials in Table 1 are as follows.
(1) Polyphenylene ether ‧ PPO640: Polyphenylene ether, with a number average molecular weight of about 16,000, trade name (manufactured by SABIC Innovative Plastics).
(2) Aminophenol compound (VIII)
‧P-Aminophenol: manufactured by IHARA Chemical Industry Co., Ltd.
‧M-Aminophenol: Made by Kanto Chemical Co., Ltd.
(3) bismaleimide compound (IX)
‧BMI-5100: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, trade name (made by Daiwa Chemical Industry Co., Ltd.).
‧BMI-4000: 2,2'-bis (4- (4-maleimidephenoxy) phenyl) propane, trade name (made by Daiwa Chemical Industry Co., Ltd.).
‧BMI-TMH: 1,6-bismaleimide- (2,2,4-trimethyl) hexane, trade name (made by Daiwa Chemical Industry Co., Ltd.).
(4) Reaction catalyst ‧ PERBUTYL (registered trademark) I: tertiary butyl isopropyl monocarbonate (manufactured by Nippon Oil Co., Ltd.).
‧Manganese naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.).
(5) Organic solvent-toluene (manufactured by Kanto Chemical Co., Ltd.).
‧Propylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd.).

[Production of amine bismaleimide compounds (C-1) to (C-3) and phenol modified cyanate ester prepolymer (C-4)]
According to the following steps and the blending amounts in Table 2, the thermosetting resin, that is, the amino bismaleimide compounds (C-1) to (C-3) and the phenol-modified cyanate prepolymer (C- 4).

[Production Example C-1: Production of Aminobismaleimide Compound (C-1)]
In a 1-liter glass flask, pour 2,2'-bis (4- (4-maleimidephenoxy) phenyl) propane, 2,2-bis (4- (4 -Aminophenoxy) phenyl) propane and propylene glycol monomethyl ether, and the liquid temperature was maintained at 120 ° C. In this state, the reaction was allowed to react for 3 hours while stirring, and then cooled and reused # 200 filter The mesh was filtered to prepare an amine bismaleimide compound (C-1). The flask container was equipped with a thermometer, a reflux cooling tube, and a stirring device, and was capable of heating and cooling.

[Production Examples C-2 to C-3: Production of Aminobismaleimide Compounds (C-2) to (C-3)]
Production Example C-1 was carried out in the same manner as in Production Example C-1, except that the respective raw materials and their blending amounts were changed as shown in Table 2, to produce an amine bismaleimide compound (C-2). ~ (C-3).

[Production Example C-4: Production of phenol-modified cyanate prepolymer (C-4)]
Into a 1-liter glass flask, pour toluene, 2,2'-bis (4-cyanooxybenzene) propane, and p- (α-cumene) phenol. After visually confirming that it has dissolved, directly The liquid temperature was maintained at 110 ° C, and manganese naphthenate as a reaction catalyst was poured while stirring to react for 3 hours. After that, it was cooled and filtered through a # 200 mesh (mesh) to prepare a phenol-modified cyanate prepolymer (C-4). The flask container was equipped with a thermometer, a reflux cooling tube, and a stirring device. Heating and cooling.

[Table 2]
Table 2 (C) Production of ingredients
‧The unit of blending quantity is mass

The abbreviations of the materials in Table 2 are as follows.
(1) Maleimidine compound (a)
‧BMI-5100: 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, trade name (made by Daiwa Chemical Industry Co., Ltd.).
‧BMI-4000: 2,2'-bis (4- (4-maleimidephenoxy) phenyl) propane, trade name (made by Daiwa Chemical Industry Co., Ltd.).
(2) Aromatic diamine compound (b)
‧BAPP: 2,2-bis (4- (4-aminophenoxy) phenyl) propane, trade name (manufactured by Wakayama Seika Co., Ltd.).
‧Diphenylamine-P: 4,4 '-[1,4-phenylenebis (1-methylethylene)] bisaniline, trade name (Mitsui Chemical Co., Ltd.).
‧Diphenylamine-M: 4,4 '-[1,3-phenylenebis (1-methylethylene)] bisaniline, trade name (manufactured by Mitsui Chemicals Co., Ltd.).
(3) Cyanate resin ‧ BADCy: Primaset (registered trademark) BADCy, 2,2'-bis (4-cyanooxybenzene) propane (manufactured by Lonza Co., Ltd.).
(4) Monophenol compounds and p- (α-cumene) phenol (Mitsui Precision Chemical Co., Ltd.).
(5) Reaction solvent, manganese naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.).
(6) Organic solvent-toluene (manufactured by Kanto Chemical Co., Ltd.).
‧Propylene glycol monomethyl ether (manufactured by Kanto Chemical Co., Ltd.).

[Examples 1 to 21 and Comparative Examples 1 to 17: Preparation of resin composition]
Each component described in Table 3 and Table 4 was prepared in accordance with the compounding amount (unit: part by mass) described in Table 3 and Table 4, and heated and stirred at room temperature or 50 to 80 ° C. to prepare Table 3. And the resin composition of solid content concentration shown in Table 4.
Here, as the compounding amount of the inorganic filler, the density of the resin composition (excluding the inorganic filler) is generally 1.20 to 1.25 g / cm ³ , and the density of the inorganic filler used is 2.2 to 3.01 g / cm ³ Therefore, when 160 parts by mass of the inorganic filler is blended with 100 parts by mass of the resin composition (excluding the inorganic filler), it will be about 39 to 48% by volume.
In addition, since the raw materials and intermediate products used in the aforementioned manufacturing examples are extremely trace or inactivated, they can be ignored even if they remain in the resin composition.

[Evaluation and measurement methods]
Using the resin compositions obtained in the examples and comparative examples, prepregs and copper-clad laminates were produced in accordance with the following methods, and each measurement and evaluation was performed using these prepregs and copper-clad laminates. The results are shown in Tables 5 to 6. In addition, the results of Examples 1 to 21 and Comparative Examples 1 to 17 in Tables 5 to 6 are prepared by modulation examples 1 to 21 and comparative modulation examples 1 to 17 in Tables 3 and 5 Measurement and evaluation results of the composition.

(Manufacture of prepreg and copper clad laminate)
The resin composition obtained in each example was coated on a glass fiber cloth (E glass fiber cloth, manufactured by Nitto Textile Co., Ltd.) having a thickness of 0.1 mm, and then heated and dried at 160 ° C for 7 minutes to prepare a resin composition. The prepreg with a substance content (including an organic solvent) of about 54% by mass.
Six pieces of this prepreg were stacked, and a low profile copper foil (FV-WS, M surface Rz: 1.5 μm) with a thickness of 18 μm was arranged above and below to contact the M surface. Furukawa Electric Co., Ltd. (Manufactured by the company), and subjected to heat and pressure molding under the conditions of a temperature of 230 ° C., a pressure of 3.9 MPa, and a time of 180 minutes to produce a double-sided copper clad laminate (thickness: 0.8 mm).

(Appearance Evaluation of Prepreg)
The appearance of the prepreg obtained from the above was observed. The appearance was evaluated visually, and evaluated based on the following criteria.
A: There are no abnormalities in appearance.
C: There are slight variations, streaks, foaming and phase separation on the surface of the prepreg, but the surface smoothness is lacking.

(Measurement of exhaust volume of prepreg)
First, the mass of the prepreg (pre-preg before heat treatment) produced in each example was measured. Then, the prepreg was heat-treated at a temperature of 163 ° C for 15 minutes, and then the mass of the prepreg (pre-preg after heat treatment) was measured. The exhaust gas amount of the prepreg was obtained from the measured values using the following formula.
Exhaust volume (% by mass) = {(mass of prepreg before heat treatment-mass of prepreg after heat treatment) / mass of prepreg before heat treatment} × 100

(Characteristic evaluation of copper clad laminates)
The copper-clad laminated board obtained as described above was evaluated for its high-frequency characteristics, copper foil peel strength, glass transition temperature, thermal expansion coefficient, solder heat resistance, and flame retardancy. The method of evaluating the characteristics of the copper-clad laminated board is as follows.

(1) High-frequency characteristics After the copper foil on both sides of the copper-clad laminated board is etched to remove it, it is cut to a size of 60 mm × 2 mm, and a test piece is dried at 105 ° C./hour to obtain a test piece. Dk (dielectric coefficient) and Df (dielectric loss tangent) in 10 GHz were calculated from the resonance frequency obtained by the cavity resonator method and the no-load Q value.
For the testers, a parallel vector type network analyzer E8364B manufactured by Agilent Technologies Co., Ltd., and CP531 (10GHz resonator) and CPMA-V (program) manufactured by Kanto Electronics Application Development Co., Ltd. were used. The measurement was performed at an ambient temperature of 25 ° C.
(2) Peel strength of copper foil was measured in accordance with Japanese Industrial Standard JIS C6481 (1996).
(3) Welding heat resistance (hygroscopic heat resistance)
A 50 mm square test piece obtained by etching the double-sided copper foil of a copper-clad laminate is processed in a normal state and pressure cooker test device (condition: 121 ° C, 2.2 atmospheres) for a specific time (1 hour) , 3 hours, and 5 hours), immersed in molten solder at 288 ° C for 20 seconds, and then visually observed the appearance of the test piece after the solder was immersed. In addition, the numbers in the table mean the number of pieces in which no abnormality such as swelling, measling, or the like was confirmed among the three test pieces after dipping solder.
(4) Glass transition temperature (Tg) and coefficient of thermal expansion The glass transition temperature (Tg) and the coefficient of thermal expansion (thickness direction [Z direction], temperature range 30 to 150 ° C) are copper foil on both sides of a copper-clad laminate A 5 mm square test piece was etched, and a thermomechanical measuring device [manufactured by TA Instruments Japan Co., Ltd., Q400 (model)] was used, and according to IPC (The Institute for Interconnecting and Packaging Electronic Circuits, (Association) specifications to measure the glass transition temperature and the coefficient of thermal expansion (coefficient of linear expansion).
(5) Self-evaluation substrate for flame retardance A test piece having a length of 127 mm and a width of 12.7 mm was cut out, and the test piece was tested and evaluated for the flame retardance according to the UL94 test method (Method V). It is obtained by immersing a copper-clad laminated board in a copper etching solution, that is, a 10% by mass solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) to remove copper foil.
That is, the lower end of the test piece held vertically was subjected to flame contact for 10 seconds with a flame of 20 mm twice. The evaluation is performed in accordance with the UL method V94 standard.

[table 3]

‧The unit of content is mass part. When it is a solution, it means the total amount of the solution.

[Table 4]












‧The unit of content is mass part. When it is a solution, it means the total amount of the solution.

In addition, the abbreviations, etc. of each material in Table 4 and Table 5 are as follows.
(1) Polyphenylene ether derivative ‧A-1: The polyphenylene ether derivative (A-1) obtained in Production Example (A-1) was appropriately removed by removing an organic solvent or adding toluene and propylene glycol monomethyl Ether was used to produce the solid content concentrations shown in the table.
‧A-2: The polyphenylene ether derivative (A-2) obtained in Production Example (A-2) was appropriately prepared by removing an organic solvent or adding toluene and propylene glycol monomethyl ether, as described in the table. Solid content concentration.
‧A-3: The polyphenylene ether derivative (A-3) obtained in Production Example (A-3) was appropriately prepared as described in the table by removing an organic solvent or adding toluene and propylene glycol monomethyl ether. Solid content concentration.

(2) Hardening accelerator (B)
<Organic peroxide>
‧PERBUTYL (registered trademark) P: α, α'-bis (tertiary butyl peroxide) dicumene, trade name (manufactured by Nippon Oil Co., Ltd.), one minute half-life temperature 175.4 ° C.
‧PERCUMYL (registered trademark) D: bis (1-phenyl-1-methylethyl) peroxide, trade name (manufactured by Nippon Oil Co., Ltd.), one-minute half-life temperature of 175.2 ° C.
‧PERCUMYL (registered trademark) P: dicumyl hydroperoxide, trade name (manufactured by Nippon Oil Co., Ltd.), one-minute half-life temperature of 232.5 ° C.
<Imidazole-based hardener>
‧G-8009L: Isocyanate-shielding imidazole (addition reaction product of dihexyl diisocyanate resin and 2-ethyl-4methylimidazole), trade name (manufactured by Daiichi Kogyo Co., Ltd.).
‧2MZ-H: 2-methylimidazole, trade name (manufactured by Shikoku Chemical Co., Ltd.).
‧2E4MZ: 2-ethyl-4-methylimidazole, trade name (manufactured by Shikoku Chemical Co., Ltd.).
‧1B2MZ: 1-benzyl-2-methylimidazole, trade name (manufactured by Shikoku Chemical Co., Ltd.).
‧C11Z: Undecyl imidazole, trade name (manufactured by Shikoku Chemical Co., Ltd.).
‧2MA-OK: Addition product of 2,4-diamino-6- [2'-methylimidazolyl- (1 ')] ethylsymmetric triazabenzene and trimellitic acid, trade name (four Guohuacheng Co., Ltd.).
<Phosphorus-based hardening accelerator>
‧TPP-MK: Tetraphenylhydrazone, trade name (Bei Hing Industrial Co., Ltd.).
‧TPP-S: Triphenylhydrazone, trade name (Bei Hing Industrial Co., Ltd.).

(3) Thermosetting resin (C)
‧C-1: The amine bismaleimide (C-1) obtained in Production Example (C-1) was appropriately prepared by removing an organic solvent or adding propylene glycol monomethyl ether, as shown in the table. The solid content concentration.
‧C-2: The amine bismaleimide (C-2) obtained in Production Example (C-2) was appropriately prepared by removing an organic solvent or adding propylene glycol monomethyl ether, as described in the table. The solid content concentration.
‧C-3: The amine bismaleimide (C-3) obtained in Production Example (C-3) was appropriately prepared by removing an organic solvent or adding propylene glycol monomethyl ether, as described in the table. The solid content concentration.
‧C-4: The phenol-modified cyanate prepolymer (C-4) obtained in Production Example (C-4) was prepared by removing an organic solvent or adding toluene as appropriate to obtain the solid components described in the table. concentration.
‧NC-7000L: Naphthol novolac epoxy resin, trade name (made by Nippon Kayaku Co., Ltd.)

(4) Inorganic filler (D)
‧SO-C2: Spherical fused silica, with an average particle diameter of 0.5 μm, a density of 2.2 g / cm ³ , and a trade name (manufactured by Admatechs Co., Ltd.).

(5) Flame retardant (E)
‧OP-930: Aluminum dialkylphosphonic acid salt, metal salt of phosphonic acid substituted with two functional groups, phosphorus content of 23.5 mass%, trade name (made by Clariant Chemical Co., Ltd.).
‧HCA-HQ: 10- (2,5-dihydroxybenzene) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, cyclic organic phosphide, phosphorus content 9.6 mass %, Trade name (manufactured by Sanguang Co., Ltd.)

[table 5]

[TABLE 6]

Examples 1 to 16 are examples using a resin composition containing a polyphenylene ether derivative (A) and a hardening accelerator (B). The hardening accelerator (B) is selected from organic peroxides and imidazole-based hardening. At least one of the group consisting of an accelerator and a phosphorus-based hardening accelerator.
Comparing the laminated boards in Examples 1 to 12 with each of Comparative Examples 1 to 12 to be described later, it can be seen that the examples have excellent high-frequency characteristics, and have a good balance with good moisture absorption and heat resistance, adhesion to conductors, Glass transition temperature, thermal expansion characteristics and flame resistance. In particular, it was found that the high-frequency characteristics are affected by the solid content concentration in the resin composition.

Examples 17 to 21 are examples in which a resin composition containing a polyphenylene ether derivative (A) was used, and a resin composition not containing the aforementioned hardening accelerator (B) was used. Comparing the laminated boards in Examples 17 to 21 with Comparative Examples 13 to 17 described below, it can be seen that the examples have excellent high-frequency characteristics (especially, dielectric loss tangent at 10 GHz) and are subject to the resin composition. The effect of solids concentration.
[Industrial availability]

The prepreg and resin composition of the present invention can exhibit high adhesion to a conductor, excellent heat resistance, high glass transition temperature, low thermal expansion coefficient, and flame resistance, and can exhibit stable and excellent high-frequency characteristics (in Dielectric properties in the high frequency region). The prepreg and a laminated board including the prepreg can be suitably used for electronic component applications such as a multilayer printed wiring board and a semiconductor package.

no

no

Domestic storage information (please note in order of storage organization, date, and number)
no

Information on foreign deposits (please note according to the order of the country, institution, date, and number)
no

Claims (19)

A prepreg comprising a resin composition and a sheet-like fiber reinforced base material, and The amount of exhaust gas generated when the prepreg was heated at a temperature of 163 ° C. for 15 minutes was less than 0.7% by mass based on the entire prepreg. The prepreg according to claim 1, wherein the resin composition contains a polyphenylene ether derivative (A), and the polyphenylene ether derivative (A) has a group containing an N-substituted maleimide structure . The prepreg according to claim 2, wherein the group containing the N-substituted maleimide structure is a group containing a bismaleimide structure, and in the bismaleimide structure, The nitrogen atoms of the two maleimidine groups are bonded to each other via an organic group. The resin composition according to claim 2 or 3, wherein the group containing the N-substituted maleimide structure is a group represented by the following general formula (Z): In the general formula (Z), R ^{2 is} each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, y is an integer of 0 to 4, and A ¹ is represented by the following general formulae (II), (III), (IV) or (V); In the general formula (II), R ^{3 is} each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and p is an integer of 0 to 4; In the general formula (III), R ⁴ and R ⁵ are each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and A ² is an alkylene group having 1 to 5 carbon atoms and an alkylene group having 2 to 5 carbon atoms. Group, ether group, thioether group, sulfofluorenyl group, carbonyloxy group, keto group, single bond or group represented by the following general formula (III-1), q and r are each independently an integer of 0 to 4 , In the general formula (III-1), R ⁶ and R ⁷ are each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and A ³ is an alkylene group, isopropylidene group, or ether having 1 to 5 carbon atoms. Group, thioether group, sulfofluorenyl group, carbonyloxy group, keto group or single bond, and s and t are each independently an integer of 0 to 4; In the general formula (IV), n is an integer from 0 to 10; In the general formula (V), R ⁸ and R ⁹ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and u is an integer of 1 to 8. The prepreg according to any one of claims 1 to 4, wherein the resin composition further comprises a hardening accelerator (B), the hardening accelerator (B) is selected from the group consisting of an organic peroxide and an imidazole-based hardening agent. At least one of the group consisting of an accelerator and a phosphorus-based hardening accelerator. The prepreg according to any one of claims 1 to 5, wherein the resin composition further comprises a thermosetting resin (C), and the thermosetting resin (C) is selected from the group consisting of epoxy resin and cyanic acid. At least one member of the group consisting of an ester resin and a maleimide compound. The prepreg according to claim 6, wherein the maleimide compound in the thermosetting resin (C) is selected from the group consisting of a maleimide compound (a) and a compound represented by the following general formula (VI) At least one of the group consisting of the aminobismaleimide compound (c) represented by), and the maleimide compound (a) has at least two N-substituted maleimide structures Group, In the general formula (VI), A ^{4 has} the same definition as A ¹ in the general formula (Z) described in claim 4, and A ⁵ is a group represented by the following general formula (VII): In the general formula (VII), R ¹⁷ and R ¹⁸ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom, and A ⁸ is one having 1 to 5 carbon atoms. An alkylene group, an alkylene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfofluorenyl group, a carbonyloxy group, a keto group, a fluorenyl group, a single bond or the following general formula (VII-1) A group represented by (VII-2), q 'and r' are each independently an integer of 0 to 4; In the general formula (VII-1), R ¹⁹ and R ²⁰ are each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and A ⁹ is an alkylene group, an isopropylidene group, or an intermediate group having 1 to 5 carbon atoms. Benzene isopropylidene or p-phenylene isopropylidene, ether group, thioether group, sulfofluorenyl group, carbonyloxy group, keto group, or single bond, and s 'and t' are each independently an integer of 0 to 4 ; In the general formula (VII-2), R ²¹ is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and A ¹⁰ and A ¹¹ are each independently an alkylene group, isopropylidene group, or ether having 1 to 5 carbon atoms. Group, thioether group, sulfofluorenyl group, carbonyloxy group, keto group, or single bond, and w is an integer of 0 to 4. A laminated board comprising the prepreg according to any one of claims 1 to 7 and a metal foil. A multilayer printed wiring board comprising a prepreg according to any one of claims 1 to 7 or a laminated board according to claim 8. A semiconductor package comprising a semiconductor element mounted on the multilayer printed wiring board according to claim 9. A resin composition containing a polyphenylene ether derivative (A) and an organic solvent, the polyphenylene ether derivative (A) having a group containing an N-substituted maleimide structure, and The solid content concentration was 50.5 mass% or more. The resin composition according to claim 11, wherein the polyphenylene ether derivative (A) having a group containing an N-substituted maleimide structure has a structural unit represented by the following general formula (I) : In the general formula (I), each of R ^{1 is} independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom, and x is an integer of 0 to 4. The resin composition according to claim 11 or 12, wherein the group containing the N-substituted maleimide structure is a group represented by the following general formula (Z): In the general formula (Z), R ^{2 is} each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, y is an integer of 0 to 4, and A ¹ is represented by the following general formulae (II), (III), (IV) or (V); In the general formula (II), R ^{3 is} each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and p is an integer of 0 to 4; In the general formula (III), R ⁴ and R ⁵ are each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and A ² is an alkylene group having 1 to 5 carbon atoms and an alkylene group having 2 to 5 carbon atoms. Group, ether group, thioether group, sulfofluorenyl group, carbonyloxy group, keto group, single bond or group represented by the following general formula (III-1), q and r are each independently an integer of 0 to 4 , In the general formula (III-1), R ⁶ and R ⁷ are each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and A ³ is an alkylene group, isopropylidene group, or ether having 1 to 5 carbon atoms. Group, thioether group, sulfofluorenyl group, carbonyloxy group, keto group or single bond, and s and t are each independently an integer of 0 to 4; In the general formula (IV), n is an integer of 1 to 10; In the general formula (V), R ⁸ and R ⁹ are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and u is an integer of 1 to 8. The resin composition according to any one of claims 11 to 13, further comprising a hardening accelerator (B) selected from an organic peroxide, an imidazole-based hardening accelerator, and phosphorus It is at least one member of the group consisting of hardening accelerators. The resin composition according to any one of claims 11 to 14, further comprising a thermosetting resin (C) selected from an epoxy resin, a cyanate resin, and a horse At least one member of the group consisting of lyme imine. The resin composition according to claim 15, wherein the maleimide compound in the thermosetting resin (C) is selected from the group consisting of a maleimide compound (a) and a compound selected from the following general formula (VI) At least one of the group consisting of the aminobismaleimide compound (c) represented by), and the maleimide compound (a) has at least two N-substituted maleimide structures Group, In the general formula (VI), A ^{4 has} the same definition as A ¹ in the general formula (Z) described in claim 13, and A ⁵ is a group represented by the following general formula (VII): In the general formula (VII), R ¹⁷ and R ¹⁸ are each independently an aliphatic hydrocarbon group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom, and A ⁸ is one having 1 to 5 carbon atoms. An alkylene group, an alkylene group having 2 to 5 carbon atoms, an ether group, a thioether group, a sulfofluorenyl group, a carbonyloxy group, a keto group, a fluorenyl group, a single bond or the following general formula (VII-1) A group represented by (VII-2), q 'and r' are each independently an integer of 0 to 4; In the general formula (VII-1), R ¹⁹ and R ²⁰ are each independently an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and A ⁹ is an alkylene group, an isopropylidene group, or an intermediate group having 1 to 5 carbon atoms. Benzene isopropylidene or p-phenylene isopropylidene, ether group, thioether group, sulfofluorenyl group, carbonyloxy group, keto group or single bond, s 'and t' are each independently an integer of 0 to 4 ; In the general formula (VII-2), R ²¹ is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms, and A ¹⁰ and A ¹¹ are each independently an alkylene group, isopropylidene group, or ether having 1 to 5 carbon atoms. Group, thioether group, sulfofluorenyl group, carbonyloxy group, keto group, or single bond, and w is an integer of 0 to 4. A method for producing a prepreg, comprising impregnating or coating a resin composition on a sheet-like fiber-reinforced base material and drying the prepreg to produce a prepreg, and the method includes satisfying the following conditions: The treatment step (X) under the above conditions, the conditions of the exhaust volume are: The amount of exhaust gas generated when the prepreg was heated at a temperature of 163 ° C. for 15 minutes was less than 0.7% by mass based on the entire prepreg. A method for manufacturing a laminated board, which comprises manufacturing a laminated board by laminating a prepreg with a metal foil, and heating and pressing by a pressing method. The prepreg is the prepreg according to claim 17 Derived from the manufacturing method. A method for manufacturing a multilayer printed wiring board, which comprises manufacturing a multilayer printed wiring board by performing circuit forming processing and multilayer adhesion processing on a prepreg or a laminated board, the prepreg being prepared by the prepreg described in claim 17 The laminated board is obtained by the laminated board manufacturing method according to claim 18.