Low-dielectric resin composition, adhesion promoter, low-dielectric adhesive molding, low-dielectric adhesive, laminate, and method for producing low-dielectric resin composition

Abstract

To provide a low-dielectric resin composition having excellent compatibility with a thermosetting resin and a low coefficient of linear expansion, and also to provide an adhesion promoter, a low-dielectric adhesive molding, a low-dielectric adhesive, a laminate, and a method for producing a low-dielectric resin composition.SOLUTION: This low-dielectric resin composition comprises a polyphenylene ether resin, a styrenic elastomer, a cyclic olefin polymer having an alicyclic structure in its main chain, and a reaction product of the polyphenylene ether resin with the styrenic elastomer and / or the cyclic olefin polymer.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a low dielectric resin composition, an adhesion promoter, a low dielectric adhesive molded product, a low dielectric adhesive, a laminate, and a method for producing a low dielectric resin composition. [Background technology]

[0002] In recent years, in order to cope with high frequencies, materials used in communication devices and electronic devices are required to have low dielectric properties.

[0003] As such a material, for example, a low dielectric resin composition containing a styrene-based elastomer and a cyclic olefin-based polymer having an alicyclic ring in the main chain has been proposed (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2024 / 038794 Brochure Summary of the Invention [Problem to be solved by the invention]

[0005] On the other hand, the low dielectric resin composition of Patent Document 1 is used by mixing with a thermosetting resin (for example, polyphenylene ether resin), and therefore, there is a demand for improved compatibility with the thermosetting resin.

[0006] Furthermore, the low dielectric resin composition of Patent Document 1 is used, for example, to form an adhesive layer that bonds an insulating layer and a conductor layer, but from the viewpoint of dimensional stability, it is required that the linear expansion coefficient be low.

[0007] The present invention provides a low dielectric resin composition having excellent compatibility with thermosetting resins and a low linear expansion coefficient, an adhesion promoter, a low dielectric adhesive molded product, a low dielectric adhesive, a laminate, and a method for producing the low dielectric resin composition. [Means for solving the problem]

[0008] The present invention [1] is a low dielectric resin composition comprising a polyphenylene ether resin, a styrene-based elastomer, a cyclic olefin-based polymer having an alicyclic ring in its main chain, and a reaction product of the polyphenylene ether resin with the styrene-based elastomer and / or the cyclic olefin-based polymer.

[0009] The present invention [2] includes the low dielectric resin composition according to the above [1], wherein the polyphenylene ether resin has a number average molecular weight of 500 or more and 50,000 or less.

[0010] The present invention [3] includes the low dielectric resin composition according to the above [1] or [2], wherein the polyphenylene ether resin has a radical polymerizable group.

[0011] The present invention [4] includes the low dielectric resin composition according to any one of the above [1] to [3], wherein at least one selected from the group consisting of the polyphenylene ether resin, the styrene-based elastomer, and the cyclic olefin-based polymer is modified with a functional group-containing monomer.

[0012] The present invention [5] includes the low dielectric resin composition according to the above [4], wherein the functional group-containing monomer includes a carboxy group-containing monomer.

[0013] The present invention [6] includes an adhesion promoter containing the low dielectric resin composition according to any one of the above [1] to [5].

[0014] The present invention [7] is a cured product of a low dielectric adhesive molding material containing the adhesion promoter described in [6] above and a thermosetting resin, and the thermosetting resin includes at least one selected from the group consisting of epoxy resin, polyphenylene ether resin, fluororesin, polyimide resin, phenolic resin, melamine resin, polyolefin resin having an unsaturated double bond, and liquid crystal polymer.

[0015] The present invention [8] includes the low dielectric adhesive molding according to the above [7], which has a dielectric loss tangent of less than 0.0050.

[0016] The present invention [9] includes a laminate comprising an insulating layer containing the low dielectric adhesive molding described in [7] or [8] above, and a conductor layer arranged on at least one side of the insulating layer.

[0017] The present invention

[10] includes a low dielectric adhesive containing the low dielectric resin composition according to any one of the above [1] to [5].

[0018] The present invention

[11] is a semiconductor device comprising an insulating layer, a conductor layer disposed opposite to the insulating layer, and an adhesive layer disposed between the insulating layer and the conductor layer and adhering the insulating layer and the conductor layer, The adhesive layer includes a laminate containing the low dielectric adhesive described in

[10] above.

[0019] The present invention

[12] includes a laminate comprising a first conductor layer, a second conductor layer arranged opposite the first conductor layer, and an adhesive layer arranged between the first conductor layer and the second conductor layer and adhering the first conductor layer and the second conductor layer, wherein the adhesive layer comprises the low dielectric adhesive described in

[10] above.

[0020] The present invention

[13] is a method for producing a low dielectric adhesive molded article according to any one of the above [1] to [5], and includes a method for producing a low dielectric resin composition, comprising a first step of mixing the polyphenylene ether resin, the styrene-based elastomer, the cyclic olefin-based polymer, and a peroxide, and a second step of reacting the polyphenylene ether resin with the styrene-based elastomer and / or the cyclic olefin-based polymer.

[0021] The present invention

[14] includes the method for producing a low dielectric resin composition according to the above

[13] , wherein the blending ratio of the polyphenylene ether resin is 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of the total amount of the polyphenylene ether resin, the styrene-based elastomer, and the cyclic olefin-based polymer.

[0022] The present invention

[15] includes the method for producing a low dielectric resin composition according to the above

[13] or

[14] , wherein the blending ratio of the styrene-based elastomer is 10 parts by mass or more and 90 parts by mass or less per 100 parts by mass of the total amount of the styrene-based elastomer and the cyclic olefin-based polymer. [Effects of the Invention]

[0023] The low dielectric resin composition of the present invention contains a polyphenylene ether resin, a styrene-based elastomer, a cyclic olefin-based polymer having an alicyclic ring in the main chain, and a reaction product of the polyphenylene ether resin with the styrene-based elastomer and / or the cyclic olefin-based polymer, and therefore has excellent compatibility with thermosetting resins and a low coefficient of linear expansion.

[0024] The adhesion promoter of the present invention contains the low dielectric resin composition of the present invention, and therefore has excellent compatibility with thermosetting resins and a low coefficient of linear expansion.

[0025] The low dielectric adhesive molded article of the present invention includes a cured product of a low dielectric adhesive molding material containing the low dielectric resin composition of the present invention, and therefore has excellent dimensional stability.

[0026] The low dielectric adhesive of the present invention contains the low dielectric resin composition of the present invention, and therefore has excellent compatibility with thermosetting resins and a low coefficient of linear expansion.

[0027] The laminate of the present invention has an insulating layer containing the low dielectric adhesive molded article of the present invention or an adhesive layer containing the low dielectric adhesive of the present invention, and therefore has excellent dimensional stability.

[0028] The method for producing a low dielectric resin composition of the present invention includes a second step of reacting a polyphenylene ether resin with a styrene-based elastomer and / or a cyclic olefin-based polymer, thereby producing a low dielectric resin composition that has excellent compatibility with thermosetting resins and a low linear expansion coefficient. [Brief explanation of the drawings]

[0029] [Figure 1] FIG. 1 is a schematic diagram showing a copper clad laminate as a first embodiment of the laminate. [Figure 2] FIG. 2 is a schematic diagram showing a circuit board as a second embodiment of the laminate. [Figure 3] FIG. 3 is a schematic diagram showing a copper clad laminate as a third embodiment of the laminate. [Figure 4] FIG. 4 is a schematic diagram showing a circuit board as a fourth embodiment of the laminate. [Figure 5] FIG. 5A shows a process diagram for manufacturing a circuit board as a fifth embodiment of the laminate, illustrating the process of preparing a carrier-attached copper foil, FIG. 5B shows the process of forming a first resist layer, and FIG. 5C shows the process of forming a first conductor layer. [Figure 6] Figure 6D shows a process diagram for manufacturing a circuit board following Figure 5, showing the step of removing the first resist layer, Figure 6E shows the step of removing the copper foil exposed from the first conductor layer, Figure 6F shows the step of laminating an adhesive layer, and Figure 6G shows the step of laminating a carrier-attached copper foil onto the adhesive layer. [Figure 7] Figure 7H shows the step of peeling off the carrier layer in a process diagram for manufacturing a circuit board following Figure 6, Figure 7I shows the step of forming a via hole, Figure 7J shows the step of forming a via fill, and Figure 7K shows the step of forming a second resist layer. [Figure 8] Figure 8L shows the step of forming a second conductor layer in a process diagram for manufacturing a circuit board, following Figure 7, Figure 8M shows the step of removing the second resist layer, Figure 8N shows the step of removing the copper foil exposed from the second conductor layer, and Figure 8O shows the step of peeling off the carrier layer. DETAILED DESCRIPTION OF THE INVENTION

[0030] 1. Low dielectric resin composition The low dielectric resin composition contains a polyphenylene ether resin, a styrene-based elastomer, a cyclic olefin-based polymer having an alicyclic ring in its main chain (hereinafter sometimes referred to as a cyclic olefin-based polymer), and a reaction product of the polyphenylene ether resin with a styrene-based elastomer and / or a cyclic olefin-based polymer. That is, the low dielectric resin composition contains at least one selected from the group consisting of a polyphenylene ether resin, a styrene-based elastomer, a cyclic olefin-based polymer, a reaction product of the polyphenylene ether resin with a styrene-based elastomer, a reaction product of the polyphenylene ether resin with a cyclic olefin-based polymer, and a reaction product of the polyphenylene ether resin, a styrene-based elastomer, and a cyclic olefin-based polymer.

[0031] <Polyphenylene ether resin> Examples of polyphenylene ether resins include radically polymerizable group-containing polyphenylene ether resins that have at least one radically polymerizable group, and radically polymerizable group-free polyphenylene ether resins that do not have any radically polymerizable group.

[0032] The radically polymerizable group-containing polyphenylene ether resin preferably has a radically polymerizable group at the molecular chain terminal.

[0033] An example of such a radically polymerizable group-containing polyphenylene ether resin is a polyphenylene ether resin represented by the following formula (1). [ka] In the above formula (1), two R 1represent a hydrogen atom or a methyl group, and may be the same or different from each other. s and t are integers, for example, from 0 to 20. The sum of s and t is, for example, from 1 to 30.

[0034] Alternatively, the radically polymerizable group-containing polyphenylene ether resin may be a commercially available product, such as Noryl SA9000 resin (manufactured by SHPP Japan LLC).

[0035] Examples of the polyphenylene ether resin not containing a radical polymerizable group include a polyphenylene ether resin represented by the following formula (2) and a polyphenylene ether resin represented by the following formula (3). [ka] [ka] In the above formula (2), s and t have the same meanings as s and t in the above formula (1).

[0036] In the above formula (3), m is an integer of 1 to 20.

[0037] Alternatively, the polyphenylene ether resin not containing a radical polymerizable group may be commercially available, such as Noryl SA90 resin (manufactured by SHPP Japan LLC) and Noryl SA120 resin (manufactured by SHPP Japan LLC).

[0038] As the polyphenylene ether resin, from the viewpoint of reliably producing a reaction product (described later) of the polyphenylene ether resin with a styrene-based elastomer and / or a cyclic olefin-based polymer, a radically polymerizable group-containing polyphenylene ether resin is preferable.

[0039] The polyphenylene ether resin can be produced by a conventionally known method (for example, JP-A-2010-111758).

[0040] The number average molecular weight of the polyphenylene ether resin is, for example, 500 to 50,000, preferably 700 to 10,000, more preferably 1,000 to 5,000, still more preferably 1,200 to 3,000, and particularly preferably 1,500 to 2,000.

[0041] Specifically, the number average molecular weight of the polyphenylene ether resin is, from the viewpoint of the linear expansion coefficient, for example, 500 or more, preferably 700 or more, more preferably 1000 or more, even more preferably 1200 or more, and particularly preferably 1500 or more, and, from the viewpoint of solubility, for example, 50000 or less, preferably 10000 or less, more preferably 5000 or less, even more preferably 3000 or less, and particularly preferably 2000 or less.

[0042] The weight average molecular weight and number average molecular weight are polystyrene-equivalent molecular weights determined by gel permeation chromatography (GPC) (the same applies hereinafter).

[0043] The content of the polyphenylene ether resin is the remainder obtained by subtracting the amount of polyphenylene ether resin consumed in the reaction with the styrene-based elastomer and / or the cyclic olefin-based polymer in the second step (described later) from the blending ratio of the polyphenylene ether resin in the first step of the production method for a low dielectric resin composition (described later). Specifically, the content of the polyphenylene ether resin is, for example, 0.5 to 49.5 parts by mass, preferably 2 to 30 parts by mass, per 100 parts by mass of the total amount of the polyphenylene ether resin, the styrene-based elastomer, and the cyclic olefin-based polymer. The content of the polyphenylene ether resin is, for example, 0.5 to 49.5% by mass, preferably 2 to 30% by mass, relative to the low dielectric resin composition.

[0044] The polyphenylene ether resins can be used alone or in combination of two or more kinds.

[0045] <Styrene-based elastomer> The styrene-based elastomer is, for example, a copolymer of styrene and a chain olefin.

[0046] Examples of the chain olefin include chain olefins having 2 to 8 carbon atoms. Examples of the chain olefin include ethylene, propylene, butylene (butene), butadiene, pentene, hexene, octene, and 3-methyl-1-pentene. Preferred examples of the chain olefin include ethylene, propylene, butylene, and butadiene.

[0047] The chain olefins can be used alone or in combination of two or more kinds. As the chain olefins, a combination of ethylene and propylene is preferable.

[0048] The styrene elastomer is produced by a known method. For example, the styrene elastomer is produced by polymerizing styrene and a chain olefin in the presence of a known initiator (for example, an alkyllithium compound). The polymerization conditions are appropriately set depending on the purpose and application.

[0049] The styrene-based elastomer contains structural units derived from styrene and structural units derived from a chain olefin. The styrene-based elastomer preferably comprises structural units derived from styrene and structural units derived from a chain olefin.

[0050] The content of structural units derived from styrene is, for example, 10 to 70% by mass, preferably 15 to 60% by mass, and more preferably 20 to 50% by mass, relative to the total amount of the styrene-based elastomer.

[0051] Specifically, the content of structural units derived from styrene relative to the total amount of the styrene-based elastomer is, from the viewpoint of solution stability, for example, 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and from the viewpoint of low dielectric properties, for example, 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less.

[0052] The content of the structural units derived from the chain olefin is, for example, 30% by mass to 90% by mass, preferably 40% by mass to 85% by mass, and more preferably 50% by mass to 80% by mass, relative to the total amount of the styrene-based elastomer.

[0053] Specifically, the content of structural units derived from chain olefins is 30% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, and for example, 90% by mass or less, preferably 85% by mass or less, more preferably 80% by mass or less, relative to the total amount of the styrene-based elastomer.

[0054] The content ratio of the structural unit derived from styrene and the content ratio of the structural unit derived from a chain olefin are calculated based on the formulation of the polymerization raw materials of the styrene-based elastomer. Specifically, the content ratio of the structural unit derived from styrene is calculated as the ratio of styrene to the total amount of the polymerization raw materials (styrene and a chain olefin). Furthermore, the content ratio of the structural unit derived from a chain olefin is calculated as the ratio of the chain olefin to the total amount of the polymerization raw materials (styrene and a chain olefin).

[0055] Specific examples of such styrene-based elastomers include styrene-ethylene-propylene copolymer (SEP), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-butadiene-styrene copolymer (SBS), styrene-ethylene-butylene-styrene copolymer (SEBS), and styrene-isobutylene-styrene copolymer (SIBS). These copolymers are random copolymers or block copolymers.

[0056] As the styrene-based elastomer, from the viewpoint of low dielectric properties, preferred examples include styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-butadiene-styrene copolymer (SBS), and styrene-ethylene-butylene-styrene copolymer (SEBS). As the styrene-based elastomer, more preferred example is styrene-ethylene-propylene-styrene copolymer (SEPS).

[0057] As the styrene-based elastomer, commercially available products can also be used.

[0058] Commercially available styrene elastomers include, for example, the SEPTON series (manufactured by Kuraray) and the Kraton series (manufactured by Kraton Polymer Japan).

[0059] The weight average molecular weight of the styrene elastomer is 10,000 to 500,000, preferably 30,000 to 100,000, more preferably 40,000 to 70,000, and even more preferably 50,000 to 60,000.

[0060] The content of the styrene elastomer is the remainder obtained by subtracting the amount of styrene elastomer consumed by the reaction between the polyphenylene ether resin and the cyclic olefin polymer in the second step (described later) from the blending ratio of the styrene elastomer in the first step of the production method for a low dielectric resin composition (described later). Specifically, the content of the styrene elastomer is, for example, 5 to 90 parts by mass, or preferably 10 to 70 parts by mass, per 100 parts by mass of the total amount of the polyphenylene ether resin, the styrene elastomer, and the cyclic olefin polymer. The content of the styrene elastomer is, for example, 5 to 90% by mass, or preferably 10 to 70% by mass, relative to the low dielectric resin composition.

[0061] The styrene elastomers can be used alone or in combination of two or more kinds.

[0062] <Cyclic olefin polymer> Examples of cyclic olefin polymers include polymers of cyclic olefins and hydrogenated products thereof, and copolymers of cyclic olefins and chain olefins (cyclic olefin copolymers) and hydrogenated products thereof.

[0063] [Cyclic olefin polymers and their hydrogenated products] Examples of cyclic olefins include cyclic hydrocarbon compounds containing an ethylenically unsaturated bond, such as cyclic hydrocarbon compounds having 6 to 30 carbon atoms. More specifically, examples of cyclic olefins include bicyclo[2.2.1]-hept-2-ene (also known as norbornene) and derivatives thereof, tricyclo[4.3.0.12.5]-3-decene and derivatives thereof, tricyclo[4.4.0.12.5]-3-decene and derivatives thereof, tetracyclo[4.4.0.12,5.17,10]-3-dodecene and derivatives thereof, pentacyclo[6.5.1.13.6.02.7.09.13]-4-pentadecene and derivatives thereof, hexacyclo[6.6.1.13.6.110.13.02.7.09.14]-4-heptadecene and derivatives thereof, and heptacyclo[8.7.0.12.9.14.7.111.17.03.8.012.16]-5-eicosene and derivatives thereof.

[0064] The cyclic olefins can be used alone or in combination of two or more kinds.

[0065] The cyclic olefin polymer is produced by a known method. For example, the cyclic olefin is subjected to ring-opening metathesis polymerization by a known method. This results in a ring-opening metathesis polymer of the cyclic olefin. The polymerization conditions are appropriately set depending on the purpose and application.

[0066] If necessary, the ring-opening metathesis polymer of cyclic olefin can be hydrogenated by a known method to obtain a hydrogenated product of the ring-opening metathesis polymer of cyclic olefin.

[0067] [Cyclic olefin and chain olefin copolymers and their hydrogenated products]

[0068] Examples of the cyclic olefin include the cyclic hydrocarbon compounds described above. A preferred example of the cyclic olefin is tetracyclo[4.4.0.12,5.17,10]-3-dodecene.

[0069] Examples of the chain olefin include the chain olefins listed above for the styrene-based elastomer, and preferably ethylene.

[0070] A specific example of the copolymer of a cyclic olefin and a chain olefin is a copolymer of tetracyclo[4.4.0.12,5.17,10]-3-dodecene and ethylene.

[0071] The copolymer of a chain olefin and a cyclic olefin is produced by a known method. For example, the chain olefin and the cyclic olefin are polymerized in the presence of a known catalyst (e.g., a vanadium-based catalyst, an aluminum-based catalyst, or a metallocene catalyst). This results in a copolymer of the chain olefin and the cyclic olefin. The polymerization conditions are appropriately set depending on the purpose and application.

[0072] If necessary, the copolymer of the chain olefin and the cyclic olefin can be hydrogenated by a known method, thereby obtaining a hydrogenated copolymer of the chain olefin and the cyclic olefin.

[0073] As the cyclic olefin polymer, commercially available products can also be used.

[0074] Examples of commercially available products include the ZEONEX series (hydrogenated cyclic monomer polymers, manufactured by Zeon Corporation), the ZEONOR series (hydrogenated cyclic monomer polymers, manufactured by Zeon Corporation), and the APEL series (copolymers of chain olefins and cyclic olefins, manufactured by Mitsui Chemicals).

[0075] The cyclic olefin-based polymer is preferably a copolymer of a cyclic olefin and a chain olefin. That is, the cyclic olefin-based polymer preferably contains structural units derived from a cyclic olefin and structural units derived from a chain olefin. The cyclic olefin-based polymer is more preferably composed of structural units derived from a cyclic olefin and structural units derived from a chain olefin.

[0076] In the copolymer of a cyclic olefin and a chain olefin, the content of the structural units derived from the cyclic olefin is appropriately set.

[0077] The content ratio of the structural unit derived from the cyclic olefin and the content ratio of the structural unit derived from the chain olefin are calculated based on the blending recipe of the polymerization raw materials for the cyclic olefin polymer.

[0078] The weight average molecular weight of the cyclic olefin polymer is, for example, 10,000 to 500,000, preferably 50,000 to 300,000, more preferably 80,000 to 200,000, still more preferably 100,000 to 150,000, and particularly preferably 112,000 to 118,000.

[0079] The glass transition temperature of the cyclic olefin polymer is, for example, 60°C to 200°C, preferably 70°C to 175°C, more preferably 80°C to 150°C, even more preferably 90°C to 140°C, and particularly preferably 100°C to 130°C.

[0080] Specifically, from the viewpoint of heat resistance, the glass transition temperature of the cyclic olefin polymer is, for example, 60°C or higher, preferably 70°C or higher, more preferably 80°C or higher, even more preferably 90°C or higher, and particularly preferably 100°C or higher. From the viewpoint of compatibility with thermosetting resins, the glass transition temperature is, for example, 200°C or lower, preferably 175°C or lower, more preferably 150°C or lower, even more preferably 140°C or lower, and particularly preferably 130°C or lower.

[0081] The method for measuring the glass transition temperature will be described in detail in the examples below.

[0082] The cyclic olefin polymers may be used alone or in combination of two or more.

[0083] The content of the cyclic olefin polymer is the remainder obtained by subtracting the amount of the cyclic olefin polymer consumed in the reaction with the polyphenylene ether resin and the styrene elastomer in the second step (described later) from the blending ratio of the cyclic olefin polymer in the first step of the production method for a low dielectric resin composition (described later). Specifically, the content of the cyclic olefin polymer is, for example, 5 to 90 parts by mass, preferably 10 to 70 parts by mass, per 100 parts by mass of the total amount of the polyphenylene ether resin, the styrene elastomer, and the cyclic olefin polymer. The content of the styrene elastomer is, for example, 5 to 90% by mass, preferably 10 to 70% by mass, relative to the low dielectric resin composition.

[0084] <Modification of polyphenylene ether resin, styrene-based elastomer, and cyclic olefin-based polymer> At least one selected from the group consisting of polyphenylene ether resin, styrene-based elastomer, and cyclic olefin-based polymer is preferably modified with a functional group-containing monomer from the viewpoint of adhesion to the conductor layer described below. That is, the polyphenylene ether resin is preferably a polyphenylene ether resin modified with a functional group-containing monomer, the styrene-based elastomer is preferably a styrene-based elastomer modified with a functional group-containing monomer, and the cyclic olefin-based polymer is preferably a cyclic olefin-based polymer modified with a functional group-containing monomer.

[0085] Examples of functional group-containing monomers include carboxy group-containing monomers, sulfonyl group-containing monomers, amino group-containing monomers, hydroxyl group-containing monomers, glycidyl group-containing monomers, and halogen-containing monomers. From the viewpoint of further improving adhesion to the conductor layer described below, the functional group-containing monomer is preferably a carboxy group-containing monomer. That is, the functional group-containing monomer preferably includes a carboxy group-containing monomer. Furthermore, the polyphenylene ether resin is preferably a carboxy group-containing monomer-modified polyphenylene ether resin, the styrene-based elastomer is preferably a carboxy group-containing monomer-modified styrene-based elastomer, and the cyclic olefin-based polymer is preferably a carboxy group-containing monomer-modified cyclic olefin-based polymer.

[0086] Examples of the carboxy group-containing monomer include unsaturated acids. Examples of the unsaturated acids include maleic acid, fumaric acid, itaconic acid, and (meth)acrylic acid. Examples of the unsaturated acids also include anhydrides of these acids. Examples of the carboxy group-containing monomer include maleic anhydride. That is, the polyphenylene ether resin is preferably a maleic anhydride-modified polyphenylene ether resin, the styrene-based elastomer is preferably a maleic anhydride-modified styrene-based elastomer, and the cyclic olefin-based polymer is preferably a maleic anhydride-modified cyclic olefin-based polymer.

[0087] The functional group-containing monomers can be used alone or in combination of two or more kinds.

[0088] The functional group-containing monomer-modified polyphenylene ether resin is obtained by mixing and reacting a polyphenylene ether resin with a functional group-containing monomer, the functional group-containing monomer-modified styrene-based elastomer is obtained by mixing and reacting a styrene-based elastomer with a functional group-containing monomer, and the functional group-containing monomer-modified cyclic olefin-based polymer is obtained by mixing and reacting a cyclic olefin-based polymer with a functional group-containing monomer. In the following explanation, a case where all of the polyphenylene ether resin, the styrene-based elastomer, and the cyclic olefin-based polymer are modified with the functional group-containing monomer will be described in detail.

[0089] In such a case, in the first step described below, a functional group-containing monomer is blended together with the polyphenylene ether resin, the styrene-based elastomer, and the cyclic olefin-based polymer, and the polyphenylene ether resin and the functional group-containing monomer are reacted, the styrene-based elastomer and the functional group-containing monomer are reacted, and the cyclic olefin-based polymer and the functional group-containing monomer are reacted.

[0090] The mixing ratio of the functional group-containing monomer is, for example, 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, more preferably 0.7 to 5 parts by mass, and even more preferably 0.8 to 2 parts by mass, per 100 parts by mass of the total amount of the polyphenylene ether resin, styrene-based elastomer, and cyclic olefin-based polymer.

[0091] In the above reaction, a peroxide is added.

[0092] The peroxide is added to generate radicals when reacting the polyphenylene ether resin with a styrene-based elastomer and / or a cyclic olefin-based polymer in the second step described below. On the other hand, if a functional group-containing monomer is added to the polyphenylene ether resin, styrene-based elastomer, and cyclic olefin-based polymer in the first step, the peroxide acts as a graft catalyst in the reactions between the polyphenylene ether resin and the functional group-containing monomer, the styrene-based elastomer and the functional group-containing monomer, and the cyclic olefin-based polymer and the functional group-containing monomer in the second step. In other words, in this case, the polyphenylene ether resin reacts with the styrene-based elastomer and / or cyclic olefin-based polymer, while the polyphenylene ether resin reacts with the functional group-containing monomer, the styrene-based elastomer reacts with the functional group-containing monomer, and the cyclic olefin-based polymer reacts with the functional group-containing monomer in the second step. Therefore, the reaction conditions for the reaction of the polyphenylene ether resin with the functional group-containing monomer, the reaction conditions for the reaction of the styrene-based elastomer with the functional group-containing monomer, and the reaction conditions for the reaction of the cyclic olefin-based polymer with the functional group-containing monomer are the same as the reaction conditions for the reaction of the polyphenylene ether resin with the styrene-based elastomer and / or the cyclic olefin-based polymer described below.

[0093] The peroxide will be described later.

[0094] As a result, a functional group-containing monomer-modified polyphenylene ether resin, a functional group-containing monomer-modified styrene-based elastomer, and a functional group-containing monomer-modified cyclic olefin-based polymer are obtained.

[0095] <Reaction product of polyphenylene ether resin with styrene-based elastomer and / or cyclic olefin-based polymer> The reaction product of a polyphenylene ether resin with a styrene-based elastomer and / or a cyclic olefin-based polymer is produced by reacting a polyphenylene ether resin with a styrene-based elastomer and / or a cyclic olefin-based polymer in the presence of a peroxide, as will be described in detail later.

[0096] The content of the reaction product of the polyphenylene ether resin with the styrene elastomer and / or cyclic olefin polymer is, for example, 0.5 to 40% by mass, or preferably 1 to 20% by mass, relative to the low dielectric resin composition.

[0097] <Other reaction products> Although the details will be described later, a reaction product of the polyphenylene ether resin and the styrene-based elastomer and / or the cyclic olefin-based polymer is produced by reacting the polyphenylene ether resin with the styrene-based elastomer and / or the cyclic olefin-based polymer in the presence of a peroxide, but other reaction products may be produced as by-products of the reaction. In such cases, the low dielectric resin composition contains the other reaction products.

[0098] Other reaction products include, for example, reaction products of styrene-based elastomers and cyclic olefin-based polymers.

[0099] <Other resins> The low dielectric resin composition may also contain other resins.

[0100] Examples of other resins include olefin polymers.

[0101] Examples of olefin polymers include polyethylene, polypropylene, polyisobutylene, poly-1-butene, poly-4-methylpentene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-butene copolymer, ethylene-4-methyl-1-pentene copolymer, and propylene-4-methyl-1-pentene copolymer.

[0102] The other resins can be used alone or in combination of two or more kinds.

[0103] The content of the other resin relative to the low dielectric resin composition is, for example, 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0% by mass. In other words, more preferably, the low dielectric resin composition does not contain any other resin.

[0104] <Additives> The low dielectric resin composition may contain additives in an appropriate proportion as needed, such as plasticizers, antifoaming agents, leveling agents, mildew inhibitors, rust inhibitors, matting agents, flame retardants, thixotropic agents, tackifiers, thickeners, lubricants, antistatic agents, surfactants, reaction retarders, antioxidants, ultraviolet absorbers, hydrolysis inhibitors, weather stabilizers, heat stabilizers, dyes, inorganic pigments, organic pigments, curing agents, crosslinking agents, silane coupling agents, anti-tack agents, inorganic particles, and organic particles.

[0105] The additives can be used alone or in combination of two or more kinds.

[0106] <Method for producing low dielectric resin composition> The method for producing a low dielectric resin composition includes a first step of mixing a polyphenylene ether resin, a styrene-based elastomer, a cyclic olefin-based polymer, and a peroxide, and a second step of reacting the polyphenylene ether resin with the styrene-based elastomer and / or the cyclic olefin-based polymer.

[0107] [1st step] In the first step, a polyphenylene ether resin, a styrene-based elastomer, a cyclic olefin-based polymer, a peroxide, and optional additives are mixed to prepare a mixture. Examples of the mixing method include melt-kneading.

[0108] Furthermore, as described above, when the polyphenylene ether resin, the styrene-based elastomer, and the cyclic olefin-based polymer are modified with a functional group-containing monomer, the functional group-containing monomer is blended together with the above components.

[0109] The blending ratio of the polyphenylene ether resin is, for example, 1 to 50 parts by mass, preferably 2 to 40 parts by mass, more preferably 2 to 30 parts by mass, and even more preferably 2 to 25 parts by mass, per 100 parts by mass of the total amount of the polyphenylene ether resin, styrene-based elastomer, and cyclic olefin-based polymer.

[0110] Specifically, the blending ratio of the polyphenylene ether resin is, for example, 1 part by mass or more, preferably 2 parts by mass or more, from the viewpoint of compatibility with the thermosetting resin (described later), relative to 100 parts by mass of the total amount of the polyphenylene ether resin, styrene-based elastomer, and cyclic olefin-based polymer; and, from the viewpoint of low dielectric properties, is 50 parts by mass or less, preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 25 parts by mass or less.

[0111] The blending ratio of the styrene-based elastomer is, for example, 10 parts by mass to 90 parts by mass, preferably 30 parts by mass to 70 parts by mass, and more preferably 40 parts by mass to 60 parts by mass, relative to 100 parts by mass of the total amount of the styrene-based elastomer and the cyclic olefin-based polymer.

[0112] Specifically, the blending ratio of the styrene-based elastomer is, relative to 100 parts by mass of the total amount of the styrene-based elastomer and the cyclic olefin-based polymer, for example, 10 parts by mass or more, preferably 30 parts by mass or more, more preferably 40 parts by mass or more, from the viewpoint of compatibility with the thermosetting resin, and for example, 90 parts by mass or less, preferably 70 parts by mass or less, more preferably 60 parts by mass or less, from the viewpoint of the linear expansion coefficient.

[0113] The blending ratio of the styrene-based elastomer is, for example, 5 parts by mass to 95 parts by mass, preferably 15 parts by mass to 80 parts by mass, more preferably 20 parts by mass to 60 parts by mass, and even more preferably 30 parts by mass to 50 parts by mass, relative to 100 parts by mass of the total amount of the polyphenylene ether resin, the styrene-based elastomer, and the cyclic olefin-based polymer.

[0114] Specifically, the blending ratio of the styrene-based elastomer relative to 100 parts by mass of the total amount of the polyphenylene ether resin, the styrene-based elastomer, and the cyclic olefin-based polymer is, from the viewpoint of low dielectric property, for example, 5 parts by mass or more, preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 30 parts by mass or more, and from the viewpoint of, for example, the linear expansion coefficient, is 95 parts by mass or less, preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less.

[0115] The blending ratio of the cyclic olefin polymer is, for example, 10 parts by mass to 90 parts by mass, preferably 30 parts by mass to 70 parts by mass, and more preferably 40 parts by mass to 60 parts by mass, per 100 parts by mass of the total amount of the styrene elastomer and the cyclic olefin polymer.

[0116] Specifically, the blending ratio of the cyclic olefin-based polymer is, relative to 100 parts by mass of the total amount of the styrene-based elastomer and the cyclic olefin-based polymer, for example, 10 parts by mass or more, preferably 30 parts by mass or more, more preferably 40 parts by mass or more, from the viewpoint of the linear expansion coefficient, and for example, 90 parts by mass or less, preferably 70 parts by mass or less, more preferably 60 parts by mass or less, from the viewpoint of compatibility with the thermosetting resin.

[0117] The blending ratio of the cyclic olefin-based polymer is, for example, 5 parts by mass to 95 parts by mass, preferably 15 parts by mass to 80 parts by mass, more preferably 20 parts by mass to 60 parts by mass, and even more preferably 30 parts by mass to 50 parts by mass, per 100 parts by mass of the total amount of the polyphenylene ether resin, the styrene-based elastomer, and the cyclic olefin-based polymer.

[0118] Specifically, the blending ratio of the cyclic olefin-based polymer is, from the viewpoint of low dielectric properties, for example, 5 parts by mass or more, preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and even more preferably 30 parts by mass or more, relative to 100 parts by mass of the total amount of the polyphenylene ether resin, the styrene-based elastomer, and the cyclic olefin-based polymer; and, from the viewpoint of compatibility with the thermosetting resin, for example, 95 parts by mass or less, preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less.

[0119] Examples of peroxides include 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, di-t-butyl peroxide, t-butyl hydroperoxide, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, t-butyl peroxybenzoate, and lauroyl peroxide. More preferred examples of peroxides include 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane.

[0120] The blending ratio of the peroxide is, for example, 0.1 to 5 parts by mass, preferably 0.2 to 1 part by mass, and more preferably 0.4 to 0.8 parts by mass, per 100 parts by mass of the total amount of the polyphenylene ether resin, styrene-based elastomer, and cyclic olefin-based polymer.

[0121] The peroxides can be used alone or in combination of two or more kinds.

[0122] [Second process] In the second step, the polyphenylene ether resin is reacted with a styrene-based elastomer and / or a cyclic olefin-based polymer.

[0123] In this reaction, the peroxide first decomposes to generate radicals. These radicals abstract hydrogen from at least one of the polyphenylene ether resin, the styrene-based elastomer, and the cyclic olefin-based polymer, generating radicals on the hydrocarbon. The polyphenylene ether resin then reacts with the styrene-based elastomer and / or the cyclic olefin-based polymer via these radicals. In particular, when the polyphenylene ether resin is a polyphenylene ether resin containing a radical-polymerizable group, radicals are generated by cleavage of the radical-polymerizable group in the polyphenylene ether resin. The polyphenylene ether resin then reacts with the styrene-based elastomer and / or the cyclic olefin-based polymer via these radicals.

[0124] The reaction product of the polyphenylene ether resin with the styrene-based elastomer and / or cyclic olefin-based polymer can be confirmed by, for example, pulse NMR.

[0125] In the reaction, the reaction temperature is, for example, 150° C. to 280° C., or preferably 180° C. to 250° C. The reaction time is, for example, 0.5 minutes to 12 minutes.

[0126] In addition, the above-mentioned by-products may be produced in the above reaction. Furthermore, as described above, when a functional group-containing monomer is blended in the first step, the polyphenylene ether resin reacts with the functional group-containing monomer, the styrene-based elastomer reacts with the functional group-containing monomer, and the cyclic olefin-based polymer reacts with the functional group-containing monomer.

[0127] The mixture is then cooled, and other resins and additives are added as needed. That is, the other resins are added as needed under conditions that do not cause reaction with the polyphenylene ether resin, styrene-based elastomer, and cyclic olefin-based polymer, thereby producing a low dielectric resin composition.

[0128] The low dielectric resin composition can also be diluted with a known organic solvent to form a diluted solution of the low dielectric resin composition. The solid content concentration of the diluted solution of the low dielectric resin composition is, for example, 10% by mass to 40% by mass, preferably 15% by mass to 30% by mass.

[0129] The low dielectric resin composition contains a polyphenylene ether resin, a styrene-based elastomer, a cyclic olefin-based polymer, and a reaction product of the polyphenylene ether resin with the styrene-based elastomer and / or the cyclic olefin-based polymer, and therefore has excellent compatibility with thermosetting resins and a low coefficient of linear expansion.

[0130] Regarding the linear expansion coefficient, in the evaluation of the linear expansion coefficient described in detail below, the linear expansion coefficient is less than 60 ppm / °C, and for example, -500 ppm / °C or more.

[0131] If the linear expansion coefficient is less than the upper limit, the dimensional stability can be improved.

[0132] Furthermore, the low dielectric resin composition has excellent compatibility with thermosetting resins and a low coefficient of linear expansion, and is therefore suitable for use as an adhesion promoter and / or a low dielectric adhesive in the production of laminates described below. That is, the adhesion promoter and the low dielectric adhesive each contain the low dielectric resin composition.

[0133] 2. Effects The low dielectric resin composition contains a polyphenylene ether resin, a styrene-based elastomer, a cyclic olefin-based polymer having an alicyclic ring in the main chain, and a reaction product of the polyphenylene ether resin with the styrene-based elastomer and / or the cyclic olefin-based polymer, and therefore has excellent compatibility with thermosetting resins and a low coefficient of linear expansion.

[0134] Specifically, since the low dielectric resin composition contains a reaction product of a polyphenylene ether resin with a styrene-based elastomer and / or a cyclic olefin-based polymer, this reaction product acts as a compatibilizer, thereby improving the compatibility between the polyphenylene ether resin, the styrene-based elastomer, and the cyclic olefin-based polymer.

[0135] Furthermore, by blending such a low dielectric resin composition with a thermosetting resin, compatibility with the thermosetting resin can be improved. In particular, if the thermosetting resin is a polyphenylene ether resin, the reaction product of the polyphenylene ether resin with a styrene-based elastomer and / or a cyclic olefin-based polymer acts as a compatibilizer, improving compatibility with the thermosetting resin (polyphenylene ether resin). On the other hand, even if the thermosetting resin is a resin other than a polyphenylene ether resin, compatibility can be improved from the viewpoint of structural similarity with the thermosetting resin.

[0136] 3.Laminate The laminate is a circuit board or a circuit board material. The circuit board is, for example, a laminate having a conductor layer (circuit layer) with a circuit pattern. The circuit board material is a laminate that can be processed into a circuit board. More specifically, the circuit board material is, for example, a laminate having a conductor layer (non-circuit layer) without a circuit pattern, and that can be processed to form a circuit pattern. An example of the circuit board material is a copper-clad laminate.

[0137] The laminate is produced by using a low dielectric resin composition. A method for producing a circuit board or a circuit board material as a laminate using the low dielectric resin composition will be described in detail below.

[0138] (1) First embodiment 1 is a schematic cross-sectional view showing a copper-clad laminate as a first embodiment of the laminate, in which the above-mentioned low dielectric resin composition is used as an adhesion promoter.

[0139] More specifically, in FIG. 1, the copper-clad laminate 1 comprises an adhesive insulating layer (hereinafter referred to as adhesive insulating layer) 2 and a conductor layer 4 disposed on at least one side of the adhesive insulating layer 2.

[0140] The adhesive insulating layer 2 includes a low-dielectric adhesive molding having low dielectric properties and adhesiveness. The adhesive insulating layer 2 is preferably made of a low-dielectric adhesive molding or an impregnated substrate and a low-dielectric adhesive molding.

[0141] The low dielectric adhesive molding is, for example, a cured product (cured molding product) of a low dielectric adhesive molding material.

[0142] The low dielectric adhesive molding material contains, for example, a thermosetting resin (uncured thermosetting resin) and an adhesion promoter (additive).

[0143] Examples of thermosetting resins include epoxy resins, polyphenylene ether resins, fluororesins, polyimide resins, phenolic resins, melamine resins, polyolefin resins having unsaturated double bonds, and liquid crystal polymers. These may be used alone or in combination of two or more. A preferred example of the thermosetting resin is polyphenylene ether resin.

[0144] In other words, the thermosetting resin includes at least one selected from the group consisting of epoxy resin, polyphenylene ether resin, fluororesin, polyimide resin, phenolic resin, melamine resin, polyolefin resin having an unsaturated double bond, and liquid crystal polymer. The thermosetting resin preferably includes polyphenylene ether resin. The thermosetting resin preferably consists of polyphenylene ether resin.

[0145] The adhesion promoter (additive) contains the above-mentioned low dielectric resin composition, and preferably consists of the above-mentioned low dielectric resin composition.

[0146] The low dielectric adhesive molding material is prepared, for example, by mixing a thermosetting resin and an adhesion promoter by a known method.

[0147] The blending ratio of the thermosetting resin and the adhesion promoter is not particularly limited, but is, for example, 1 to 400 parts by mass, or preferably 5 to 150 parts by mass, of the adhesion promoter per 100 parts by mass of the thermosetting resin.

[0148] The amount of the thermosetting resin relative to the total amount of the thermosetting resin and the adhesion promoter is, for example, 20% by mass to 99% by mass, or preferably 40% by mass to 95% by mass.

[0149] The amount of the adhesion promoter relative to the total amount of the thermosetting resin and the adhesion promoter is, for example, 1 to 80 mass %, or preferably 5 to 60 mass %.

[0150] The low dielectric adhesive molding material may contain additives, if necessary.

[0151] Examples of the additives include the additives exemplified in the low dielectric resin composition.

[0152] Furthermore, from the viewpoint of thermosetting properties, the low dielectric adhesive molding material preferably contains a thermal initiator.

[0153] When the adhesive insulating layer 2 is made of a low dielectric adhesive molding, the adhesive insulating layer 2 is formed by molding and curing a low dielectric adhesive molding material by a known method.

[0154] Specifically, the low dielectric adhesive molding material is applied to a known substrate (e.g., a copper plate and a release liner) and dried as necessary. This produces a coating film of the low dielectric adhesive molding material. The coating film is then cured (thermosetting) by heating.

[0155] As a result, a low dielectric adhesive molding (adhesive insulating layer 2) made of a cured product of the low dielectric adhesive molding material is obtained.

[0156] Also, when the adhesive insulating layer 2 consists of an impregnated base material and a low dielectric adhesive molding, the adhesive insulating layer 2 is formed by impregnating the impregnated base material with a low dielectric adhesive molding material, drying and curing it.

[0157] Specifically, a glass cloth as an impregnation substrate is impregnated with the low dielectric adhesive molding material, and dried as necessary. Then, the glass cloth and the low dielectric adhesive molding material impregnated in the glass cloth are cured (thermoset) by heating.

[0158] As a result, a low dielectric adhesive molding (adhesive insulating layer 2) containing the glass cloth and the cured product of the low dielectric adhesive molding material is obtained.

[0159] The shape and size of the low dielectric adhesive molding (adhesive insulating layer 2) are appropriately set depending on the purpose and application.

[0160] The conductor layer 4 is a thin film made of a known conductive material. An example of the conductive material is copper. The conductor layer 4 is formed by a known film formation method. The thickness of the conductor layer 4 is adjusted to be relatively thin, for example. This allows the circuit pattern to be formed by a subtractive method. The thickness of the conductor layer 4 is, for example, 50 μm or less.

[0161] The conductor layer 4 is disposed on at least one side of the adhesive insulating layer 2. The conductor layer 4 is preferably disposed on both sides of the adhesive insulating layer 2. In FIG. 1, the conductor layer 4 is disposed on both sides of the adhesive insulating layer 2.

[0162] More specifically, the conductor layer 4 is formed by a known method so as to be in contact with the surface of the adhesive insulating layer 2. In this way, the conductor layer 4 is adhered to the adhesive insulating layer 2. As a result, a copper-clad laminate 1 comprising the adhesive insulating layer 2 and the conductor layer 4 is obtained.

[0163] The method for obtaining the copper-clad laminate 1 is not limited to the above. For example, first, a conductor layer 4 made of metal foil is prepared. Next, a low-dielectric adhesive molding material is applied to the conductor layer 4, and dried as necessary. The low-dielectric adhesive molding material is then thermally cured. This allows an adhesive insulating layer 2 to be formed on the surface of the conductor layer 4. As a result, a copper-clad laminate 1 is obtained, which includes the adhesive insulating layer 2 and the conductor layer 4 in contact with the surface of the adhesive insulating layer 2.

[0164] The copper clad laminate 1 has an insulating layer 2. The insulating layer 2 contains the low dielectric adhesive molding. Therefore, in the copper clad laminate 1, the insulating layer 2 has excellent dimensional stability.

[0165] The adhesion promoter (additive), low dielectric adhesive molding material, and low dielectric adhesive molded product (adhesive insulating layer 2) contain the low dielectric resin composition, and therefore the adhesion promoter (additive), low dielectric adhesive molding material, and low dielectric adhesive molded product (adhesive insulating layer 2) have excellent dimensional stability.

[0166] Furthermore, the adhesion promoter (additive), low dielectric adhesive molding material and low dielectric adhesive molded product (adhesive insulating layer 2) also have excellent low dielectric properties.

[0167] Specifically, the dielectric loss tangent of the low dielectric adhesive molded article is, for example, less than 0.0050, preferably 0.0030 or less, more preferably 0.0020 or less, even more preferably 0.0010 or less, and usually 0.0002 or more.

[0168] The method for measuring the dielectric loss tangent will be described in detail in the examples below.

[0169] (2) Second embodiment 2 is a schematic cross-sectional view showing a circuit board as a second embodiment of the laminate. In the second embodiment, the low dielectric resin composition described above is used as an adhesion promoter, as in the first embodiment.

[0170] More specifically, the copper-clad laminate 1 of the first embodiment described above can be processed to form a circuit board 11. That is, the conductor layer 4 of the copper-clad laminate 1 can be etched by a known method to form a circuit 14. As a result, as shown in FIG. 2, a circuit board 11 is formed as a second embodiment of the laminate.

[0171] In such a circuit board 11, the adhesive insulating layer 2 contains a low dielectric adhesive molding. Therefore, in the circuit board 11, the adhesive insulating layer 2 has excellent dimensional stability.

[0172] (3) Third embodiment 3 is a schematic cross-sectional view showing a copper-clad laminate as a third embodiment of the laminate, in which the above-mentioned low dielectric resin composition is used as a low dielectric adhesive.

[0173] 3, copper-clad laminate 21 includes insulating layer 22, conductor layer 24 disposed opposite insulating layer 22, and adhesive layer 23 disposed between insulating layer 22 and conductor layer 24 to bond insulating layer 22 and conductor layer 24. In copper-clad laminate 21, adhesive layer 23 is formed from the above-mentioned low-dielectric adhesive.

[0174] The insulating layer 22 is, for example, an insulating layer that does not have adhesive properties (non-adhesive insulating layer). The insulating layer 22 contains, for example, the above-mentioned thermosetting resin. The insulating layer 22 is preferably made of the above-mentioned thermosetting resin.

[0175] The conductor layer 24 is a thin film made of a known conductive material, similar to the conductor layer 4. An example of the conductive material is copper. The conductor layer 24 is formed by a known film formation method. The thickness of the conductor layer 24 is adjusted to be relatively thin, for example. This allows the circuit pattern to be formed by a subtractive method. The thickness of the conductor layer 24 is, for example, 50 μm or less.

[0176] The adhesive layer 23 is interposed between the insulating layer 22 and the conductor layer 24. The adhesive layer 23 is a dried product of a low dielectric adhesive. The low dielectric adhesive includes, for example, the low dielectric resin composition described above. The low dielectric adhesive is preferably a diluted solution of the low dielectric resin composition described above.

[0177] When manufacturing the copper-clad laminate 21, for example, first, the insulating layer 22 and the conductor layer 24 are prepared. Next, a low-dielectric adhesive is applied to one side of the insulating layer 22. Thereafter, the conductor layer 24 is bonded to one side of the low-dielectric adhesive, and the low-dielectric adhesive is dried. In this way, the copper-clad laminate 21 is obtained. Note that the copper-clad laminate 21 can also be manufactured in the reverse order described above. That is, in this method, the low-dielectric adhesive is applied to one side of the conductor layer 24. Thereafter, the insulating layer 22 is bonded to one side of the low-dielectric adhesive, and the low-dielectric adhesive is dried. In this way, the copper-clad laminate 21 is obtained.

[0178] In the copper-clad laminate 21, the insulating layer 22 and the conductor layer 24 are bonded together by an adhesive layer 23 (a low-dielectric adhesive). That is, the copper-clad laminate 21 has the adhesive layer 23. The adhesive layer 23 (a low-dielectric adhesive) contains the low-dielectric resin composition. Therefore, in the copper-clad laminate 21, the adhesive layer 23 (a low-dielectric adhesive) has excellent dimensional stability.

[0179] In the copper-clad laminate 21 of the third embodiment described above, the adhesive layer 23 and the conductor layer 24 are formed only on one side of the insulating layer 22, but the adhesive layer 23 and the conductor layer 24 may be formed on both sides of the insulating layer 22. In such a case, the copper-clad laminate 21 may not have the insulating layer 22. That is, the conductor layer 24 may be formed on both sides of the adhesive layer 23. In other words, two conductor layers 24 may be bonded by the adhesive layer 23. In such a case, the adhesive layer 23 also serves as the insulating layer 22.

[0180] (4) Fourth embodiment 4 is a schematic cross-sectional view showing a circuit board as a fourth embodiment of the laminate. In the fourth embodiment, similarly to the third embodiment, the above-mentioned low dielectric resin composition is used as a low dielectric adhesive.

[0181] More specifically, the copper-clad laminate 21 of the third embodiment described above can be processed to form a circuit board 31. More specifically, the conductor layer 24 of the copper-clad laminate 21 can be etched by a known method to form a circuit 34. As a result, as shown in FIG. 4, a circuit board 31 is formed as a fourth embodiment of the laminate.

[0182] In such a circuit board, an insulating layer 22 and a circuit 34 made of a conductor layer are bonded together by an adhesive layer 23 .

[0183] In this circuit board 31, the insulating layer 22 and the circuit 34 made of a conductor layer are bonded together by an adhesive layer 23 (low dielectric adhesive). The adhesive layer 23 (low dielectric adhesive) contains the low dielectric resin composition described above. Therefore, in the circuit board 31, the adhesive layer 23 (low dielectric adhesive) has excellent dimensional stability.

[0184] In the circuit board 31 of the fourth embodiment described above, the adhesive layer 23 and the circuit 34 are formed on only one side of the insulating layer 22, but the adhesive layer 23 and the circuit 34 may be formed on both sides of the insulating layer 22. In such a case, the circuit board 31 does not need to have the insulating layer 22. That is, the circuit 34 may be formed on both sides of the adhesive layer 23. In other words, two circuits 34 may be bonded by the adhesive layer 23. In such a case, the adhesive layer 23 also serves as the insulating layer 22.

[0185] (5) Fifth embodiment 5 to 8 are cross-sectional views showing steps for producing a circuit board as a fifth embodiment of the laminate. In the fifth embodiment, the above-mentioned low dielectric resin composition is used as a low dielectric adhesive.

[0186] 5 to 8, circuit board 41 is a multilayer circuit board having at least two conductor layers. More specifically, as shown in FIG. 8O, circuit board 41 includes a first conductor layer 40, a second conductor layer 50 disposed opposite first conductor layer 40, and an adhesive layer 51 disposed between first conductor layer 40 and second conductor layer 50 and adhering first conductor layer 40 and second conductor layer 50 together. In circuit board 41, adhesive layer 51 is formed from the low dielectric adhesive (preferably a diluted solution of a low dielectric resin composition).

[0187] 5A, a carrier-attached copper foil 42 is first prepared. The carrier-attached copper foil 42 includes a carrier layer 43 and a copper foil 44 laminated on one side of the carrier layer 43.

[0188] The carrier layer 43 is not particularly limited, and may be a known release sheet. The copper foil 44 is laminated on the carrier layer 43 by a known method. The thickness of the copper foil 44 is appropriately set depending on the purpose and application. Furthermore, the copper foil 44 may be surface-treated as needed. Examples of surface treatments include roughening treatments.

[0189] Next, in this method, as shown in FIG. 5B, a first resist layer 45 having a predetermined shape is formed on one surface of the copper foil 44. The first resist layer 45 is formed, for example, by applying a known resist liquid, exposing it to light, and developing it. Alternatively, the first resist layer 45 can be formed by exposing and etching a dry film resist.

[0190] Next, in this method, as shown in FIG. 5C, a first plating layer 46 is formed. The first plating layer 46 is formed, for example, by electrolytic plating. In electrolytic plating, for example, the carrier layer 43, copper foil 44, and first resist layer 45 are immersed in an electrolytic plating solution, and then a current is applied to the copper foil 44. As a result, the first plating layer 46 is formed on one surface of the copper foil 44 in the reverse pattern of the first resist layer 45. In other words, the first plating layer 46 has a circuit pattern.

[0191] Next, in this method, as shown in Fig. 6D, the first resist layer 45 is removed by a known method. Next, in this method, as shown in Fig. 6E, the copper foil 44 exposed from the first plating layer 46 is removed by a known method. This forms the first conductor layer 40, which includes the copper foil 44 that remains without being removed and the first plating layer 46 laminated on the copper foil 44. In other words, the first conductor layer 40 includes the copper foil 44 and the first plating layer 46. The first conductor layer 40 is preferably made of the copper foil 44 and the first plating layer 46.

[0192] Next, in this method, an adhesive layer 51 made of a low dielectric adhesive is laminated to the carrier layer 43, the first plating layer 46, and the copper foil 44, as shown in FIG. 6F.

[0193] More specifically, in this method, for example, a cast film of a low-dielectric adhesive is prepared. The cast film is then pressure-bonded to the carrier layer 43, the first plating layer 46, and the copper foil 44. As a result, the cast film covers the first plating layer 46 and the copper foil 44. The cast film also forms an adhesive layer 51.

[0194] On the other hand, in this method, a carrier-attached copper foil 52 is separately prepared. The carrier-attached copper foil 52 includes a carrier layer 53 and a copper foil 54 laminated on the other surface of the carrier layer 53. Then, in this method, the copper foil 54 of the carrier-attached copper foil 52 is laminated on an adhesive layer 51, as shown in Fig. 6G.

[0195] Next, in this method, as shown in FIG. 7H, the carrier layer 53 of the carrier-attached copper foil 52 is peeled off. Next, as shown in FIG. 7I, the copper foil 54 and the adhesive layer 51 are opened by a known method to form via holes 58. The first plating layer 46 is exposed from the via holes 58. Next, in this method, as shown in FIG. 7J, the via holes 58 are filled with a conductive material to form via fills 59. The conductive material may be, for example, copper.

[0196] Next, in this method, as shown in FIG. 7K, a second resist layer 55 having a predetermined shape is formed on one surface of the copper foil 54. The second resist layer 55 is formed, for example, by applying a known resist liquid, exposing it to light, and developing it. Similarly to the first resist layer 45, the second resist layer 55 can also be formed from a dry film resist.

[0197] Next, in this method, as shown in Fig. 8L, the second plating layer 56 is formed. The second plating layer 56 is formed, for example, by electrolytic plating. As a result, the second plating layer 56 is formed on one surface of the copper foil 54 in the reverse pattern of the second resist layer 55. In other words, the second plating layer 56 has a circuit pattern.

[0198] Next, in this method, as shown in FIG. 8M, the second resist layer 55 is removed by a known method. Next, in this method, as shown in FIG. 8N, the copper foil 54 exposed from the second plating layer 56 is removed by a known method. This forms the second conductor layer 50, which includes the copper foil 54 that remains without being removed and the first plating layer 56 laminated on the copper foil 54. In other words, the second conductor layer 50 includes the copper foil 54 and the second plating layer 56. The second conductor layer 50 is preferably made of the copper foil 54 and the second plating layer 56.

[0199] 8O, the method then involves peeling off the carrier layer 43, thereby exposing the copper foil 44. As a result, the circuit board 1 is formed.

[0200] In the circuit board 41, the first conductor layer 40 and the second conductor layer 50 are bonded together by an adhesive layer 51 (low dielectric adhesive). That is, the circuit board 41 has an adhesive layer 51. The adhesive layer 51 (low dielectric adhesive) contains the low dielectric resin composition. Therefore, in the circuit board 41, the adhesive layer 51 (low dielectric adhesive) has excellent dimensional stability.

[0201] 4. Variations In the above description, all of the polyphenylene ether resin, the styrene-based elastomer, and the cyclic olefin-based polymer are modified with a functional group-containing monomer, but this is not limited thereto, and one or two of the polyphenylene ether resin, the styrene-based elastomer, and the cyclic olefin-based polymer may also be modified with a functional group-containing monomer.

[0202] In such a case, one or two of the polyphenylene ether resin, the styrene-based elastomer, and the cyclic olefin-based polymer are mixed in advance with the functional group-containing monomer, and the mixture is reacted, and then the first step is carried out. [Example]

[0203] Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the following examples. Note that "parts" and "%" are by mass unless otherwise specified. Furthermore, specific numerical values ​​such as blending ratios (content ratios), physical property values, and parameters used in the following description can be substituted with the corresponding upper limit values ​​(numeric values ​​defined as "equal to or less than") or lower limit values ​​(numeric values ​​defined as "equal to or more than" or "exceeding") of the blending ratios (content ratios), physical property values, parameters, etc. described in the above "Form for Carrying Out the Invention."

[0204] <Ingredient details> Details of the abbreviations used in each example and comparative example are given below. Resin 1: Polyphenylene ether resin represented by the above formula (1) Resin 2: Polyphenylene ether resin represented by the above formula (3) Resin 3: Polyphenylene ether resin represented by the above formula (2) SEPTON 2002: Product name "SEPTON2002", manufactured by Kuraray Co., Ltd., styrene-ethylene-propylene-styrene copolymer (SEPS), styrene unit content 30% by mass, weight average molecular weight 55,000 SEPTON 8007L: Product name "SEPTON 8007L", manufactured by Kuraray Co., Ltd., styrene-butadiene-styrene copolymer (SBS), styrene unit content 30% by mass, weight average molecular weight 75,400 Kraton G1652: Trade name "Kraton G1652", manufactured by Kraton Polymer Japan, styrene-ethylene-butylene-styrene copolymer (SEBS), styrene unit content 30% by mass, weight average molecular weight 75,000

[0205] <Production of polyphenylene ether resin> Manufacturing Example 1 A 500 mL three-neck flask was equipped with a Dimroth valve and a pressure-equalizing dropping funnel equipped with a three-way stopcock. After replacing the atmosphere in the flask with nitrogen, 100 g of resin 3 (raw materials), 150 g of toluene, and 50 g of methyl ethyl ketone were added, followed by 7.2 g of tris(4-hydroxyphenyl)methane. Next, a thermometer was installed in the flask, and the flask was heated to 90°C in an oil bath while stirring with a magnetic stirrer to dissolve the polyphenylene ether polymer.

[0206] Next, 7.5 g of a 40% meta-xylene solution (Niper BMT, manufactured by NOF Corp.) of a mixture of benzoyl peroxide, benzoyl m-methylbenzoyl peroxide, and m-toluyl peroxide was diluted with 117.5 g of toluene to prepare an initiator solution. This initiator solution was then added dropwise to the flask over 2 hours. After the addition, stirring was continued at 80°C for 4 hours. The polymer solution was then added dropwise to methanol to reprecipitate the polymer, which was then filtered off. The polymer was then dried under vacuum at 100°C for 3 hours to produce a polyphenylene ether resin. The number average molecular weight was 30,000.

[0207] <Production of Cyclic Olefin Polymers> Manufacturing Example 2 (Catalyst Preparation) VO(OC2H5)Cl2 was diluted with cyclohexane to obtain a vanadium catalyst solution, the vanadium concentration of which was 6.7 mmol / L.

[0208] Also, ethyl aluminum sesquichloride (Al(C2H5) 1.5 Cl 1.5 ) was diluted with cyclohexane to obtain an aluminum catalyst solution. The aluminum concentration in the aluminum catalyst solution was 107 mmol / L.

[0209] (polymerization) Using a stirred polymerization reactor (inner diameter 500 mm, reaction volume 100 L), ethylene and tetracyclo[4.4.0.12,5.17,10]-3-dodecene were continuously fed and copolymerized. The glass transition temperature (Tg) of the cyclic olefin polymer was adjusted by adjusting the ratio of ethylene to tetracyclo[4.4.0.12,5.17,10]-3-dodecene.

[0210] During the copolymerization, the vanadium catalyst solution was supplied to the polymerization reactor so that the vanadium catalyst concentration relative to cyclohexane in the polymerization reactor was 0.6 mmol / L. The aluminum catalyst solution was supplied to the polymerization reactor so that the molar ratio of aluminum to vanadium (Al / V) was 12.0. The polymerization temperature was 12°C. The polymerization pressure was 3.1 kg / cm. 2 G (gauge pressure).

[0211] This resulted in a copolymer of ethylene and tetracyclo[4.4.0.12,5.17,10]-3-dodecene, which was obtained as a solution in cyclohexane (solvent).

[0212] (decalcification) The copolymer solution was extracted from the polymerization reactor. A 25% by mass NaOH solution was added to the copolymer solution to terminate the reaction. This also removed catalyst residue from the copolymer solution (decalcification treatment). The copolymer concentration in the solution was 7.7% by mass.

[0213] To the copolymer solution, pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] was added as a stabilizer in an amount of 0.4 parts by mass relative to 100 parts by mass of the copolymer.

[0214] Then, a mixing vessel (effective volume 1.0 cm) was 3 The copolymer solution was stirred for 1 hour using a stirring rod. The solid content of the copolymer was 5% by mass.

[0215] (Desolvation) Double pipe heater (outer pipe diameter 2B, inner pipe diameter 3 / 4B, length 21m, heat source 20kg / cm 2 A copolymer solution (solid content concentration: 5% by mass) was supplied to the reactor (G steam) and heated to 180° C. The supply rate was 150 kg / H.

[0216] Next, a double-tube flash dryer (outer tube diameter 2B, inner tube diameter 3 / 4B, length 27m, heat source 20kg / cm 2 Cyclohexane was removed from the copolymer solution using a steam (G steam) and a flash hopper (volume 200 L). Unreacted monomers were also removed along with the cyclohexane.

[0217] This resulted in a molten cyclic olefin polymer. The cyclic olefin polymer had a glass transition temperature (Tg) of 105° C. and a weight average molecular weight of 113,000.

[0218] Manufacturing Example 3 A cyclic olefin polymer was produced according to the same procedure as in Production Example 2. However, the composition ratio of ethylene and tetracyclo[4.4.0.12,5.17,10]-3-dodecene was changed to set the glass transition temperature (Tg) to 125° C. The weight average molecular weight of the cyclic olefin polymer was 116,000.

[0219] <Production of Low Dielectric Resin Composition> Examples 1 to 14 and Comparative Examples 1 to 3 According to the formulations shown in Tables 1 and 2, polyphenylene ether resin, styrene elastomer, cyclic olefin polymer, maleic anhydride (1 part by mass per 100 parts by mass of the polyphenylene ether resin, styrene elastomer, and cyclic olefin polymer), and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane (0.6 parts by mass per 100 parts by mass of the polyphenylene ether resin, styrene elastomer, and cyclic olefin polymer) were mixed and melt-kneaded at 230°C using a vented twin-screw kneading extruder. This caused the polyphenylene ether resin, styrene elastomer, and cyclic olefin polymer to react with each other. The mixture was then cooled and pelletized to obtain pellets of the low dielectric resin composition. Next, 100 parts by mass of the pellets were dissolved in 400 parts by mass of toluene in a heated environment to obtain a diluted solution of the low dielectric resin composition (solid concentration: 20% by mass).

[0220] <Evaluation> (weight average molecular weight and number average molecular weight) The weight average molecular weight and / or number average molecular weight of the polyphenylene ether resin, styrene elastomer, and cyclic olefin polymer used in each example and comparative example was measured under the following conditions. {conditions} Analytical equipment: GPC-IR6 MCT type gel permeation chromatograph (Polymer Characterization) Detector: IR6 type MCT infrared detector Columns: 2x TSKgel GMH6-HT + 2x TSKgel GMH6-HTL (both 7.5mm I.D x 30cm, Tosoh Corporation) Mobile phase: o-dichlorobenzene (containing 0.025% BHT) Measurement temperature: 140℃ Sample concentration: 0.1% (w / v) Flow rate: 1.0ml / min Injection volume: 400μl Standard material: polystyrene

[0221] [Glass transition temperature (Tg)] The glass transition temperatures (Tg) of the cyclic olefin polymers of Production Examples 2 and 3 were measured using a differential scanning calorimeter (X-DSC7000 (manufactured by SII Corporation)) in accordance with JIS K 7122 (2012). Specifically, 10 mg of sample was placed in a dedicated aluminum pan and heated from -100°C to 200°C at 10°C / min (1st run) and held at that temperature for 5 minutes. Next, the sample was cooled to -100°C at 10°C / min, and then heated again from -100°C to 200°C at 10°C / min (2nd run). Alumina placed in the same aluminum pan was used as a reference.

[0222] In the DSC thermogram obtained in this second run, the point at which the baseline shifted downward was measured as the glass transition temperature.

[0223] (Dielectric) A diluted solution of the low dielectric resin composition of each Example and Comparative Example was applied to a release film (polyethylene terephthalate film, thickness 100 μm) and dried at 100°C for 1 minute. This resulted in a dried coating film of the low dielectric resin composition (film thickness approximately 50 μm). The resulting dried coating film was then formed into a strip, and the relative dielectric constant Dk of the dried coating film was measured in accordance with JIS R1641 (2007). Note that a cavity resonator (vector network analyzer HP8510B (manufactured by Keysight Technologies)) was used for the measurement. The measurement frequency was 10 GHz. The results are shown in Tables 1 and 2. It can be seen that the lower the relative dielectric constant Dk, the better the low dielectric property.

[0224] (compatibility) A toluene solution of polyphenylene ether resin (solid content concentration 50% by mass) and a toluene diluted solution of the low dielectric resin composition of each Example and Comparative Example were mixed at a solid content ratio of 7:3, coated on a glass plate, and dried at 100°C for 1 minute (dry film thickness approximately 20 μm). The haze of the coating film was measured in accordance with JIS K7136 using a haze meter (NDH 4000, manufactured by Nippon Denshoku Industries Co., Ltd.). Compatibility was evaluated according to the following criteria. The results are shown in Table 1. {standard} 5: The whole was homogeneous, and the haze was less than 15. 4: The whole was homogeneous, and the haze was 15 or more and less than 50. 3: The whole was homogeneous, and the haze was 50 or more. 2: A non-uniform distribution of less than 1 cm was observed. An uneven distribution of more than 1:1 cm was observed.

[0225] (Evaluation of linear expansion coefficient) A diluted solution of the low dielectric resin composition of each Example and Comparative Example was applied to a release film (polyethylene terephthalate film, thickness 100 μm) and dried at 100°C for 1 minute to obtain a coating. The thickness of the coating was then measured using a film thickness meter, and found to be approximately 10 μm. The coating was then molded into a 5 mm wide film, and the linear expansion coefficient was measured from 40 to 60°C using a TMA7100C (Hitachi High-Tech Corporation) in a film extension mode with a load of 1 gf (9.8 mN), a sample length between chucks of 10 mm, and a nitrogen atmosphere at a heating rate of 5°C / min over a test temperature range of room temperature to 200°C. The results are shown in Tables 1 and 2.

[0226] [Table 1]

[0227] [Table 2] [Explanation of symbols]

[0228] 1, 21 Copper-clad laminate 2. Adhesive insulating layer 4, 24 Conductor layers 22 Insulating layer 23, 51 Adhesive layer 40 First conductor layer 50 Second conductor layer

Claims

1. a polyphenylene ether resin; a styrene-based elastomer; a cyclic olefin polymer having an alicyclic ring in its main chain; A low dielectric resin composition comprising a reaction product of the polyphenylene ether resin with the styrene-based elastomer and / or the cyclic olefin-based polymer.

2. 2. The low dielectric resin composition according to claim 1, wherein the polyphenylene ether resin has a number average molecular weight of 500 or more and 50,000 or less.

3. The low dielectric resin composition according to claim 1 , wherein the polyphenylene ether resin has a radical polymerizable group.

4. 2. The low dielectric resin composition according to claim 1, wherein at least one selected from the group consisting of the polyphenylene ether resin, the styrene-based elastomer, and the cyclic olefin-based polymer is modified with a functional group-containing monomer.

5. The low dielectric resin composition according to claim 4 , wherein the functional group-containing monomer includes a carboxy group-containing monomer.

6. An adhesion promoter comprising the low dielectric resin composition of claim 1.

7. A cured product of a low dielectric adhesive molding material comprising the adhesion promoter according to claim 6 and a thermosetting resin, A low dielectric adhesive molded article, wherein the thermosetting resin comprises at least one selected from the group consisting of epoxy resin, polyphenylene ether resin, fluororesin, polyimide resin, phenolic resin, melamine resin, polyolefin resin having an unsaturated double bond, and liquid crystal polymer.

8. 8. The low dielectric adhesive molding according to claim 7, having a dielectric loss tangent of less than 0.0050.

9. An insulating layer comprising the low dielectric adhesive molding according to claim 7; a conductor layer disposed on at least one surface of the insulating layer; A laminate comprising:

10. A low dielectric adhesive comprising the low dielectric resin composition according to any one of claims 1 to 5.

11. an insulating layer; a conductor layer disposed opposite the insulating layer; an adhesive layer disposed between the insulating layer and the conductor layer and adhering the insulating layer and the conductor layer; Equipped with A laminate wherein the adhesive layer comprises the low dielectric adhesive of claim 10.

12. a first conductor layer; a second conductor layer disposed opposite the first conductor layer; an adhesive layer disposed between the first conductor layer and the second conductor layer and adhering the first conductor layer and the second conductor layer; Equipped with A laminate wherein the adhesive layer comprises the low dielectric adhesive of claim 10.

13. A method for producing the low dielectric adhesive molded article according to any one of claims 1 to 5, a first step of mixing the polyphenylene ether resin, the styrene-based elastomer, the cyclic olefin-based polymer, and a peroxide; and a second step of reacting the polyphenylene ether resin with the styrene-based elastomer and / or the cyclic olefin-based polymer.

14. 14. The method for producing a low dielectric resin composition according to claim 13, wherein a blending ratio of the polyphenylene ether resin is 1 part by mass or more and 50 parts by mass or less per 100 parts by mass of the total amount of the polyphenylene ether resin, the styrene-based elastomer, and the cyclic olefin-based polymer.

15. 14. The method for producing a low dielectric resin composition according to claim 13, wherein a blending ratio of the styrene-based elastomer is 10 parts by mass or more and 90 parts by mass or less, relative to 100 parts by mass of the total amount of the styrene-based elastomer and the cyclic olefin-based polymer.

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