Resin compositions and metal-resin composites

Abstract

The present invention provides a resin composition with a low dielectric constant and a lower dielectric loss tangent, and a metal-resin composite containing the resin composition. [Solution] A resin composition (X) comprising a resin (A) and a 4-methyl-1-pentene polymer (B), wherein the resin (A) has a relative permittivity of 2.3 or more at a frequency of 1 MHz after being heated to 300°C for 120 minutes under a nitrogen atmosphere.

Description

[Technical Field]

[0001] This invention relates to resin compositions and metal-resin composites. [Background technology]

[0002] Traditionally, plastic materials have been widely used in electronic devices and components such as circuit boards as insulating materials where reliability is required, due to their characteristics such as high insulation, dimensional stability, and ease of molding. Recently, with the increasing speed of processing and transmission in electronic devices, the frequency of electrical signals has also increased.

[0003] Generally, the transmission loss of an electrical signal is proportional to the product of frequency, relative permittivity, and dielectric loss tangent. Therefore, the higher the frequency of the electrical signal used, the greater the transmission loss. To reduce this transmission loss and accommodate higher frequencies of electrical signals, plastic materials with low dielectric constant and low dielectric loss tangent are required.

[0004] Generally, since dielectric constant depends on the type of material, it has been suggested to select plastic materials with low dielectric constant. Examples of plastic materials with low dielectric constant include olefin resins such as polyethylene (PE) and fluororesins such as polytetrafluoroethylene (PTFE). However, fluororesins have sufficient heat resistance but poor moldability, and olefin resins have the problem of low heat resistance, below 100°C.

[0005] In contrast, polyimide possesses high heat resistance among plastic materials, but most are known to have a high dielectric constant. For this reason, various methods have been proposed to lower the dielectric constant of polyimide. For example, a method has been proposed to lower the dielectric constant of polyimide by introducing fluorine groups into the polyimide skeleton. However, introducing too many fluorine groups into the polyimide skeleton has resulted in problems such as reduced adhesion to Cu wiring materials and reduced solvent resistance when used as a printed circuit board.

[0006] Another proposed method involves introducing a bulky framework into the polyimide backbone to lower the resin density and thereby reduce the dielectric constant. However, introducing a bulky framework impairs the packing between the polyimide main chains, leading to problems such as reduced mechanical strength and increased thermal expansion coefficient. In particular, plastic materials used in circuit boards and the like require low thermal expansion to minimize dimensional changes, and furthermore, the difference in thermal expansion coefficient with that of Cu wiring materials must be as small as possible.

[0007] Patent Document 1 discloses a composite film of polyimide and polyethylene, and proposes using such a composite film in a metal-resin laminate. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] International Publication No. 2011 / 093079 [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] However, the metal-resin composite described in Patent Document 1 had room for improvement in terms of electrical properties such as dielectric loss tangent. The present invention has been made in view of these circumstances, and aims to provide a resin composition with a lower dielectric loss tangent while maintaining a low dielectric constant, and to provide a metal-resin composite containing the resin composition. [Means for solving the problem]

[0010] [1] Resin (A) and 4-methyl-1-pentene polymer (B) and Includes, The resin (A) is a resin composition (X) having a relative permittivity of 2.3 or more at a frequency of 1 MHz after being heated to 300°C for 120 minutes under a nitrogen atmosphere.

[0011] [2] The resin composition (X) according to [1], wherein the relative permittivity of the resin composition (X) at a frequency of 1 MHz is lower than the relative permittivity of the resin (A) at a frequency of 1 MHz after heating at 300 °C for 120 minutes in a nitrogen atmosphere.

[0012] [3] The resin composition (X) according to [1] or [2], wherein the resin (A) is at least one selected from the group consisting of polyamic acid, polyimide, polyamideimide, liquid crystal polymer, and polyphenylene ether.

[0013] [4] The resin composition (X) according to any one of [1] to [3], wherein the resin (A) is polyamic acid.

[0014] [5] The resin composition (X) according to any one of [1] to [4], wherein the 4-methyl-1-pentene polymer (B) has a polar group.

[0015] [6] The resin composition (X) according to [5], wherein the polar group is at least one functional group selected from the group consisting of hydroxyl group, carboxyl group, amino group, amide group, imide group, ether group, urethane group, urea group, phosphate group, sulfonic acid group, and carboxylic anhydride group.

[0016] [7] The resin composition (X) according to any one of [1] to [6], which contains 5 to 200 parts by mass of the 4-methyl-1-pentene polymer (B) with respect to 100 parts by mass of the resin (A).

[0017] [8] The resin composition (X) according to any one of [1] to [7], which further contains a solvent.

[0018] [9] A metal resin composite having a metal and a resin layer (I) that is in direct contact with the metal or in contact with the metal via an intermediate layer, The metal resin composite, wherein the resin layer (I) contains the resin composition (X) according to any one of [1] to [7].

[0019]

[10] A metal resin composite having a metal and a resin layer (I) directly or indirectly contacting the metal through an intermediate layer, The metal resin composite, wherein the resin layer (I) contains a cured product or a dried product of the resin composition (X) described in [8].

[0020]

[11] The metal is a metal layer, The metal resin composite according to [9] or

[10] , which is a metal laminate in which the metal layer and the resin layer (I) are laminated directly or through an intermediate layer.

[0021]

[12] The metal laminate according to

[11] , which is a circuit board.

[0022]

[13] The metal laminate according to

[11] , which is a high-frequency circuit board.

[0023] ​​​​​​​​​​​​​​​​​​​​​​​​Regarding the resin composition (X): The resin composition (X) comprises a resin (A) and a 4-methyl-1-pentene polymer (B). Here, the resin (A) satisfies the requirement that its dielectric constant at a frequency of 1 MHz after being heated to 300°C for 120 minutes under a nitrogen atmosphere is 2.3 or more. Furthermore, the resin (A) may change into a different substance from the one before heating when heated to 300°C for 120 minutes under a nitrogen atmosphere, or it may remain the same substance as before heating even when heated to 300°C for 120 minutes under a nitrogen atmosphere. For example, the resin (A) may be a polyamic acid that changes into polyimide when heated to 300°C for 120 minutes under a nitrogen atmosphere. Furthermore, the resin (A) may be a polyimide that does not change when heated to 300°C for 120 minutes under a nitrogen atmosphere.

[0028] The resin composition (X) may be in solid form, or it may be a varnish in which resin (A) and a 4-methyl-1-pentene polymer (B) are dissolved in a solvent. If resin (A) is a substance that does not change when heated under the above conditions, such as polyimide, and the resin composition (X) is a varnish, a dried product of the resin composition (X) can be obtained by heating the resin composition (X). On the other hand, if resin (A) is a substance that changes when heated under the above conditions, such as polyamic acid, and the resin composition (X) is a varnish, a cured product of the resin composition (X) can be obtained by heating the resin composition (X). In these cases, the relative permittivity of the cured or dried product of resin (A) at a frequency of 1 MHz is 2.3 or higher.

[0029] <Regarding resin (A)> Resin (A) has a dielectric constant of 2.3 or higher, preferably 3.0 or higher, and more preferably 3.0 to 4.0, at a frequency of 1 MHz after being heated to 300°C for 120 minutes under a nitrogen atmosphere. Such resin (A) typically has a higher dielectric constant and dielectric loss tangent compared to 4-methyl-1-pentene polymers.

[0030] From the viewpoint of increasing the heat resistance of the resin composition (X) and lowering the coefficient of thermal expansion, resin (A) is preferably a resin with a glass transition temperature of 150°C or higher.

[0031] The resin (A) is not particularly limited as long as its dielectric constant at a frequency of 1 MHz after heating to 300°C for 120 minutes under a nitrogen atmosphere is 2.3 or higher; known thermosetting resins and thermoplastic resins can be used. Specific examples of such resin (A) include polyamic acid, polyimide, polyamide-imide, polyphenylene ether, polyphenylene sulfide, polyether, polyether ketone, polyether ether ketone, polyethylene terephthalate, polycarbonate, liquid crystal polymer, epoxy resin, polyether sulfone, and phenolic resin. A liquid crystal polymer is a polymer that exhibits liquid crystallinity in a solution or molten state, and is preferably a thermotropic liquid crystal polymer that exhibits liquid crystallinity in a molten state due to its excellent mechanical strength and heat resistance. Resin (A) is preferably at least one selected from the group consisting of polyamic acid, polyimide, polyamide-imide, liquid crystal polymer, and polyphenylene ether.

[0032] Among the resins (A), polyamic acid or polyimide is more preferred, and polyamic acid is even more preferred, from the viewpoint of having particularly excellent heat resistance and dimensional stability. The polyimide is preferably a polyimide having a constituent unit represented by general formula (1), where m is an integer of 1 or more. Polyimides that contain a relatively large number of aromatic rings in the molecule and have a rigid molecular structure have high heat resistance and a low coefficient of thermal expansion. [ka]

[0033] In general formula (1), A is selected from the divalent groups represented by the following formula. In the following formula, X1 to X6 are a single bond, -O-, -S-, -CO-, -COO-, -C(CH3)2-, -C(CF3)2-, -SO2-, or -NHCO-, respectively. X1 to X6 contained in multiple A groups may be the same or different from each other. In the following formula, R1, R2, R3, and R4 may be the same or different from each other, and each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. [ka]

[0034] In general formula (1), A can be a divalent group derived from an aromatic diamine. Examples of aromatic diamines include m-phenylenediamine, o-phenylenediamine, and p-phenylenediamine. These may be used individually or in combination of two or more.

[0035] In general formula (1), A may include a divalent group derived from an aliphatic diamine other than the divalent group derived from the aromatic diamine compound.

[0036] In general formula (1), B is selected from the tetravalent group represented by the following formula. In the following formula, Y1 to Y6 are a single bond, -O-, -S-, -CO-, -COO-, -C(CH3)2-, -C(CF3)2-, -SO2-, or -NHCO-, respectively. Y1 to Y6 contained in multiple B may be the same or different from each other. [ka]

[0037] In general formula (1), B can be a tetravalent group derived from aromatic tetracarboxylic dianhydrides. Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride and 3,3',4,4'-biphenyltetracarboxylic dianhydride. These may be used individually or in combination of two or more types.

[0038] In general formula (1), B may include a tetravalent group derived from a tetravalent group other than the tetravalent group derived from the aromatic tetracarboxylic dianhydride, derived from a tetravalent group derived from another tetracarboxylic dianhydride.

[0039] Polyimides having the constituent units represented by general formula (1) are obtained by heating and imidizing a polyamic acid containing the constituent units represented by the following general formula (2). In general formula (2), A, B, and m are the same as A, B, and m in general formula (1) mentioned above.

[0040] [ka]

[0041] The aforementioned polyamic acid can be obtained, for example, by polycondensation reaction of a diamine represented by the following general formula (2A) and a tetracarboxylic dianhydride represented by the following general formula (2B). [ka]

[0042] It is preferable to set the charging ratio of tetracarboxylic dianhydride to diamine to satisfy M1:M2 = 0.900~0.999:1.00 (M1: number of moles of tetracarboxylic dianhydride, M2: number of moles of diamine). M1:M2 is preferably 0.920~0.995:1.00, more preferably 0.950~0.995:1.00, and even more preferably 0.970~0.995:1.00. This is to make the polyamic acid an amine terminus.

[0043] The logarithmic viscosity of the polyamic acid, with a solid content of 15% by mass and N-methyl-2-pyrrolidone as the solvent, measured at 25°C using an Ubbelohde viscometer, is preferably 0.5 to 5.0 dl / g, and more preferably 1.0 to 2.0 dl / g.

[0044] <Regarding 4-methyl-1-pentene polymer (B)> Because the 4-methyl-1-pentene polymer (B) has a low dielectric constant and dielectric loss tangent, the dielectric constant of the resin composition (X) containing resin (A) and the 4-methyl-1-pentene polymer (B) tends to be low. In the following description, the constituent unit derived from 4-methyl-1-pentene in 4-methyl-1-pentene polymer (B) may be referred to as "constituent unit (i)". Similarly, the constituent unit derived from ethylene or α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) in 4-methyl-1-pentene polymer (B) may be referred to as "constituent unit (ii)". Furthermore, in the present invention, the term "4-methyl-1-pentene polymer" is a general term encompassing both a homopolymer of 4-methyl-1-pentene and a copolymer of 4-methyl-1-pentene and a polymerizable monomer other than 4-methyl-1-pentene.

[0045] The 4-methyl-1-pentene polymer (B), when prepared by the method described in the examples below, has a melting point (Tm) measured by differential scanning calorimeter (DSC) preferably of 180 to 220°C, more preferably of 190 to 215°C, and even more preferably of 195 to 210°C. When the melting point (Tm) measured by differential scanning calorimeter (DSC) is within the above range, the heat resistance of the resin layer (I) obtained from the resin composition (X) is good. If the resin composition (X) is a varnish containing a solvent, the resin layer (I) includes a cured product obtained by curing the resin composition (X) or a dried product obtained by drying it. Alternatively, the resin layer (I) may also be a cured product obtained by curing the resin composition (X) or a dried product obtained by drying it. The melting point (Tm) value tends to depend on the stereoregularity of the 4-methyl-1-pentene polymer (B) and the content of constituent unit (ii) in the 4-methyl-1-pentene polymer (B). Therefore, the melting point (Tm) can be adjusted by using the olefin polymerization catalyst described later and by controlling the content of constituent unit (ii).

[0046] The 4-methyl-1-pentene polymer (B), when melted (endothermally) by differential scanning calorimeter (DSC) using the method described in the examples below, has an endothermic termination temperature (TmE) of 200-230°C, more preferably 205-225°C, and even more preferably 205-220°C. Here, the endothermic termination temperature refers to the temperature at which melting is completed. The endothermic termination temperature and the exothermic onset temperature described below are indicators different from the onset and offset, which are generally considered to be the intersection points of the baseline and the steady-state line tangent. The endothermic termination temperature can be set to a desired value by, for example, appropriately selecting an olefin polymerization catalyst when polymerizing the 4-methyl-1-pentene polymer (B), controlling the content of the constituent unit (ii), etc.

[0047] 4-methyl-1-pentene polymers (B) whose endothermic termination temperature is within the aforementioned range exhibit excellent heat resistance. Therefore, resin layers obtained from resin compositions (X) containing 4-methyl-1-pentene polymers (B) whose endothermic termination temperature is within the aforementioned range also tend to exhibit excellent heat resistance. Furthermore, 4-methyl-1-pentene polymers (B) whose endothermic termination temperature is within the aforementioned range are more easily soluble in solvents usable during varnish preparation compared to 4-methyl-1-pentene polymers whose endothermic termination temperature is outside the aforementioned range. Therefore, the properties of varnishes and the like prepared using 4-methyl-1-pentene polymers (B) whose endothermic termination temperature is within the aforementioned range tend to be more uniform.

[0048] The 4-methyl-1-pentene polymer (B) is prepared by the method described in the examples below, and its crystallization temperature (Tc), as determined by differential scanning calorimeter (DSC), is preferably 150 to 220°C, more preferably 155 to 200°C, and even more preferably 160 to 190°C. The crystallization temperature can be set to a desired value by, for example, appropriately selecting an olefin polymerization catalyst when polymerizing the 4-methyl-1-pentene polymer (B), controlling the content of constituent unit (ii), etc. A 4-methyl-1-pentene polymer (B) having a crystallization temperature within the aforementioned range is preferred from the viewpoint of heat resistance. Furthermore, varnishes and the like obtained from compositions containing a 4-methyl-1-pentene polymer (B) having a crystallization temperature within the aforementioned range tend to have good properties and storage stability. As a result, the properties of the resin layer (I) formed using the varnish become uniform.

[0049] The 4-methyl-1-pentene polymer (B), when prepared by the method described in the examples below, has an exothermic onset temperature (TcS) in the crystallization (exothermic) curve measured by differential scanning calorimeter (DSC) that is preferably 150 to 210°C, more preferably 160 to 200°C, and even more preferably 165 to 195°C. The aforementioned exothermic onset temperature can be set to a desired value by, for example, appropriately selecting an olefin polymerization catalyst when polymerizing the 4-methyl-1-pentene polymer (B), controlling the content of the constituent unit (ii), etc.

[0050] 4-methyl-1-pentene polymers (B) whose exothermic onset temperature is within the aforementioned range exhibit excellent heat resistance. Therefore, resin layers obtained from resin compositions (X) containing 4-methyl-1-pentene polymers (B) whose exothermic onset temperature is within the aforementioned range also tend to exhibit excellent heat resistance. Furthermore, 4-methyl-1-pentene polymers (B) whose exothermic onset temperature is within the aforementioned range are more easily soluble in solvents usable during varnish preparation compared to 4-methyl-1-pentene polymers whose exothermic onset temperature is outside the aforementioned range. Therefore, the properties of varnishes and the like prepared using 4-methyl-1-pentene polymers (B) whose exothermic onset temperature is within the aforementioned range tend to be more uniform.

[0051] The 4-methyl-1-pentene polymer (B) has an intrinsic viscosity [η] of 4-methyl-1-pentene polymer (B) measured in decalin at 135°C by the method described in the examples below, preferably 0.5 to 6.0 dl / g, more preferably 0.6 to 3.0 dl / g, and even more preferably 0.7 to 1.5 dl / g. A 4-methyl-1-pentene polymer (B) with an intrinsic viscosity [η] within the aforementioned range exhibits good heat resistance. Furthermore, a varnish obtained by dissolving a composition (X) containing a 4-methyl-1-pentene polymer (B) with an intrinsic viscosity [η] within the aforementioned range exhibits good coatability, and a film that forms the resin layer (I) is easily formed. A varnish containing a polymer with an intrinsic viscosity [η] in the range of 0.5 to 6.0 dl / g may exhibit good coatability, such as being less prone to clumping during application, resulting in a more uniform coated surface, and being easier to apply smoothly over a wide area. The intrinsic viscosity [η] can be adjusted, for example, by the amount of hydrogen added during the polymerization process when producing a 4-methyl-1-pentene polymer (B).

[0052] In the 4-methyl-1-pentene polymer (B), if the structural unit derived from 4-methyl-1-pentene is referred to as "structural unit (i)" and the structural unit derived from ethylene or α-olefins having 3 to 20 carbon atoms (excluding 4-methyl-1-pentene) is referred to as "structural unit (ii)", then the 4-methyl-1-pentene polymer (B) preferably satisfies the following (b1) and (b2). (b1) The amount (U1) of constituent unit (i) in the 4-methyl-1-pentene polymer (B) is preferably 80.0 to 100 mol%, more preferably 85.0 to 99.5 mol%, and even more preferably 90.0 to 99.0 mol% (provided that the sum of constituent unit (i) and constituent unit (ii) is 100 mol%). (b2) In the 4-methyl-1-pentene polymer (B), the amount (U2) of constituent unit (ii) is preferably 0 to 20.0 mol%, more preferably 0.5 to 15.0 mol%, and even more preferably 1.0 to 10.0 mol% (provided that the sum of constituent unit (i) and constituent unit (ii) is 100 mol%). Furthermore, U1 and U2 are determined by the method described in the examples. 4-methyl-1-pentene polymers (B) in which U1 and U2 are within the aforementioned ranges exhibit excellent heat resistance. Therefore, resin layers formed using varnishes obtained from compositions containing 4-methyl-1-pentene polymers (B) in which U1 and U2 are within the aforementioned ranges also tend to exhibit excellent heat resistance.

[0053] The α-olefin that leads to the aforementioned structural unit (ii) can be a linear α-olefin. Examples of α-olefins that lead to the aforementioned structural unit (ii) include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-eicosene, and the like. Among these, linear α-olefins having 6 to 18 carbon atoms are preferred from the viewpoint of heat resistance. Specifically, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-heptadecene, 1-octadecene, etc. are preferred, and among these, 1-decene, 1-hexadecene, and 1-octadecene are particularly preferred. The aforementioned constituent unit (ii) may be derived from only one selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms, or it may be derived from two or more selected from the group consisting of ethylene and α-olefins having 3 to 20 carbon atoms.

[0054] Here, the 4-methyl-1-pentene polymer (B) can be a copolymer consisting only of constituent unit (i) and constituent unit (ii). In this case, the total of constituent unit (i) and constituent unit (ii) is 100 mol%.

[0055] The 4-methyl-1-pentene polymer (B) may further contain, in addition to structural units (i) and (ii), structural units derived from 4-methyl-1-pentene, ethylene, and other polymerizable monomers other than α-olefins having 3 to 20 carbon atoms, in amounts that do not impair the objectives of the present invention, specifically 10 mol% or less, preferably 5 mol% or less, and more preferably 3 mol% or less. The constituent units derived from other polymerizable monomers in the 4-methyl-1-pentene polymer (A) may be one type or two or more types.

[0056] Preferred examples of such other polymerizable monomers include vinyl compounds having a cyclic structure such as styrene, vinylcyclopentane, vinylcyclohexane, and vinylnorbornane; vinyl esters such as vinyl acetate; unsaturated organic acids or their derivatives such as maleic anhydride; conjugated dienes such as butadiene, isoprene, pentadiene, and 2,3-dimethylbutadiene; 1,4-hexadiene, 1,6-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, and 7-methyl-1,6-octadiene. Examples of non-conjugated polyenes include dienes, dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylenenorbornene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, and 2-propenyl-2,2-norbornadiene.

[0057] Here, if the 4-methyl-1-pentene polymer (B) contains structural units derived from other polymerizable monomers, it is preferable that the total content of structural unit (ii) and structural units derived from other polymerizable monomers satisfies the range of content of structural unit (ii). In this case, the total of structural unit (i), structural unit (ii), and structural units derived from other polymerizable monomers is 100 mol%.

[0058] The 4-methyl-1-pentene polymer (B) preferably has polar groups. When the 4-methyl-1-pentene polymer (B) has polar groups, it is easier for the 4-methyl-1-pentene polymer (B) to disperse uniformly in the resin composition (X) containing resin (A). Therefore, it is easier to suppress the increase in the coefficient of thermal expansion in the resin composition (X) obtained using the 4-methyl-1-pentene polymer (B). In addition, when the 4-methyl-1-pentene polymer (B) has polar groups, the surface smoothness of the resin layer obtained from the resin composition (X) is improved, so the transmission loss of the circuit board using the resin layer is less likely to increase.

[0059] The polar group is, for example, at least one functional group selected from the group consisting of hydroxyl group, carboxyl group, amino group, amide group, imide group, ether group, urethane group, urea group, phosphoric acid group, sulfonic acid group, and carboxylic acid anhydride group, and preferably at least one functional group selected from the group consisting of hydroxyl group, carboxyl group, and carboxylic acid anhydride group.

[0060] A 4-methyl-1-pentene polymer (B) having polar groups can be obtained by methods such as graft modification of the 4-methyl-1-pentene polymer (B) with a polar group-containing compound. That is, the 4-methyl-1-pentene polymer (B) is preferably a graft-modified product. The graft modification method will be described later.

[0061] When the 4-methyl-1-pentene polymer (B) is graft-modified, the amount of graft modification is preferably 0.1 to 5.0% by mass, more preferably 0.5 to 3.0% by mass, and even more preferably 1.0 to 2.0% by mass, based on the mass of the modified 4-methyl-1-pentene polymer (B) being 100% by mass. When the amount of graft modification of the 4-methyl-1-pentene polymer (B) is within the above range, it tends to exhibit excellent adhesion to metals.

[0062] [Method for producing 4-methyl-1-pentene polymer (B)] The 4-methyl-1-pentene polymer (B) can be obtained by polymerizing 4-methyl-1-pentene with a specific olefin that leads to the above-described structural unit (ii), and optionally with the other polymerizable monomers, in the presence of an olefin polymerization catalyst, using a known method.

[0063] Examples of olefin polymerization catalysts that can be used in the production of 4-methyl-1-pentene polymers (B) include metallocene catalysts. Preferred metallocene catalysts include those described in International Publication No. 01 / 53369, International Publication No. 01 / 27124, Japanese Patent Publication No. 3-193796, Japanese Patent Publication No. 02-41303, International Publication No. 06 / 025540, or International Publication No. 2014 / 123212.

[0064] The 4-methyl-1-pentene polymer (B) may be a commercially available 4-methyl-1-pentene polymer (for example, TPX manufactured by Mitsui Chemicals, Inc.). Alternatively, the 4-methyl-1-pentene polymer (B) may be a 4-methyl-1-pentene polymer (B) obtained by adjusting various physical properties by heat-treating a 4-methyl-1-pentene polymer produced with the catalyst or a commercially available 4-methyl-1-pentene polymer (for example, TPX manufactured by Mitsui Chemicals, Inc.) in an extruder or mixer.

[0065] If the 4-methyl-1-pentene polymer (B) has polar groups, these can be introduced by graft modification of the 4-methyl-1-pentene polymer (B). In this case, graft modification of the 4-methyl-1-pentene polymer (B) can be carried out by reacting a mixture of the 4-methyl-1-pentene polymer (B) and a polar group-containing compound in a molten state (using a kneading extruder, etc.) in or without a radical polymerization initiator; or by dissolving the 4-methyl-1-pentene polymer (B) and the polar group-containing compound in a good solvent and reacting them in the presence of a radical polymerization initiator.

[0066] The polar group-containing compound is preferably an ethylenically unsaturated monomer, more preferably an unsaturated carboxylic acid and / or its derivative. Examples of unsaturated carboxylic acids and / or their derivatives include unsaturated compounds having one or more carboxylic acid groups, esters of compounds having carboxylic acid groups with alkyl alcohols, and unsaturated compounds having one or more anhydride carboxylic acid groups.

[0067] Examples of unsaturated groups in unsaturated compounds include vinyl groups, vinylene groups, and unsaturated cyclic hydrocarbon groups. Unsaturated carboxylic acids and / or derivatives thereof can be used individually or in combination of two or more. Among these ethylenically unsaturated monomers, unsaturated dicarboxylic acids or their acid anhydrides are preferred, with maleic acid, nadic acid, or their acid anhydrides being particularly preferred.

[0068] <Resin composition (X)> The content of the 4-methyl-1-pentene polymer (B) in the resin composition (X) is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, and even more preferably 25 to 70 parts by mass, per 100 parts by mass of resin (A). When the content of the 4-methyl-1-pentene polymer (B) is within the above range, it is easy to obtain the effect of lowering the dielectric constant of the resin composition (X), and the heat resistance of the resin composition (X) does not decrease easily (the coefficient of thermal expansion does not increase easily).

[0069] [Regarding other components that may be included in the resin composition (X) (excluding the solvent)] The resin composition (X) may optionally contain inorganic fillers such as silica to enhance heat resistance and heat dissipation. The resin composition (X) may also optionally contain various additives such as flame retardants, antioxidants, heat stabilizers, weather stabilizers, antistatic agents, slip agents, leveling agents, strengthening agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, and fillers. The amounts of other components can be any amount that does not impair the purpose of the present invention, but the total amount of other components is usually 0.005 to 5 parts by mass, preferably 0.01 to 3 parts by mass, per 100 parts by mass of resin composition (X).

[0070] [solvent] Furthermore, the resin composition (X) may also contain a solvent. If the resin composition (X) contains a solvent, the resin composition (X) is a varnish in which the resin (A) and the 4-methyl-1-pentene polymer (B) are dissolved in the solvent.

[0071] The solvent that may be included in the resin composition (X) is not particularly limited, but is preferably an aprotic polar solvent, and more preferably an aprotic amide solvent. Examples of aprotic amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, and 1,3-dimethyl-2-imidazolidinone. These solvents may be used individually or in combination of two or more.

[0072] In addition to these solvents, other solvents may be included as needed. Examples of other solvents include organic solvents, such as aromatic hydrocarbons like benzene, toluene, o-xylene, m-xylene, p-xylene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, p-bromotoluene, chlorobenzene, and bromobenzene; and aliphatic hydrocarbons like methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, n-hexane, n-heptane, n-octane, cyclohexane, methylcyclohexane, and ethylcyclohexane; and so on. Among these, toluene, cyclohexane, methylcyclohexane, and the like can be suitably used.

[0073] The amount of solvent that may be contained in the resin composition (X) is preferably 60 to 99% by mass, and more preferably 70 to 95% by mass, as this simplifies the stirring and coating processes.

[0074] [Physical properties of resin composition (X)] As mentioned above, in order to reduce the transmission loss of electrical signals, resin compositions suitable for high frequencies are required to have a low dielectric constant (or relative dielectric constant) or a low dielectric loss tangent. Relative dielectric constant is the ratio of the dielectric constant ε of the medium to the dielectric constant ε0 of vacuum. The resin composition (X) of the present invention contains a low dielectric constant 4-methyl-1-pentene polymer (B), and therefore has low dielectric constant and dielectric loss tangent. The relative permittivity of the resin composition (X) at a frequency of 1 MHz is preferably less than 3.0. The lower limit of the relative permittivity of the resin composition (X) is not particularly limited, but is usually 2.3 or higher. Furthermore, the relative permittivity of the resin composition (X) at a frequency of 1 MHz is lower than that of resin (A) at a frequency of 1 MHz after heating to 300°C for 120 minutes in a nitrogen atmosphere. The procedure for measuring the relative permittivity of the resin composition (X) is as described in the examples below.

[0075] The dielectric loss tangent of the resin composition (X) at a frequency of 1 MHz is preferably less than 0.0050, and more preferably less than 0.0032. If the dielectric loss tangent of the resin composition (X) is 0.0050 or higher, the transmission loss may increase. The lower limit of the dielectric loss tangent of the resin composition (X) is not particularly limited, but is usually 0.0025 or higher. The procedure for measuring the dielectric loss tangent of the resin composition (X) is as described in the examples below.

[0076] [Method for producing resin composition (X)] The resin composition (X) can be obtained, for example, by melt-kneading resin (A) and a 4-methyl-1-pentene polymer (B); or by mixing monomers constituting resin (A) or precursors of resin (A) with poly-4-methyl-1-pentene polymer (B) and then carrying out a polymerization reaction.

[0077] If resin (A) is polyamic acid, then the resin composition (X) is 1) Steps to prepare polyamic acid varnish, 2) Add 4-methyl-1-pentene polymer (B) to the polyamic acid varnish and stir the varnish. It can be manufactured through the following process. If resin (A) is polyimide, 1) Steps to prepare polyamic acid varnish, 2) Adding a 4-methyl-1-pentene polymer (B) to the polyamic acid varnish and stirring the varnish, 3) A step of imidizing the polyamic acid in the obtained polyamic acid varnish by heating, A resin composition (X) can be manufactured through the following process.

[0078] The polyamic acid varnish in 1) contains a polyamic acid and, preferably, a solvent. The solvents that can be used in the polyamic acid varnish are as described above. The resin solids content concentration in the polyamic acid varnish is preferably 1 to 40% by mass, and more preferably 10 to 30% by mass. This is to appropriately control the stirring conditions described later.

[0079] 2) In this step, the aforementioned 4-methyl-1-pentene polymer (B) is added to the polyamic acid varnish and stirred to disperse the 4-methyl-1-pentene polymer (B) in the polyamic acid varnish. Stirring can be done using conventional stirring with a stirring blade or by stirring with a rotating / revolving mixer. The added 4-methyl-1-pentene polymer (B) may be the polymer itself or the varnish dissolved in a solvent.

[0080] In step 3), a polyamic acid varnish to which a 4-methyl-1-pentene polymer (B) has been added is applied to a glass substrate or the like, and then heated to remove the solvent and imide (ring-close) the polyamic acid remaining on the glass substrate or the like. For this reason, the heating temperature is, for example, around 100 to 400°C, and the heating time is, for example, around 3 minutes to 12 hours.

[0081] The imidation of polyamic acids can usually be carried out at atmospheric pressure, but it may also be carried out under pressure. The atmosphere during imidation is not particularly limited, but is usually air, nitrogen, helium, neon, or argon, and preferably an inert gas such as nitrogen or argon.

[0082] ≪Metal-resin composite≫ The metal-resin composite of the present invention comprises a metal and a resin layer (I) in direct contact with its surface or via an intermediate layer. The intermediate layer may be, for example, an adhesive layer. There may be multiple metals and resin layers (I). The metal-resin composite of the present invention may further include other layers other than the metal, resin layer (I), and intermediate layer (for example, a resin layer other than the resin layer (I)).

[0083] The thickness of the metal layer in the metal laminate is preferably 2 μm to 150 μm, more preferably 3 μm to 50 μm. The thickness of the insulating layer (a layer made of resin composition (X)) in the metal laminate is preferably 0.1 μm to 100 μm, more preferably 0.5 μm to 50 μm.

[0084] <About metals> The metal contained in the metal-resin composite of the present invention can function as a conductor. The metal is not particularly limited, but examples include copper, copper alloys, aluminum, nickel, gold, silver, and stainless steel. Among these, copper or copper alloys are preferred from the viewpoint of obtaining high conductivity. The metal may be a metal layer or a metal wire. The metal layer may be a metal foil, a metal plate, etc.

[0085] <Regarding the resin layer (I)> The resin layer (I) may function as an insulating layer that insulates the metal from other materials. The resin layer (I) may be a molded article, such as a film or sheet, obtained from the resin composition (X). If the resin composition (X) is a solvent-containing varnish, the resin layer (I) may be a thin film of the resin composition (X) obtained by applying the varnish to at least a portion of the surface of the metal and drying or heating it. Furthermore, if the resin composition (X) is a solvent-containing varnish, the resin layer (I) may be a thin film of the resin composition (X) obtained by applying the varnish directly to the surface of the metal or to at least a portion of an intermediate layer formed via another layer, and drying or heating it. Note that in the following description, these thin films obtained from varnishes may also be described as a type of sheet.

[0086] Applications of metal-resin composites The metal-resin composite of the present invention may be a metal laminate in which the aforementioned metal layer and a resin layer (I) obtained from the aforementioned resin composition (X) are laminated directly or via an intermediate layer; or it may be a metal coating in which the outer surface of the aforementioned metal wire is coated directly or via an intermediate layer with a resin layer (I) obtained from the aforementioned resin composition (X).

[0087] As described above, the metal laminate of the present invention has an insulating layer obtained from a resin composition (X) with a low dielectric constant and high heat resistance. For this reason, the metal laminate of the present invention is preferably used as a substrate for various circuits, and in particular as a substrate for high-frequency circuits.

[0088] Such circuit boards include, for example, 1) A method for heat-pressing a sheet obtained from the aforementioned resin composition (X) with a metal foil; 2) A method for forming a conductive layer on a sheet obtained from the aforementioned resin composition (X) by sputtering, vapor deposition, or the like; 3) A method of applying the varnish of the aforementioned resin composition (X) to metal foil and curing it. It can be obtained by the following means.

[0089] 1) In this case, the sheet obtained from the resin composition (X) is obtained by applying varnish to a support substrate, drying it, and then performing heat treatment, and finally peeling it off the support substrate. The means of applying the varnish are not particularly limited, but include, for example, a spin coater, a spray coater, or a bar coater. The thickness of the sheet obtained from the resin composition (X) is preferably about 0.1 to 200 μm, given that it is used as a circuit board. The thermocompression bonding temperature depends on the combination of the resin composition (X) and the metal foil, but is above the glass transition temperature of the resin composition (X), and is specifically about 130 to 300°C.

[0090] The circuit board of the present invention has a highly heat-resistant and low dielectric constant insulating layer, and can therefore be widely applied to various applications using high frequencies, such as electronic components with high-frequency circuits, like built-in antennas for mobile phones, antennas for on-board radar in automobiles, and high-speed wireless communication for home use.

[0091] In the metal-resin composite of the present invention, a metal wire may be used as the metal. In this case, the metal-resin composite is a metal coating in which the outer surface of the metal wire is coated with the resin layer (I) directly or via an intermediate layer. The resin layer (I) in the metal coating functions as an insulating layer. The thickness of the resin layer (I) can be about 0.05 to 5 mm, depending on the diameter of the metal wire and the required insulation properties.

[0092] The metal coating of the present invention is characterized in that a metal wire is coated with a resin layer (I) made of a resin composition (X) with a low dielectric constant and high heat resistance. For this reason, the metal coating of the present invention is preferably used as an electric wire, such as various cables and cords.

[0093] Such electric wires can be obtained, for example, by extruding the resin composition (X) onto the outer surface of a metal wire (extrusion molding) or by injection molding. Alternatively, a metal coating may be manufactured by immersing the longitudinal surface of the electric wire in a varnish of the resin composition (X) and then drying or heating it.

[0094] Furthermore, the resin composition (X) constituting the resin layer (I) in the metal-resin composite has a low dielectric constant and high heat resistance. For this reason, the resin composition (X) can also be preferably used as a low dielectric constant insulating material (such as a low dielectric constant insulating substrate, insulating layer, or insulating coating). [Examples]

[0095] The present invention will be described in more detail below based on examples. However, the present invention is not limited to these examples.

[0096] <Evaluation method for 4-methyl-1-pentene polymers> [composition] The amount of constituent unit (i) (the amount of constituent unit derived from 4-methyl-1-pentene, U1) and the amount of constituent unit (ii) (the amount of constituent unit derived from α-olefin, U2) in the 4-methyl-1-pentene polymer (B) are determined by the following apparatus and conditions: 13 The result was obtained from the 1C-NMR spectrum.

[0097] A JEOL Ltd. ECP500 nuclear magnetic resonance spectrometer was used, with a mixed solvent of o-dichlorobenzene / deuterated benzene (80 / 20 vol%) as the solvent, a sample concentration of 55 mg / 0.6 mL, a measurement temperature of 120°C, and the observed nucleus was 13 The measurement was performed using C (125 MHz), a single-pulse proton decoupling sequence, a pulse width of 4.7 μs (45° pulse), a repetition time of 5.5 seconds, and an accumulation count of over 10,000 times, with 27.50 ppm as the reference value for chemical shift. 13 The composition of 4-methyl-1-pentene and α-olefin was quantified by 13C-NMR spectroscopy.

[0098] [Intrinsic viscosity [η]] The intrinsic viscosity [η] was measured at 135°C using decalin solvent. Specifically, approximately 20 mg of the sample 4-methyl-1-pentene polymer (B) was weighed out, dissolved in 15 mL of decalin, and the specific viscosity [η] was measured in an oil bath at 135°C. sp The specific viscosity η was measured. After diluting this decalin solution by adding 5 mL of decalin solvent, the specific viscosity η was measured in the same manner.sp was measured. This dilution operation was repeated two more times, and the value of η sp / C when extrapolating the concentration (C) to 0 was determined as the intrinsic viscosity (see the following formula). [η]=lim(η sp / C) (C→0) For the 4-methyl-1-pentene polymer used in the comparative example described later, the intrinsic viscosity [η] was also determined in the same manner.

[0099] [Degree of graft modification] When the 4-methyl-1-pentene polymer (B) is graft-modified, the degree of graft modification (that is, the content of the structural unit derived from the ethylenically unsaturated monomer used for modification when the mass of the modified 4-methyl-1-pentene polymer (B) is 100% by mass) was determined by the following method. First, the 4-methyl-1-pentene polymer (B) as a sample was treated at 250 °C for 5 minutes of preheating and 3 minutes of pressing to prepare a pressed film. For this pressed film, IR measurement was performed by the transmission method using a Fourier transform infrared spectrophotometer (FT-IR410 type, manufactured by JASCO Corporation). In the following examples, since maleic anhydride was used for graft modification, the degree of graft modification was calculated from the peak intensities at 1860 cm -1 and 4321 cm -1 .

[0100] [Melting point (Tm), end temperature of heat absorption (TmE), start temperature of heat generation (TcS), crystallization temperature (Tc)] Using a DSC measuring device (DSC220C) manufactured by Seiko Instruments Inc., an exothermic / endothermic curve was obtained in accordance with ASTM D3418, and the melting point (Tm) and crystallization temperature (Tc) were determined as follows.

[0101] Approximately 5 mg of the sample was placed in an aluminum pan for measurement. The temperature was increased from 20°C to 280°C at a heating rate of 10°C / min, held at 280°C for 5 minutes, then cooled down to 20°C at a cooling rate of 10°C / min, held at 20°C for 5 minutes, and then heated again from 20°C to 280°C at a heating rate of 10°C / min. The crystallization peak that appeared during the first cooling was defined as the crystallization temperature (Tc). If multiple crystallization peaks were detected, the one with the highest temperature was defined as the crystallization temperature (Tc). The melting peak that appeared during the second heating was defined as the melting point (Tm). If multiple melting peaks were detected, the one with the highest temperature was defined as the melting point (Tm).

[0102] The temperature at which endothermic melting (endothermic) ceases in the aforementioned melting (endothermic) curve is defined as the endothermic termination temperature (TmE). Similarly, the temperature at which exothermic melting (exothermic) begins in the aforementioned crystallization (exothermic) curve is defined as the exothermic start temperature (TcS).

[0103] The aforementioned start and end points are points where, in endothermic or exothermic processes, the curve deviates from the baseline, indicating a difference in heat quantity, compared to a baseline where the heat quantity is constant at the start or end of the process.

[0104] The abbreviations used in this example and comparative example are shown below. (1) Solvent NMP: N-methyl-2-pyrrolidone (2) Substances used in the preparation of polyamic acid (A1) used as resin (A) PDA: p-phenylenediamine BPDA: 3,3',4,4'-biphenyltetracarboxylic acid dianhydride

[0105] <Preparation Example 1: Preparation of Varnish Containing Polyamic Acid (A1)> In a container equipped with a stirrer and a nitrogen inlet tube, 20.55 g of PDA and 301 g of NMP as a solvent were charged, and the solution was heated to 50°C and stirred until the PDA dissolved. After the solution was cooled to room temperature, 55.34 g of BPDA was added over approximately 30 minutes, followed by the addition of 129 g of NMP, and the mixture was stirred for 20 hours to obtain a varnish containing polyamic acid (A1). The resulting varnish had a polyamic acid (A1) solid content of 15% by mass, and its logarithmic viscosity, measured at 25°C using an Ubbelohde viscometer, was 1.3 dl / g.

[0106] <Production of 4-methyl-1-pentene polymer (B)> <Manufacturing Example 1: Manufacturing of Polymer 1> [Synthesis Example 1-1: Production of Olefin Polymerization Catalyst] At 30°C, 30 mL of purified decane and 14.65 mmol (in terms of aluminum atoms) of solid polymethylaluminoxane (synthesized using the method described in International Publication No. 2014 / 123212), which is particulate, has a D50 of 28 μm, and an aluminum atom content of 43% by mass, were charged into a 200 mL three-necked flask equipped with a stirrer under a nitrogen stream to form a suspension. To this suspension, 50.0 mg (0.0586 mmol) of (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene)) zirconium dichloride was added as a 4.58 mmol / L toluene solution with stirring. Furthermore, the (8-octamethylfluoren-12'-yl-(2-(adamantan-1-yl)-8-methyl-3,3b,4,5,6,7,7a,8-octahydrocyclopenta[a]indene))zirconium dichloride used was synthesized using the method described in Preliminary Experiment 5 (paragraphs 0346-0348) of International Publication No. 2014 / 123212. After 1 hour, stirring was stopped, and the resulting mixture was washed with 100 mL of decane by decantation. Decane was then added to obtain a 50 mL slurry (zirconium atom loading rate 98%).

[0107] [Synthesis Example 1-2: Preparation of Prepolymerization Catalyst Components] To the slurry prepared in Synthesis Example 1-1, 1.0 mL of a decane solution of triisobutylaluminum (TIBAL) (0.5 mmol / mL in terms of aluminum atoms) was added under a nitrogen atmosphere at 25°C. After cooling to 15°C, 10 mL of 4-methyl-1-pentene was added to the reactor over 60 minutes. The start of the addition of 4-methyl-1-pentene was defined as the start of prepolymerization. Stirring was stopped 2.0 hours after the start of prepolymerization, and the resulting mixture was washed three times with 100 mL of decane by decantation. The prepolymerization catalyst component was a decane slurry (9.5 g / L, 0.56 mmol / L in terms of zirconium atoms).

[0108] [Production of Polymer 1a] At room temperature and under a nitrogen atmosphere, 425 mL of purified decane was placed in a SUS polymerizer equipped with a stirrer with an internal volume of 1 L, and the temperature was raised to 40°C. After reaching 40°C, 0.8 mL (0.4 mmol in terms of aluminum atoms) of a decane solution of triisobutylaluminum (TIBAL) (0.5 mmol / mL in terms of aluminum atoms) was added, followed by 0.0020 mmol (in terms of zirconium atoms) of the decane slurry of the prepolymerization catalyst component from Synthesis Example 1-2. 16.25 N mL of hydrogen was added, followed by a mixture of 231 mL of 4-methyl-1-pentene and 20.6 mL of Linearene 168 (manufactured by Idemitsu Kosan, a mixture of 1-hexadecene and 1-octadecene) which was continuously added to the polymerizer at a constant rate over 2 hours. Polymerization began at the start of the addition of the mixture and was maintained at 45°C for 4.5 hours. 16.25 N mL of hydrogen was added 1 hour and 2 hours after the start of polymerization. After 4.5 hours from the start of polymerization, the temperature was lowered to room temperature, and after depressurization, the polymerization solution containing the white solid was immediately filtered to obtain a solid substance. This solid substance was dried under reduced pressure at 80°C for 8 hours to obtain polymer 1a. The yield was 128 g. When the content of constituent units in polymer 1a was determined, the amount of constituent units derived from 4-methyl-1-pentene was 97.0 mol%, and the total amount of constituent units derived from α-olefins was 3.0 mol%. The melting point (Tm) of polymer 1a was 203°C, and the intrinsic viscosity [η] (in decalin at 135°C) was 5.3 dl / g.

[0109] [Production of Polymer 1] Polymer 1 was obtained by blending polymer 1a (100 parts by mass), maleic anhydride (2 parts by mass), and 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyn-3 (Perhexyn 25B, manufactured by NOF Corporation) as an organic peroxide, and kneading the mixture using a Laboplast Mill mixer manufactured by Toyo Seiki Seisakusho Co., Ltd. at a resin temperature of 280°C and a screw rotation speed of 150 rpm. The amount of constituent units in polymer 1 was assumed to be the same as that of polymer 1a. The melting point (Tm) of polymer 1 was 203°C, the intrinsic viscosity [η] (in decalin at 135°C) was 0.8 dl / g, and the graft modification amount was 1.5 mass%. Other physical properties of polymer 1 are shown in Table 1.

[0110] <Manufacturing Example 2: Manufacturing of Polymer 2> [Production of Polymer 2a] At room temperature and under a nitrogen atmosphere, 425 mL of purified decane was placed in a SUS polymerizer equipped with a stirrer with an internal volume of 1 L, and the temperature was raised to 40°C. After reaching 40°C, 0.8 mL (0.4 mmol in terms of aluminum atoms) of a decane solution of triisobutylaluminum (TIBAL) (0.5 mmol / mL in terms of aluminum atoms) was charged in, followed by 0.00175 mmol (in terms of zirconium atoms) of the decane slurry of the prepolymerization catalyst component from Synthesis Example 1-2. 23.75 N mL of hydrogen was charged in, followed by a mixture of 230 mL of 4-methyl-1-pentene and 22.4 mL of Linearene 168 (manufactured by Idemitsu Kosan, a mixture of 1-hexadecene and 1-octadecene) being continuously charged into the polymerizer at a constant rate over 2 hours. Polymerization began at the start of the charging of the mixture, and was maintained at 45°C for 4.5 hours. 23.75 N mL of hydrogen was added 1 hour and 2 hours after the start of polymerization. After 4.5 hours from the start of polymerization, the temperature was lowered to room temperature, and after depressurization, the polymerization solution containing the white solid was immediately filtered to obtain a solid substance. This solid substance was dried under reduced pressure at 80°C for 8 hours to obtain polymer 2a. The yield was 142 g. When the content of constituent units in polymer 2a was determined, the amount of constituent units derived from 4-methyl-1-pentene was 96.5 mol%, and the total amount of constituent units derived from α-olefins was 3.5 mol%. The melting point (Tm) of polymer 2a was 201°C, and the intrinsic viscosity [η] (in decalin at 135°C) was 4.2 dl / g.

[0111] <Manufacturing Example 2: Manufacturing of Polymer 2> Polymer 2 was obtained by manufacturing it in the same manner as polymer 1, except that polymer 2a was used instead of polymer 1a. The amount of constituent units in polymer 2 was assumed to be the same as that of polymer 2a. The melting point (Tm) of polymer 2 was 201°C, the intrinsic viscosity [η] (in decalin at 135°C) was 0.9 dl / g, and the graft modification amount was 1.5 mass%. Other physical properties of polymer 2 are shown in Table 1.

[0112] <Manufacturing Example 3: Manufacturing of Polymer 3> [Manufacturing of Polymer 3a] At room temperature and under a nitrogen atmosphere, 425 mL of purified decane was placed in a SUS polymerizer equipped with a stirrer with an internal volume of 1 L, and the temperature was raised to 40°C. After reaching 40°C, 0.8 mL (0.4 mmol in terms of aluminum atoms) of a decane solution of triisobutylaluminum (TIBAL) (0.5 mmol / mL in terms of aluminum atoms) was charged in, followed by 0.00175 mmol (in terms of zirconium atoms) of the decane slurry of the prepolymerization catalyst component from Synthesis Example 4-2. 23.75 N mL of hydrogen was charged in, followed by a mixture of 232 mL of 4-methyl-1-pentene and 19.6 mL of Linearene 168 (manufactured by Idemitsu Kosan, a mixture of 1-hexadecene and 1-octadecene) being continuously charged into the polymerizer at a constant rate over 2 hours. Polymerization began at the start of the charging of the mixture, and was maintained at 45°C for 4.5 hours. 23.75 N mL of hydrogen was added 1 hour and 2 hours after the start of polymerization. After 4.5 hours from the start of polymerization, the temperature was lowered to room temperature, and after depressurization, the polymerization solution containing the white solid was immediately filtered to obtain a solid substance. This solid substance was dried under reduced pressure at 80°C for 8 hours to obtain polymer 3a. The yield was 146 g. When the content of constituent units in polymer 3a was determined, the amount of constituent units derived from 4-methyl-1-pentene was 96.7 mol%, and the total amount of constituent units derived from α-olefins was 3.3 mol%. The melting point (Tm) of polymer 3a was 203°C, and the intrinsic viscosity [η] (in decalin at 135°C) was 4.0 dl / g.

[0113] [Production of Polymer 3] Polymer 3 was obtained by manufacturing it in the same manner as polymer 1, except that polymer 3a was used instead of polymer 1a. The amount of constituent units in polymer 3 was assumed to be the same as that of polymer 3a. The melting point (Tm) of polymer 3 was 203°C, the intrinsic viscosity [η] (in decalin at 135°C) was 0.9 dl / g, and the graft modification amount was 1.6 mass%. Other physical properties of polymer 3 are shown in Table 1.

[0114] [Table 1]

[0115] <Preparation Example 2: Preparation of Varnish Containing Polymer 1> To 10 g of polymer 1 (i.e., with polymer 1 as 100% by mass), 0.1% by mass of tri(2,4-di-t-butylphenyl) phosphate as an antioxidant and 0.1% by mass of n-octadecyl-3-(4'-hydroxy-3',5'-di-t-butylphenyl)propionate as a heat stabilizer were added. Methylcyclohexane (manufactured by Wako Pure Chemical Industries, Ltd.) was then added to bring the solid content to 5% by mass, and the mixture was stirred at 90°C for 1 hour at 200 rpm to produce a varnish containing polymer 1.

[0116] <Preparation Example 3: Preparation of Varnish Containing Polymer 2> The varnish was prepared in the same manner as in Preparation Example 1, except that polymer 2 was used instead of polymer 1.

[0117] <Preparation Example 4: Preparation of Varnish Containing Polymer 3> The varnish was prepared in the same manner as in Preparation Example 1, except that polymer 3 was used instead of polymer 1.

[0118] (Example 1) <Preparation of resin composition (X1)> A resin composition (X1) was prepared by adding 50 g of the polyamic acid (A1) varnish prepared in Preparation Example 1 and 60 g of the varnish prepared in Preparation Example 2 to a plastic container and stirring at 60°C for 10 minutes at 200 rpm.

[0119] <Preparation of polyimide / 4-methyl-1-pentene polymer composite films> The obtained resin composition (X1) was applied to a glass plate using a baker applicator to a dry film thickness of approximately 30 μm, and then dried in an inert oven at 300°C for 120 minutes under a nitrogen atmosphere. The glass plate with the thus formed coating was then immersed in water at approximately 40°C to peel off the coating, thereby obtaining a polyimide / 4-methyl-1-pentene polymer composite film with a thickness of 30 μm.

[0120] (Example 2) A polyimide / 4-methyl-1-pentene polymer composite film was obtained by the same method as in Example 1, except that the varnish prepared in Preparation Example 3 was used instead of the varnish prepared in Preparation Example 2.

[0121] (Example 3) A polyimide / 4-methyl-1-pentene polymer composite film was obtained by the same method as in Example 1, except that the varnish prepared in Preparation Example 4 was used instead of the varnish prepared in Preparation Example 2.

[0122] (Comparative Example 1) A polyimide film was obtained by the same method as in Example 1, except that a composition containing a 4-methyl-1-pentene polymer was not added.

[0123] [Relative permittivity, dielectric loss tangent] Electrodes with a thickness of 20-30 μm were formed by applying conductive paste to both sides of the obtained film. The conductive paste was composed of silver. Current was passed through the electrodes formed on this film using an HP4294A precision impedance analyzer manufactured by Yokogawa Hewlett-Packard, Ltd., to determine the capacitance (C) of the polyimide film under conditions of 23°C and 50% humidity. p The dielectric constant (ε) and conductance (G) were measured. By substituting the obtained values ​​into the following equation, the relative permittivity (ε) at a measurement frequency of 1 MHz was calculated. r The dielectric loss tangent (tanδ) was calculated. The evaluation results are shown in Table 2.

number

[0124] (Evaluation criteria for relative permittivity) A: The relative permittivity is less than 3.0. B: The relative permittivity is 3.0 or higher.

[0125] (Evaluation criteria for dielectric loss tangent) A: The dielectric loss tangent is less than 0.0032. B: The dielectric loss tangent is 0.0032 or greater, and less than 0.0050. C: The dielectric loss tangent value is 0.0050 or greater.

[0126] [Table 2]

Claims

1. Resin (A) and 4-methyl-1-pentene polymer (B) and Includes, The resin (A) is a resin composition (X) having a relative permittivity of 2.3 or more at a frequency of 1 MHz after being heated to 300°C for 120 minutes under a nitrogen atmosphere.

2. The resin composition (X) according to claim 1, wherein the relative permittivity of the resin composition (X) at a frequency of 1 MHz is lower than the relative permittivity of the resin (A) at a frequency of 1 MHz after heating to 300°C for 120 minutes in a nitrogen atmosphere.

3. The resin composition (X) according to claim 1 or 2, wherein the resin (A) is at least one selected from the group consisting of polyamic acid, polyimide, polyamideimide, liquid crystal polymer, and polyphenylene ether.

4. The resin composition (X) according to claim 1 or 2, wherein the resin (A) is a polyamic acid.

5. The resin composition (X) according to claim 1 or 2, wherein the 4-methyl-1-pentene polymer (B) has a polar group.

6. The resin composition (X) according to claim 5, wherein the polar group is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, an amide group, an imide group, an ether group, a urethane group, a urea group, a phosphoric acid group, a sulfonic acid group, and a carboxylic acid anhydride group.

7. The resin composition (X) according to claim 1 or 2, wherein the resin composition (X) comprises 5 to 200 parts by mass of the 4-methyl-1-pentene polymer (B) per 100 parts by mass of the resin (A).

8. The resin composition (X) according to claim 1, further comprising a solvent.

9. A metal-resin composite comprising a metal and a resin layer (I) in direct contact with the metal or via an intermediate layer, A metal-resin composite wherein the resin layer (I) comprises the resin composition (X) described in claim 1.

10. A metal-resin composite comprising a metal and a resin layer (I) in direct contact with the metal or via an intermediate layer, A metal-resin composite wherein the resin layer (I) comprises a cured or dried product of the resin composition (X) described in claim 8.

11. The aforementioned metal is a metal layer, The metal-resin composite according to claim 9 or 10, wherein the metal-resin composite is a metal laminate in which the metal layer and the resin layer (I) are laminated directly or via an intermediate layer.

12. The metal-resin composite according to claim 11, wherein the metal laminate is a circuit board.

13. The metal-resin composite according to claim 11, wherein the metal laminate is a substrate for high-frequency circuits.

14. The aforementioned metal is a metal wire, The metal-resin composite according to claim 9 or 10, wherein the metal-resin composite is a metal coating in which the outer surface of the metal wire is coated with the resin layer (I) directly or via an intermediate layer.

15. The metal-resin composite according to claim 14, wherein the metal coating is an electric wire.

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