Resin composition, resin sheet, laminate, sheet cured product, and circuit board material

Abstract

To provide a resin composition, a resin sheet, a laminate, a sheet cured product, and a circuit board material that exhibit low dielectric characteristics and superior adhesion to a conductor and a low dielectric component.SOLUTION: A resin composition, comprising a hydrocarbon-based polymer compound (A) free of oxygen atoms in the main chain, and a fluorine-containing radically polymerizable compound (B).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition, a resin sheet, a laminate, a cured sheet, and a circuit board material. . [Background technology]

[0002] In recent years, with the increasing performance and functionality of electrical and electronic devices, the speed of communication and the amount of information transmitted have increased. To achieve this, communication frequencies are becoming higher and higher. When a digital signal is sent to a circuit board, part of the transmitted digital signal undergoes thermal transformation within the circuit board. The amount of transmission loss is expressed as the product of the dielectric constant and the dielectric loss tangent, To achieve low-loss communication, materials with low dielectric constant and dielectric loss tangent, i.e., low dielectric properties, are required. In particular, transmission signals in the high frequency range are more likely to be converted into heat. Due to these characteristics, there is a demand for materials with lower dielectric properties. Generally, electronic substrates made of materials with low dielectric properties, such as PTFE, have low polarity. Therefore, it is known that it has poor adhesion to conductors such as copper foil and copper plating used in circuit formation. In order to ensure adhesion to the conductor, the surface of the substrate may be roughened. However, there was a problem of transmission loss due to surface irregularities. It is also required to ensure adhesion to materials with low dielectric properties, such as base resins.

[0003] An example of a material having low dielectric properties is a mixture of an epoxy compound and a cyanate compound. Polyphenylene ether resin compositions containing maleimide (see, for example, Patent Document 1) thermosetting resins such as resins (see, for example, Patent Document 2), cyclic olefin resin compositions (e.g., For example, thermoplastic resins such as those disclosed in Patent Document 3 are known. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-059363 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-255059 [Patent Document 3] International Publication No. 2006 / 095511 Summary of the Invention [Problem to be solved by the invention]

[0005] However, conventional thermosetting resins have lower dielectric constants and dielectric loss tangents than thermoplastic resins. Therefore, in order to achieve low dielectric properties, it has been necessary to add a large amount of inorganic particles or the like. On the other hand, conventional thermoplastic resins have low dielectric properties but often lack good heat resistance. there were. In addition, when the above materials are used as circuit board materials, conductors such as copper foil and low dielectric properties such as fluororesin are required. Since it is used by laminating with a material having low dielectric constant, it is possible to bond it to the conductor and low dielectric material without peeling or deformation. It is required to have adhesive strength.

[0006] Therefore, the present invention provides a method for bonding a low dielectric material such as a conductor or a low dielectric material such as a fluororesin, which has low dielectric properties. To provide a resin composition, a resin sheet, a laminate, a cured sheet, and a circuit board material having excellent properties The purpose is to: [Means for solving the problem]

[0007] As a result of extensive research into solving the above problems, the present inventors have discovered a hydrocarbon polymer that does not contain oxygen atoms in the main chain. A resin composition comprising a fluorine-containing polymer compound (A) and a fluorine-containing radical polymerizable compound (B) This allows for both low dielectric properties and adhesion to adherends, especially conductors and members with low dielectric properties. We found that this is the case.

[0008] The gist of the present invention is as follows. [1] A hydrocarbon polymer compound (A) that does not contain oxygen atoms in the main chain and a fluorine-containing radical A resin composition containing a polymerizable compound (B). [2] The resin according to the above [1], wherein the hydrocarbon polymer compound (A) is a thermoplastic resin. Fat composition. [3] The hydrocarbon polymer compound (A) is a styrene-based thermoplastic elastomer, an olefin At least one selected from the group consisting of vinyl-based thermoplastic elastomers and ethylene-based polymers. The resin composition according to the above [1] or [2], which is a seed. [4] The hydrocarbon polymer compound (A) contains a styrene-based thermoplastic elastomer. The resin composition according to any one of the above [1] to [3]. [5] The styrene content of the styrene-based thermoplastic elastomer is 10% by mass or more and 70% by mass or less. % or less. [6] The hydrocarbon polymer compound (A) has a mass average molecular weight (Mw) of 30,000 or more. The resin composition according to any one of the above [1] to [5], [7] The fluorine-containing radical relative to 100 parts by mass of the hydrocarbon polymer compound (A). [1] to [6], wherein the content of the polymerizable compound (B) is 1 part by mass or more and 30 parts by mass or less. The resin composition according to any one of the above. [8] The mass average molecular weight (Mw) of the fluorine-containing radical polymerizable compound (B) is 100 or more. The resin composition according to any one of [1] to [7], wherein the molecular weight is at most 5,000. [9] Any of [1] to [8] containing a radical polymerizable compound (C) other than component (B). The resin composition according to claim 1.

[10] The fluorine-containing radical relative to 100 parts by mass of the hydrocarbon-based polymer compound (A). the sum of the contents of the radical polymerizable compound (B) and the radical polymerizable compound (C) is 2 parts by mass or more; The resin composition according to [9], wherein the content is 100% by mass or less.

[11] The resin composition was subjected to heat pressing under conditions of 200°C and 2 MPa for 30 minutes to obtain a hardened film. The dielectric loss tangent of the compound at a frequency of 10 GHz is 0.002 or less.[1]~

[10] The resin composition according to any one of the preceding claims.

[12] A resin sheet comprising the resin composition according to any one of [1] to

[11] .

[13] A laminate comprising the resin sheet according to

[12] , which has a release film on one or both surfaces thereof. Layered body.

[14] A sheet cured product obtained by curing the resin sheet described in

[12] above.

[15] A circuit board comprising an insulating layer made of the resin sheet according to

[12] above and a conductor laminated thereon. Road board material. [Effects of the Invention]

[0009] According to the present invention, the present invention provides a method for manufacturing a semiconductor device having low dielectric properties and being compatible with low dielectric materials such as conductors and fluororesins. and a resin composition having excellent adhesiveness, a resin sheet, a laminate, a cured sheet, and a circuit board material. can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0010] An example of an embodiment of the present invention will be described in detail below. The present invention is not limited to the embodiments described above. In the present invention, the term "film" conceptually includes sheets, films, and tapes. This is what is done. In addition, when the term "substrate" is used, such as a circuit board or a resin board, it does not include plates, sheets, or films. It encompasses the rum.

[0011] In the present invention, when it is written as "x to y" (x and y are arbitrary numbers), unless otherwise specified, It means "greater than or equal to x and less than or equal to y", as well as "preferably greater than x" or "preferably greater than or equal to y". It also includes the meaning of "smaller than." Also, when we say "x or more" (x is any number), unless otherwise specified, it means "preferably" "Greater than x" is included, and "less than y" (y is any number) means "equal to or less than y" unless otherwise specified. Unless otherwise specified, the meaning of "preferably smaller than y" is also included. Furthermore, "x and / or y (x and y are optional configurations)" means that at least one of x and y is It means three things: x only, y only, and x and y. In the present invention, the term "(meth)acrylic" encompasses acrylic and methacrylic. "(Meth)acrylate" means acrylate and methacrylate inclusively. "(Meth)acryloyl" means both acryloyl and methacryloyl. This means that.

[0012] <Resin composition> The resin composition according to one embodiment of the present invention (hereinafter also referred to as "the present resin composition") has a main chain a hydrocarbon polymer compound (A) containing no oxygen atoms and one or more ethylene The polymerizable composition contains a fluorine-containing radically polymerizable compound (B) having a radically unsaturated bond. The composition has low dielectric properties as a cured sheet and a circuit board material, and is also suitable for use in conductors and fluorine resins. The reason why the adhesion to the oily substrate is good is not clear, but the following points are thought to be the cause. When the composition is cured, the hydrocarbon polymer compound (A) is converted into a fluorine-containing radical. The molecular chains of the polymerizable compound (B) are partially and physically entangled with each other, so that the hydrocarbon polymer It is believed that the molecular compound (A) can be provided with adhesiveness while maintaining its low dielectric properties. Each component of the resin composition will now be described.

[0013] 1. Hydrocarbon polymer compounds (A) The hydrocarbon polymer compound (A) of the present composition is characterized in that it does not contain oxygen atoms in the main chain. The hydrocarbon polymer compound (A) that does not contain oxygen atoms in the main chain has a molecular structure with low polarity. This composition exhibits low dielectric properties, and is made of a hydrocarbon polymer compound ( When A) does not contain an oxygen atom in the main chain, the effects of the present invention are suitably exhibited. Furthermore, the hydrocarbon polymer compound (A) does not contain a fluorine atom. Methods for analyzing the main chain structure include NMR, IR, and MALDI-TOFMS. Examples include:

[0014] The molecular structure of the hydrocarbon polymer compound (A) is not particularly limited, and may be an aliphatic hydrocarbon, an alicyclic hydrocarbon, or the like. The hydrocarbon may be either a hydrocarbon or an aromatic hydrocarbon.

[0015] The hydrocarbon polymer compound (A) is a thermoplastic resin from the viewpoint of low dielectric properties. Among them, styrene-based thermoplastic elastomers and olefin-based thermoplastic elastomers are preferred. a copolymer selected from the group consisting of an ethylene-based polymer, an ethylene-based polymer, and a cyclic polyolefin resin copolymer; At least one hydrocarbon polymer compound (A) is preferably used alone. Alternatively, two or more of them may be used in combination.

[0016] Examples of the styrene-based thermoplastic elastomer include styrene-butadiene-styrene. styrene-isoprene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer ( SIS) and hydrogenated styrene-ethylene-butadiene-styrene block copolymers Styrene-ethylene-propylene-styrene block copolymer (SEBS), PS), styrene-isobutylene-styrene block copolymer (SIBS), etc. can be. Examples of the styrene-based thermoplastic elastomer include styrene-butadiene-styrene. styrene-isoprene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer ( SIS) and hydrogenated styrene-ethylene-butadiene-styrene block copolymers Styrene-ethylene-propylene-styrene block copolymer (SEBS), PS), styrene-isobutylene-styrene block copolymer (SIBS), etc. can be.

[0017] The above olefin-based thermoplastic elastomer contains polyolefin ( However, cyclic polyolefins, which will be described later, are excluded), and the soft segment is a rubber component. include. The olefin-based thermoplastic elastomer is a mixture of polyolefin and rubber component (polyolefin). It may be a crosslinked product obtained by crosslinking a polyolefin and a rubber component. Alternatively, it may be a polymer obtained by polymerizing a polyolefin and a rubber component. Examples of the polyolefin include polypropylene and polyethylene. The rubber component may be isoprene rubber, butadiene rubber, butyl rubber, propylene- Butadiene rubber, acrylonitrile-butadiene rubber, acrylonitrile-isoprene rubber Diene rubbers such as ethylene-propylene non-conjugated diene rubber, ethylene-butadiene co- Polymer rubber and the like are included.

[0018] The ethylene polymers include homopolymers of ethylene and polymers of ethylene and other monomers. Examples of copolymers include: The copolymer of ethylene and another monomer preferably contains ethylene as a main component. Here, "mainly composed of ethylene" means that the copolymer contains 50 mol of ethylene structural units. % or more, preferably 60 mol % or more. In addition, the other monomers copolymerized with ethylene are particularly suitable as long as they are copolymerizable with ethylene. Not limited to. Preferred examples of the ethylene polymer include low density polyethylene (LDPE), linear polyethylene (LDPE), Low-density polyethylene (LLDPE), a polyethylene obtained by polymerization using a metallocene catalyst Among these, linear low density polyethylene ( It is particularly preferred to use LLDPE.

[0019] The cyclic polyolefin resin copolymer is a copolymer having an alicyclic structure, and specifically The copolymer is a copolymer having an alicyclic structure in the side chain of a polyolefin. Suitable examples include cycloalkanes, bicycloalkanes, polycyclic compounds, etc. Of these, cycloalkanes are preferred, and cyclohexane is more preferred. The alicyclic structure is a hydrogenated aromatic vinyl polymer block unit which will be described later. More preferably, it is an alicyclic structure formed by hydrogenation of an aromatic ring.

[0020] The cyclic polyolefin resin copolymer preferably has a crystal melting peak temperature of less than 100°C. Desirable. The crystalline melting peak temperature of the cyclic polyolefin resin copolymer is preferably 50°C or higher, The temperature is more preferably 0°C or higher, and even more preferably 65°C or higher. The crystalline melting peak temperature of the copolymer is preferably 90°C or lower, more preferably 85°C or lower. The crystalline melting peak temperature in the present invention is the differential scanning calorimetry (DSC) temperature measured at a heating rate of 10°C / min. This is the temperature at which a crystalline melting peak is detected in the differential scanning calorimetry (DSC). The cyclic polyolefin resin copolymer used in the product has a crystal melting peak at less than 100°C. For example, the crystal melting peaks are at two points, one below 100°C and one above 100°C. This includes cases where it exists.

[0021] The known cyclic polyolefins include monocyclic norbornene monomers and polycyclic norbornene monomers. Hydrogenated ring-opening polymers having repeating units derived from tetrahydrofuran monomers (e.g., International Publication No. 2012 / 046443, International Publication No. 2012 / 033076, etc. This cyclic polyolefin has an alicyclic structure in the polymer main chain, and The melting peak temperature does not exist below 100°C, or the material is amorphous. The crystallinity of polymers usually changes depending on the regularity of the molecular structure and steric hindrance. Polymers with alicyclic structures in the chain or main chain are difficult to crystallize due to large steric hindrance, and remain amorphous. It's easy to become. On the other hand, the cyclic polyolefin resin copolymer of the present resin composition is a hydrogenated conjugated diene copolymer, which will be described later. The polymer block unit structure provides crystallinity and polyolefin The alicyclic structure in the side chain of the vinyl acetate keeps the crystal melting peak temperature below 100°C. It can be done.

[0022] The melt flow rate (MFR) of the cyclic polyolefin resin copolymer is not particularly limited. However, it is usually 0.1 g / 10 min or more, and is preferred from the viewpoint of the molding method and the appearance of the molded product. The melt flow rate (MFR) is usually 0.5 g / 10 min or more. , 200g / 10min or less, and from the viewpoint of material strength, preferably 100g / 10min or less More preferably, the MFR is 90.0 g / 10 min or less. Therefore, compatibility with the thermoplastic resin described below is improved. MFR is measured at a temperature of 230°C and a load of 2.16 kg in accordance with ISO R1133. It can be determined by measuring under certain conditions.

[0023] In the present invention, a "block" refers to a structurally or compositionally distinct polymeric segment of a copolymer. Microphase separation refers to polymerized segments of a copolymer that exhibit microphase separation from the stratum. It occurs due to the immiscibility of polymerized segments in block copolymers. Microphase separation and block copolymers were discussed in a 1999 issue of PHYSICS TODAY. “Block Copolymers-Designer So This is extensively discussed in "Finite Materials."

[0024] The cyclic polyolefin (a) is a hydrogenated aromatic vinyl polymer block unit (hereinafter referred to as "block"). Block A) and hydrogenated conjugated diene polymer block units (hereinafter referred to as "Block B"). a diblock copolymer consisting of at least one of block A and block B; Triblock copolymers, tetrablock copolymers, pentablock copolymers containing 2 or more Marr et al. The cyclic polyolefin (a) preferably contains at least two blocks A, for example Suitable examples include the ABA type, ABAB type, and ABABA type.

[0025] The cyclic polyolefin (a) is a cyclic polyolefin having an aromatic vinyl polymer at each end. Therefore, the hydrogenated block copolymer of the present resin composition preferably contains a hydroxyl group. has at least two hydrogenated aromatic vinyl polymer block units (block A), Between the two hydrogenated aromatic vinyl polymer block units (block A), there is at least It is preferable that the copolymer has one or more hydrogenated conjugated diene polymer block units (block B). From these viewpoints, the cyclic polyolefin (a) is an ABA type or ABAB- Type A is more preferred.

[0026] Hydrogenated aromatic vinyl polymer block units (blocks) in cyclic polyolefin (a) The content of (A) is preferably 30 to 99 mol %, more preferably 40 to 90 mol %. Among these, more preferably 50 mol % or more, and even more preferably 60 mol % or more is. If the ratio of the hydrogenated aromatic vinyl polymer block unit (block A) is equal to or greater than the above lower limit, If the ratio is high, the rigidity will not decrease and the heat resistance and linear thermal expansion coefficient will be good. If it is equal to or less than the upper limit, flexibility is good.

[0027] In addition, the hydrogenated conjugated diene polymer block unit (block unit) in the cyclic polyolefin (a) The content of block B) is preferably 1 to 70 mol %, more preferably 10 to 60 mol %. Among these, it is more preferable that the content is 50 mol % or less, and even more preferable that the content is 40 mol % or less. Below. If the ratio of hydrogenated conjugated diene polymer block units (block B) is above the lower limit On the other hand, if the ratio is equal to or less than the upper limit, the rigidity will not decrease. The heat resistance and linear thermal expansion coefficient are also good.

[0028] The hydrogenated aromatic vinyl polymer block units constituting the cyclic polyolefin (a) and water The halogenated conjugated diene polymer block units are each formed of an aromatic vinyl monomer and a and 1,3-butadiene. This can be obtained by converting The cyclic polyolefin (a) is preferably a block copolymer having no functional groups. "No functional group" means that there are no functional groups in the block copolymer, i.e. That is, it means that there are no groups containing atoms other than carbon and hydrogen atoms.

[0029] Hereinafter, the aromatic vinyl polymer block units and the conjugated diene polymer block units before hydrogenation will be referred to as "aromatic vinyl polymer block units and conjugated diene polymer block units before hydrogenation." The monomers for forming the block units are described below.

[0030] (aromatic vinyl monomer) The aromatic vinyl monomers used as raw materials for the aromatic vinyl polymer block units before hydrogenation are: It is a monomer represented by the following general formula (1).

[0031] [ka]

[0032] In the above general formula (1), R is hydrogen or an alkyl group, and Ar is a phenyl group, a halo group, or a phenyl group. Phenyl group, alkylphenyl group, alkylhalophenyl group, naphthyl group, pyridinyl group Or an anthracenyl group.

[0033] When R is an alkyl group, the number of carbon atoms is preferably 1 to 6. Halo groups, nitro groups, amino groups, hydroxy groups, cyano groups, carbonyl groups, and carboxyl groups The alkyl group may be mono- or polysubstituted with functional groups such as groups. The above Ar is preferably a phenyl group or an alkylphenyl group, and more preferably a phenyl group. preferable.

[0034] Examples of aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene, and the like. ene (including all isomers, especially p-vinyltoluene), ethylstyrene, propylstyrene, butylstyrene, vinylbiphenyl, vinylnaphthalene, vinylant Helical chains (including all isomers), and mixtures thereof. Styrene is preferred.

[0035] (Conjugated diene monomer) The conjugated diene monomers that are the raw materials for the conjugated diene polymer block units before hydrogenation are two There are no particular limitations on the monomer as long as it has a conjugated double bond. Examples of conjugated diene monomers include 1,3-butadiene and 2-methyl-1,3-butadiene. pentadiene (isoprene), 2-methyl-1,3-pentadiene and its analogues, Among these, bromine, which has a high structural regularity and is easily crystallized, is particularly preferred. From the viewpoint of obtaining a block, 1,3-butadiene is preferred.

[0036] When 1,3-butadiene is used as the conjugated diene monomer, its polymer Polybutadiene consists of 1,4-bonded units ([-CH2-CH=CH-CH2-]) and 1,2 -bond unit ([-CH2-CH(CH=CH2)-]), hydrogenation The former gives a structure similar to the repeating unit of polyethylene (ethylene structure), and the latter gives a 1- It gives the same structure (1-butene structure) as the repeating unit when butene is polymerized. The hydrogenated conjugated diene polymer block in the resin composition has an ethylene structure and a 1- It is preferable that the olefin contains at least one of the butene structures. In addition, when isoprene is used as the conjugated diene monomer, its polymer, polyisoprene, Prene is a 1,4-bonded unit ([-CH2-C(CH3)=CH-CH2-]), 3,4 -bond unit ([-CH2-CH(C(CH3)=CH2)-]) and 1,2-bond unit ( [-CH2-C(CH3)(CH=CH2)-]), which can be obtained by hydrogenation. The repeating unit of the present invention is a repeating unit of the present invention.

[0037] (Block structure) The cyclic polyolefin (a) is SBS, SBSB, SBSBS, SBSBSB, SIS , SISIS, and SISBS (where S is polystyrene, B is polybutadiene, and I is It means polyisoprene. It is produced by hydrogenation of multi-block copolymers such as mers, pentablock copolymers, etc. The block may be a linear block or may be branched. In this case, the polymer chain may be attached at any position along the backbone of the copolymer. In addition to linear blocks, the blocks may be tapered blocks or star blocks. It is also possible.

[0038] The block copolymer constituting the cyclic polyolefin (a) before hydrogenation is an aromatic vinyl The polymer block unit and one or more additional blocks other than the conjugated diene polymer block unit. For example, in the case of a triblock copolymer, these additional The triblock units may be attached at any position along the triblock polymer backbone.

[0039] Preferred examples of the hydrogenated aromatic vinyl polymer block units include hydrogenated polystyrene. Preferred examples of the hydrogenated conjugated diene polymer block units include Examples of suitable polymers include hydrogenated polybutadiene and hydrogenated polyisoprene. Butadiene is more preferred. A preferred embodiment of the cyclic polyolefin (a) is a mixture of styrene and butadiene. and hydrogenated triblock or pentablock copolymers of the formula: Triblock copolymers are more preferred.

[0040] (hydrogenation level) The cyclic polyolefin (a) has double bonds derived from conjugated dienes such as butadiene. In addition, aromatic rings derived from styrene etc. are also hydrogenated, and the resulting product is substantially completely hydrogenated. Specifically, it refers to products that have achieved the following hydrogenation levels. The hydrogenation level of the hydrogenated aromatic vinyl polymer block units is preferably 90% or more. More preferably, 95% or more, even more preferably 98% or more, and particularly preferably 99.5% That's all. The hydrogenation level of the hydrogenated conjugated diene polymer block units is preferably 95% or more. , more preferably 99% or more, and even more preferably 99.5% or more. This high level of hydrogenation reduces dielectric loss and provides rigidity. The hardness and heat resistance are also good. The hydrogenation level of the hydrogenated aromatic vinyl polymer block unit is The hydrogenated conjugated diene polymer indicates the percentage of the polymer block units that are saturated by hydrogenation. The hydrogenation level of the block unit is the degree to which the conjugated diene polymer block unit is saturated by hydrogenation. Indicates the sum ratio. The hydrogenation level of each block unit is determined using proton NMR.

[0041] The cyclic polyolefin resin copolymer may be used alone or in combination of two or more. Good too. As the cyclic polyolefin resin copolymer in the present resin composition, a commercially available product is used. A specific example is Tefablock (registered trademark) manufactured by Mitsubishi Chemical Corporation.

[0042] Among the hydrocarbon polymer compounds (A) exemplified above, hydrocarbon polymer compounds A combination in which (A) itself is unlikely to react with the fluorine-containing radical polymerizable compound (B) is selected. When selected, the hydrocarbon polymer compound (A) and the fluorine-containing radical polymerizable compound ( B) form an interpenetrating polymer network structure (hereinafter also referred to as "semi-IPN structure"), It is believed that the dielectric properties and heat resistance can be improved. The polymer compound (A) and the fluorine-containing radical polymerizable compound (B) form a chemical bond. The molecules of the hydrocarbon polymer compound (A) and the fluorine-containing radical polymerizable compound (B) are not The chains are partially and physically intertwined with each other. By doing so, the low dielectric properties of the hydrocarbon polymer compound (A) can be maintained while the hydrocarbon polymer compound (A) can be easily obtained. The crosslink density is increased compared to that of the compound (A) alone. From this viewpoint, it is considered that the above hydrocarbon polymer compound (A Among them, styrene-based thermoplastic elastomers are preferred, and styrene-isobutylene Styrene-block copolymer (SIBS) or styrene-ethylene-butadiene-styrene Block copolymers (SEBS) are more preferred, and styrene-ethylene-butadiene-styrene More preferred is styrene block copolymer (SEBS).

[0043] When a styrene-based thermoplastic elastomer is used as the hydrocarbon-based polymer compound (A), The styrene content is preferably 10% by mass or more, more preferably 15% by mass or more. The styrene content is preferably 70% by mass or less, more preferably 60% by mass or less, and more preferably 50% by mass or less. % by mass or less is more preferable, and 40% by mass or less is even more preferable. When the styrene content is within the above range, the dielectric loss tangent of the hydrocarbon polymer compound (A) is low. The elastic modulus is also moderate, so it has both low dielectric properties and heat resistance, and is easy to handle. It will be good.

[0044] In addition, from the viewpoint of improving adhesiveness, improving heat resistance, reducing the coefficient of thermal expansion, and reducing tackiness, As the hydrocarbon polymer compound (A), styrene-based thermoplastic elastomer, olefin At least one selected from the group consisting of ethylene-based thermoplastic elastomers and ethylene-based polymers (hereinafter also referred to as (A1)) and a cyclic polyolefin resin copolymer (hereinafter also referred to as (A2)) It is preferable that the compound contains (iii). The reasons for the improved adhesiveness, heat resistance, linear thermal expansion coefficient, and tackiness are unclear, but By containing the cyclic polyolefin resin copolymer (A2) together with (A1), This is because a rigid skeleton derived from the cyclic polyolefin resin copolymer (A2) is incorporated. It is possible. Among the above (A1), styrene-based thermoplastic elastomers are preferred from the viewpoint of low dielectric properties and processability. Styrene-ethylene-butadiene-styrene block copolymers (SE) are preferred. BS) is more preferred.

[0045] When the present composition contains the hydrocarbon polymer compound (A) as (A1) and (A2), It is preferable that (A1) is used as the main component. The "main component" in the hydrocarbon polymer compound (A) refers to the carbon contained in the composition. It refers to the resin with the highest content of the hydrogenated polymer compound (A), more specifically, When the total amount of the hydrogen-based polymer compound (A) is taken as 100% by mass, the upper limit is 100% by mass. , preferably 50% by mass or more, more preferably 55% by mass or more, and even more preferably 60% by mass or more. This refers to resins that account for more than % by volume.

[0046] In addition, when the present composition contains (A1) and (A2) as the hydrocarbon polymer compound (A), In this case, the content of (A2) is set to a value that satisfies the requirements for reducing the linear thermal expansion coefficient and reducing tackiness of the resin composition. The fat content is preferably 10% by mass or more, more preferably 15% by mass or more, and more preferably 20% by mass or more. On the other hand, the upper limit is preferably 40% by mass or less from the viewpoint of flexibility and adhesion to the substrate. It is preferably 38% by mass or less, more preferably 38% by mass or less, and even more preferably 35% by mass or less. In the present invention, the term "resin component" refers to a hydrocarbon polymer compound contained in the composition. (A) and other resins added as needed.

[0047] The mass average molecular weight (Mw) of the hydrocarbon polymer compound (A) is determined based on the weight average molecular weight (Mw) of the resulting resin sheet. From the viewpoint of preventing blockage, 30,000 or more is preferable, and 40,000 or less is preferable. On the other hand, the film is easy to handle during film formation. From the viewpoint of the above, 300,000 or less is preferable, 250,000 or less is more preferable, and 20 A value of 0,000 or less is even more preferable. The mass average molecular weight (Mw) in the present invention is measured by gel permeation chromatography. This is a polystyrene equivalent value determined.

[0048] The hydrocarbon polymer compound (A) may be modified by a known method. For example, the above-mentioned hydrocarbon polymer compound (A) and unsaturated carboxylic acid and its and at least one of the anhydrides. By modifying the hydrocarbon polymer compound (A), the polarity of the polymer increases. This is expected to improve adhesion to metal layers such as copper foil.

[0049] At least one of the unsaturated carboxylic acid and the anhydride thereof is, for example, acrylic acid. , methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid Acid, methyltetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid Examples of the unsaturated carboxylic acid include unsaturated carboxylic acids such as carboxylic acid and nadic acid, and anhydrides thereof. Specific examples of acid anhydrides include maleic anhydride, citraconic anhydride, and sodium anhydride. Examples include carboxylic acids. Nadic acids or their anhydrides include endo-cis-bicyclo[2.2.1]he buto-2,3-dicarboxylic acid (nadic acid), methyl-endo cis-bicyclo[2.2. 1] Hept-5-ene-2,3-dicarboxylic acid (methyl nadic acid) and its anhydride Examples include:

[0050] Among these unsaturated carboxylic acids and / or anhydrides thereof, acrylic acid, methyl acrylate, methyl meth ... Leic acid, nadic acid, maleic anhydride, and nadic anhydride are preferred. At least one of the unsaturated carboxylic acid and the anhydride thereof may be used alone, More than one species may be used in combination.

[0051] The content of the hydrocarbon polymer compound (A) in the composition is, from the viewpoint of low dielectric properties, The content of the resin component of the composition is preferably 60% by mass or more, more preferably 70% by mass or more, The content is more preferably 80% by mass or more, and even more preferably 85% by mass or more. The upper limit is not particularly limited, and it is possible to use a resin component of the present composition that is composed solely of a hydrocarbon polymer compound (A) (10 It may be 0% by mass. In the present invention, the term "resin component" refers to a hydrocarbon polymer compound contained in the composition. (A) and other resins added as needed.

[0052] The storage modulus of the hydrocarbon polymer compound (A) at 24°C is preferably 0.1 MPa or more. The storage modulus is preferably less than 2000 MPa, and more preferably 1 MPa or more. preferably, less than 1500 MPa, more preferably less than 1000 MPa, Even more preferably, it is less than 500 MPa, even more preferably, it is less than 300 MPa, and 100 More preferably, it is less than 50 MPa, and even more preferably less than 50 MPa. By setting the storage modulus to less than the above upper limit, the flexibility of the obtained sheet cured product is good. Furthermore, by setting the storage modulus to the above lower limit or more, the heat resistance of the obtained cured sheet can be improved. The durability and handling are improved.

[0053] The storage modulus was measured by molding the hydrocarbon polymer compound (A) into a sheet with a thickness of 300 μm. The dynamic viscoelasticity was measured using a viscoelasticity spectrometer. value.

[0054] The density of the hydrocarbon polymer compound (A) is 0.98 g / cm 3 Less than or equal to 0.9 is preferred 5g / cm 3 Less than 0.91 g / cm is more preferable. 3 The following is more preferred: The lower limit of the density is not particularly limited, but is preferably 0.80 g / cm 3 The above is preferable. When the density is equal to or less than the above value, the flexibility of the obtained cured sheet is good.

[0055] The above density was measured by molding the hydrocarbon polymer compound (A) into a sheet having a thickness of 300 μm. A test piece can be used and measurements can be made in accordance with ASTM D792.

[0056] The dielectric tangent of the hydrocarbon polymer compound (A) is preferably less than 0.002 at 10 GHz. It is preferable that the value is less than 0.0015, and more preferably less than 0.001. There is no particular limit, as long as it is 0 or greater. The smaller the dielectric loss tangent, the smaller the dielectric loss. This results in higher electrical signal transmission efficiency and speed.

[0057] The above dielectric loss tangent was measured by forming the hydrocarbon polymer compound (A) into a sheet having a thickness of 300 μm. The test specimen was measured at a temperature of 23°C and a frequency of 10 GHz in accordance with JIS C2565:1992. The values were obtained by measuring under the following conditions.

[0058] 2. Fluorine-containing radical polymerizable compound (B) The fluorine-containing radical polymerizable compound (B) in the present resin composition has a fluorine atom in the molecule. and a compound having one or more ethylenically unsaturated bonds as radically polymerizable functional groups. The radical polymerizable compound (B) may be either bifunctional or trifunctional or higher. These may be used alone or in combination of two or more. The mass average molecular weight (Mw) of the fluorine-containing radical polymerizable compound (B) is preferably 100 or more. It is preferably 120 or more, more preferably 300 or more. The molecular weight (Mw) is preferably 5,000 or less, more preferably 4,000 or less, and 00 or less is more preferable, and 1,000 or less is particularly preferable. The mass average molecular weight (Mw) of the fluorine-containing radically polymerizable compound (B) is within the above range. This suppresses foaming caused by decomposition of the fluorine-containing radical polymerizable compound (B) during curing, and Molecular chains of the hydrogen fluoride polymer compound (A) and the fluorine-containing radical polymerizable compound (B) This makes it easier for the crosslinking density to increase, and the hardness of the resulting sheet The heat resistance and dimensional stability of the product are improved. In addition, if the crosslinking agent is partially crosslinked or is not a polymer, it is called "fluorine-containing radical polymerizable The "mass average molecular weight (Mw) of the compound (B)" refers to the mass average molecular weight (Mw) of the fluorine-containing radical polymerizable compound (B). This refers to the molecular weight of the compound used.

[0059] The functional group having a carbon-carbon double bond includes a vinyl group, an acryloyl group, and a methacryloyl group. An example of such an alkyl group is methyl.

[0060] The monofunctional fluorine-containing radical polymerizable compound (B) includes fluoroethylene, vinylene, fluoride, tetrafluoroethylene, hexafluoropropylene, perfluoro butadiene, fluoroolefins such as perfluoro-2,2-dimethyl-1,3-dioxole, Fins, pentafluorostyrene, pentafluorobenzyl acrylate, pentafluoro Benzyl methacrylate, pentafluorophenyl acrylate, pentafluorophenyl Phenyl methacrylate, 3-(pentafluorophenyl)pentafluoro-1-propene , pentafluorophenyl trifluorovinyl ether, 3-(pentafluorophenyl ) Aryls such as pentafluoropropene-1, pentafluorophenyl methacrylate, Hexafluoroisopropyl acrylate, heptadecafluorodecyl acrylate, -Fluoroalkylsulfonamidoethyl acrylate, pentafluorobenzyl acrylate acrylate, pentafluorobenzyl methacrylate, perfluoroalkylamidoethyl acrylate Acrylate, pentafluorophenyl acrylate, pentafluorophenyl methacrylate acrylate, perfluorostyrene, pentafluorophenyl trifluorovinyl ether, 3 -(pentafluorophenyl)pentafluoro-1-propene, 2,3,4,5,6-pentafluorophenyl Pentafluorostilbene, 2,2,2-trifluoroethyl (meth)acrylate, 2, 2,3,3,3-Pentafluoropropyl (meth)acrylate, 1H,1H-heptafluoropropyl Fluoro-n-butyl (meth)acrylate, 1H,1H-undecafluoro-n-hexyl (meth)acrylate, 1H,1H-pentadecafluoro-n-octyl(meth)acrylate acrylate, 1H,1H-nonadecafluoro-n-decyl(meth)acrylate, 1H,1 H-Tricosafluoro-n-dodecyl(meth)acrylate, 2,2,3,3-tetrafluoroethylene 2,2,3,3,4,4-Hexafluorobutyl (meth)acrylate (Meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate 1H,1H,7H-dodecafluoroheptyl (meth)acrylate, 1H,1H,9 H-Hexadecafluorononyl (meth)acrylate, 3,3,4,4,4-pentafluoro Perfluorobutyl (meth)acrylate, 2-(perfluoro-n-butyl)ethyl (meth)acrylate Acrylate, 2-(perfluoro-n-hexyl)ethyl (meth)acrylate, 2-( Perfluoro-n-octyl)ethyl (meth)acrylate, 2-(perfluoro-n- Decyl)ethyl (meth)acrylate, 2-(perfluoro-3-methylbutyl)ethyl (Meth)acrylate, 2-(perfluoro-5-methylhexyl)ethyl (meth)acrylate Acrylate, 2-(perfluoro7-methyloctyl)ethyl (meth)acrylate, 2- Fluorine atom-containing compounds such as (perfluoro-9-methyldecyl)ethyl (meth)acrylate Examples of the monofunctional (meth)acrylate include:

[0061] The bifunctional fluorine-containing radical polymerizable compound (B) may be 1,1,2,2,3,3- Hexafluoro-1,3-bis[(1,2,2-trifluorovinyl)oxy]propane , 1,4-di(meth)acryloyloxy-2,2,3,3-tetrafluorobutane, 1 ,6-Di(meth)acryloyloxy-2,2,3,3,4,4,5,5-octafluoro Octane, 1,8-di(meth)acryloyloxy-2,2,3,3,4,4,5,5 ,6,6,7,7-dodecafluorooctane, 1,10-di(meth)acryloyloxy -2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-Hexadecaful Olodecane, 1,12-di(meth)acryloyloxy-2,2,3,3,4,4,5, 5,6,6,7,7,8,8,9,9,10,10,11,11-Icosafluorododeca 1,6-di(meth)acryloyloxy-3,3,4,4-tetrafluorohexane , 1,8-di(meth)acryloyloxy-3,3,4,4,5,5,6,6-octafluoro Fluorooctane, 3,3,4,4,5,5,6,6-octafluoroocta-1,7-di Ene, 1,10-di(meth)acryloyloxy-3,3,4,4,5,5,6,6,7 ,7,8,8-dodecafluorodecane, 3,3,4,4,5,5,6,6,7,7,8, 8-Dodecafluorodeca-1,9-diene, 1,12-di(meth)acryloyloxy- 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10-Hexadecaf Examples of suitable acrylates include bifunctional (meth)acrylates having a fluorine atom, such as fluorododecane.

[0062] The tri- or higher functional fluorine-containing radical polymerizable compound (B) is preferably triallyl cyanurate. triallyl isocyanurate compounds such as triallyl isocyanurate; Methylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane triacrylate (Meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate , ethoxylated propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol Ethritol tri(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate Acrylate, Propoxylated Pentaerythritol Tri(Meth)acrylate, Ethoxy Propoxylated pentaerythritol tri(meth)acrylate, pentaerythritol Tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated propanediol Epoxylated pentaerythritol tetra(meth)acrylate, ditrimethylolpropane Polyfunctional acrylates such as dipentaerythritol hexa(meth)acrylate Aliphatic (meth)acrylate compounds; Ethoxylated tri(meth)acrylate isocyanurate acrylate, propoxylated isocyanuric acid tri(meth)acrylate, and ethoxylated propoxylated Polyfunctional heterocyclic (meth)acrylates such as thioisocyanuric acid tri(meth)acrylate Examples include compounds in which a part of the compound is substituted with fluorine.

[0063] Among the above, from the viewpoint of imparting heat resistance, the above-mentioned bifunctional or trifunctional or higher fluorine compounds are preferred. It is preferable to use at least one compound selected from the group consisting of radical polymerizable compounds. In addition, from the viewpoint of easy availability of the compound and excellent reactivity, (meta) Acrylate compounds are preferred. Adhesion to materials with low dielectric constant properties, such as PTFE substrates From the viewpoint of improvement, a compound having 5 to 30 fluorine atoms in the molecule is preferred.

[0064] The fluorine-containing radical polymerizable compound (B) does not have a polar functional group in the molecule, or The number of polar functional groups is preferably small. If the structure is present, the substituents should not have polar functional groups or should have few polar functional groups. It is preferable that: If the number of polar functional groups is small, the compatibility with the hydrocarbon polymer compound (A) will be good, The dielectric loss tangent of the resulting cured sheet is also low. Polar functional groups have electronegative atoms (e.g., nitrogen, oxygen, chlorine, etc.) and possess a net dipole. For example, an ester group, a carbonyl group, a carboxyl group, a hydroxyl group, Examples thereof include a silyl group, an amido group, and an amino group.

[0065] The content of the fluorine-containing radically polymerizable compound (B) in the resin composition is The amount is preferably 0.01 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the aromatic polymer compound (A). Preferably, the amount is 0.05 parts by mass or more and 40 parts by mass or less, more preferably 0.1 parts by mass or more and 30 parts by mass or less. It is more preferably 0.5 parts by mass or more and 25 parts by mass or less, and particularly preferably 0.5 parts by mass or more and 25 parts by mass or less. When the content of the fluorine-containing radical polymerizable compound (B) is within the above range, the hydrocarbon-based polymerizable It is easy to increase the crosslink density artificially without deteriorating the low dielectric properties of the molecular compound (A). Therefore, the resulting cured sheet has good dielectric properties and heat resistance.

[0066] The hydrocarbon-based polymer compound (A) and the fluorine-containing radical polymerizable compound (B) The sum of the contents is preferably 30% by mass or more relative to the total mass of the resin composition, It is more preferably 0% by mass or more, and even more preferably 70% by mass or more. Contents of the hydrocarbon polymer compound (A) and the fluorine-containing radical polymerizable compound (B) By ensuring that the sum of these is within the above range, it is possible to obtain a cured product that has excellent adhesiveness and a low dielectric tangent. The upper limit of the sum of the above contents is not particularly limited, but from the viewpoint of improving adhesiveness, The content is preferably 98% by mass or less, more preferably 97% by mass or less, and even more preferably 96% by mass or less. Preferred.

[0067] 3. Radical polymerizable compound (C) The radical polymerizable compound (C) is any compound other than the above-mentioned fluorine-containing radical polymerizable compound (B). It is a compound having two or more ethylenically unsaturated bonds in the molecule. The compound (C) may be either bifunctional or trifunctional or higher. The radically polymerizable compound (C) does not contain a fluorine atom.

[0068] The bifunctional radical polymerizable compound (C) may be divinylbenzene, divinylnaphthalene, difunctional aromatic vinyl compounds such as divinylbiphenyl; ethylene glycol di(methyl) acrylate, diethylene glycol di(meth)acrylate, triethylene glycol Di(meth)acrylate, tetraethylene glycol di(meth)acrylate, poly Ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di( meth)acrylate, tetrapropylene glycol di(meth)acrylate, polypropylene Ethoxylated polypropylene glycol di(meth)acrylate ) acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol Di(meth)acrylate, Neopentyl glycol di(meth)acrylate, 3-methylpropional 1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di (Meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate Acrylate, 1,9-Nonanediol di(meth)acrylate, 1,10-Decanedio Di(meth)acrylate, Glycerin di(meth)acrylate, Tricyclodecane di Methanol di(meth)acrylate and ethoxylated 2-methyl-1,3-propanedioic acid Difunctional aliphatic (meth)acrylate compounds such as diol di(meth)acrylate; cyclohexane Sandimethanol di(meth)acrylate, ethoxylated cyclohexanedimethanol di( Meth)acrylate, propoxylated cyclohexanedimethanol di(meth)acrylate , ethoxylated propoxylated cyclohexanedimethanol di(meth)acrylate, tricyclo Cyclodecane dimethanol di(meth)acrylate, ethoxylated tricyclodecane dimethano Di(meth)acrylate, propoxylated tricyclodecane dimethanol di(meth)acrylate Acrylate, ethoxylated propoxylated tricyclodecane dimethanol di(meth)acrylate Ethoxylated hydrogenated bisphenol A di(meth)acrylate, propoxylated hydrogenated bis Phenol A di(meth)acrylate, ethoxylated propoxylated hydrogenated bisphenol A di (meth)acrylate, ethoxylated hydrogenated bisphenol F di(meth)acrylate, etc. Functional alicyclic (meth)acrylate compounds; ethoxylated bisphenol A di(meth)acrylate Propoxylated Bisphenol A Di(meth)acrylate, Ethoxylated Propoxy Ethoxylated Bisphenol A Di(meth)acrylate Ethoxylated Propoxylated Bisphenol F Di (Meth)acrylate, ethoxylated fluorene type di(meth)acrylate, propoxylated Fluorene type di(meth)acrylate and ethoxylated propoxylated fluorene type di(meth)acrylate Bifunctional aromatic (meth)acrylate compounds such as acrylate; ethoxylated isocyanates Propoxylated isocyanuric acid di(meth)acrylate, ethylenediamine dimethacrylate, Bifunctional heterocyclic (meth)acrylates such as hydroxylated propoxylated isocyanuric acid di(meth)acrylate ) acrylate compounds, etc.

[0069] The trifunctional or higher radical polymerizable compound (C) includes triallyl cyanurate and triaryl cyanurate. Triaryl isocyanurate compounds such as triaryl isocyanurate; trimethylol Propane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate Acrylate, Propoxylated Trimethylolpropane Tri(meth)acrylate, Ethoxy Propoxylated trimethylolpropane tri(meth)acrylate, pentaerythritol Pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate propoxylated pentaerythritol tri(meth)acrylate, ethoxylated propoxylated Pentaerythritol nitrate tri(meth)acrylate, pentaerythritol tetra(meth)acrylate tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, pro Ethoxylated pentaerythritol tetra(meth)acrylate, ethoxylated propoxylated pentaerythritol tetra(meth)acrylate Pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetraacrylate and polyfunctional aliphatic ( Meth)acrylate compounds; ethoxylated isocyanuric acid tri(meth)acrylate, pro Ethoxylated propoxylated isocyanuric acid tri(meth)acrylate, and ethoxylated propoxylated isocyanuric acid tri(meth)acrylate. Polyfunctional heterocyclic (meth)acrylate compounds such as anuric acid tri(meth)acrylate, etc. Examples include:

[0070] Among the above, styrene-based thermoplastic elastomers are preferred as hydrocarbon polymer compounds (A). When using a styrene-based thermoplastic elastomer, it is necessary to select a styrene-based thermoplastic elastomer that exhibits a suitable compatibility with the styrene-based thermoplastic elastomer. a difunctional aromatic vinyl compound, and a trialkenyl isocyanurate compound; Among them, divinylbenzene or triallyl isopropanol is preferred. Cyanurates are more preferred, and trialkenyl isocyanurates are preferred from the viewpoint of low dielectric properties. is more preferable.

[0071] The radical polymerizable compound (C) does not have a polar functional group in the molecule, or It is preferable that the number of groups is small. When the radical polymerizable compound (C) has a cyclic structure, It is preferred that the substituents have no polar functional groups or have only a small number of polar functional groups. If the number of polar functional groups is small, the compatibility with the hydrocarbon polymer compound (A) will be good, The dielectric loss tangent of the resulting cured sheet is also low. Polar functional groups have electronegative atoms (e.g., nitrogen, oxygen, chlorine, etc.) and possess a net dipole. For example, an ester group, a carbonyl group, a carboxyl group, a hydroxyl group, Examples thereof include a silyl group, an amido group, and an amino group. When the radical polymerizable compound (C) has an ester group, the radical polymerizable compound (C) The polar functional group equivalent weight (molecular weight of radical polymerizable compound (C) / molecular weight of polar functional group (polar functional group equivalent weight) When there are a plurality of functional groups, the total number thereof is preferably 2 or more, more preferably 3 or more, 4 or more is more preferred, 5 or more is even more preferred, and 6 or more is even more preferred.

[0072] The mass average molecular weight (Mw) of the radical polymerizable compound (C) is preferably 100 or more, and more preferably 1 It is more preferably 20 or more. In addition, the mass average molecular weight (Mw) is preferably 5,000 or less. Preferably, it is 4,000 or less, more preferably 3,000 or less, and more preferably 1,000 or less. Lower is even more preferable, with 600 or less being even more preferable. When the mass average molecular weight (Mw) of the radical polymerizable compound (C) is within the above range, hardness can be improved. During polymerization, the hydrocarbon polymer compound (A), the fluorine-containing radical polymerizable compound (B) and the radical polymerizable compound (C) are The molecular chains of the polymerizable compound (C) become more easily entangled with each other, artificially increasing the cross-link density. Therefore, the heat resistance of the resulting cured sheet is improved. In addition, when the radical polymerizable compound (C) is not a partially crosslinked or polymerized product, it is called "radical The "mass average molecular weight (Mw) of the radical polymerizable compound (C)" means the mass average molecular weight (Mw) of the radical polymerizable compound (C). This refers to the molecular weight of the compound used.

[0073] When the present composition contains a radical polymerizable compound (C), the content thereof is The amount is preferably 1 part by mass or more and 50 parts by mass or less, and more preferably 3 parts by mass or more, per 100 parts by mass of the compound (A). The amount is more preferably from 5 to 30 parts by mass, and even more preferably from 5 to 30 parts by mass. When the content of the radical polymerizable compound (C) is within the above range, the hydrocarbon polymer compound Since it is easy to increase the crosslink density artificially without decreasing the dielectric properties of (A), The resulting cured sheet has good dielectric properties and heat resistance.

[0074] In addition, when the present composition contains a radical polymerizable compound (C), a hydrocarbon polymer compound ( A) 100 parts by mass of the fluorine-containing radical polymerizable compound (B) and the radical polymerizable The total content of the compound (C) is preferably 2 parts by mass or more and 100 parts by mass or less, and more preferably 3 parts by mass or more. It is more preferably 50 parts by mass or less, and even more preferably 5 parts by mass or more and 30 parts by mass or less. Sum of the contents of the fluorine-containing radical polymerizable compound (B) and the radical polymerizable compound (C) When the value is within the above range, the dielectric properties of the hydrocarbon polymer compound (A) can be maintained without being deteriorated. This makes it easier to increase the crosslink density, improving the dielectric properties and heat resistance of the resulting cured sheet. will be good.

[0075] 4.Organic peroxide (D) The resin composition may contain an organic peroxide (D) for the purpose of accelerating the curing reaction. . Examples of the organic peroxide include hydroperoxide and dialkyl peroxide. peroxides, diacyl peroxides, peroxyesters and ketone peroxides Examples of such things include: Specifically, cumene hydroperoxide, tert-butyl hydroperoxide Hydroperoxides such as dicumyl peroxide, di-tert-butyl peroxide, etc. oxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2 ,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne, etc. alkyl peroxide; diacids such as lauryl peroxide and benzoyl peroxide tert-Butyl peroxide; tert-butyl peroxyacetate, tert-butyl peroxide Peroxy compounds such as dibenzoate and tert-butylperoxyisopropyl carbonate Esters; ketone peroxides such as cyclohexanone peroxide.

[0076] The content of the organic peroxide (D) in the composition is 10% by weight of the hydrocarbon polymer compound (A). 0 parts by mass, the amount is preferably 0.01 parts by mass or more and 5 parts by mass or less, and more preferably 0.05 parts by mass or more and 3 parts by mass or less. It is more preferable that the amount is 0.1 parts by mass or less and 1 part by mass or less, and even more preferable that the amount is 0.1 parts by mass or more and 1 part by mass or less. When the content of the organic peroxide (D) is within the above range, the curing reaction is accelerated and the sheet The dielectric properties of the cured product can be maintained at a low level.

[0077] 5. Solvent (E) The resin composition may contain a solvent (E) if necessary to adjust viscosity or the like. The solvent (E) is not particularly limited as long as it can uniformly dissolve the components of the resin composition. Examples of the solvent (E) include toluene, cyclohexane, tetrahydrofuran, and xylene. Examples of the solvents listed above include ethylene, methyl ethyl ketone, etc. Two or more kinds of solvents may be mixed in any combination and ratio. From the viewpoint of residual solvent, the temperature is preferably 200° C. or less.

[0078] The content of the solvent (E) in the resin composition is determined based on the hydrocarbon polymer from the viewpoint of film-forming properties. The amount of the compound (A) is preferably 100 parts by mass or more and 500 parts by mass or less, and more preferably 200 parts by mass or more. More preferably, the amount is from 1 part by mass to 400 parts by mass.

[0079] 6. Other Ingredients The resin composition may contain, as a component other than the above, a thermoplastic resin other than the hydrocarbon polymer compound (A). Fluorine-containing radical polymerizable compound (B) and radical polymerizable elastomer, crosslinking agent Compound (C) excluded), monofunctional vinyl compounds, ultraviolet absorbers, antistatic agents, antioxidants, carbon black Coupling agents, plasticizers, flame retardants, colorants, dispersants, emulsifiers, elasticity reducing agents, diluents, defoamers The ink may contain an ion trapping agent, a thickener, a leveling agent, inorganic particles, organic particles, etc.

[0080] Examples of the crosslinking agent include bismaleimide compounds, isocyanate compounds, epoxy compounds, and the like. Examples include silicon compounds.

[0081] Examples of inorganic particles include calcium carbonate, magnesium carbonate, barium carbonate, and sulfuric acid. Magnesium, barium sulfate, calcium sulfate, zinc oxide, magnesium oxide, calcium oxide Sodium, titanium oxide, aluminum oxide, zinc oxide, alumina, aluminum hydroxide, Hydroxyapatite, silica, magnesium silicate, mica, talc, kaolin, Examples of suitable inorganic fillers include clay, glass powder, asbestos powder, zeolite, and clay silicate. Examples of organic particles include (meth)acrylate resin particles, styrene resin particles, Silicone resin particles, nylon resin particles, polyethylene resin particles, benzoguanamine Examples of the resin particles include acrylic resin particles and urethane resin particles. When inorganic particles or organic particles are contained, the content thereof is based on 100 mass of the resin component of the composition. The amount is preferably 1 part by mass or more and 200 parts by mass or less, and more preferably 5 parts by mass or more and 150 parts by mass or less. The amount is more preferably 10 parts by mass or more and 100 parts by mass or less. When the content of the copolymer is equal to or greater than the lower limit, the dielectric properties of the cured sheet can be further reduced. Furthermore, the coefficient of linear thermal expansion of the cured sheet can be reduced, and when used as a circuit board material, On the other hand, when the content of inorganic particles or organic particles is equal to or less than the upper limit, peeling is unlikely to occur. In this case, the formability of the cured sheet product is improved.

[0082] <Physical properties of the resin composition> The present resin composition can have the following physical properties.

[0083] The adhesive strength of the resin composition is determined appropriately depending on the material of the adherend. For example, the adhesive strength of the resin composition against copper foil is The adhesive strength is preferably 0.6 kN / m or more, and particularly preferably 0.7 kN / m or more. The adhesive strength is 0.6 kN / m or more, and therefore the resin composition can be used in circuits. When used as a substrate material, it can be made to be one that does not peel off or deform. Specifically, the adhesive strength can be measured by the method described in the examples below.

[0084] In addition, the adhesive strength of the resin composition to polytetrafluoroethylene (PTFE) is as follows: It is preferably 0.5 kN / m or more, and particularly preferably 1.6 kN / m or more. stomach. In order to cope with the future trend toward higher communication frequencies, the application of PTFE substrates with excellent low dielectric properties is expected. The adhesive strength of 0.5 kN / m or more is expected to This is preferable in that when used as a substrate material, peeling and deformation do not occur. Specifically, the adhesive strength can be measured by the method described in the examples below.

[0085] The relative dielectric constant of the resin composition after curing is preferably 4 or less, more preferably 3 or less. On the other hand, the lower limit of the relative dielectric constant is not particularly limited, and it is preferably 1 or less. As long as it's above, that's fine. The dielectric loss tangent of the resin composition after curing is preferably 0.003 or less, and more preferably 0.0 It is more preferable that the dielectric loss tangent is 0.025 or less, and even more preferable that the dielectric loss tangent is 0.002 or less. The lower limit of is not particularly limited, and may be 0 or more. The above dielectric constant and dielectric loss tangent were measured by measuring the dielectric constant of the resin composition at 200°C and 2 MPa. The cured product was heat-pressed for 1 minute and used as a test piece. The values were obtained by measuring at a temperature of 23°C and a frequency of 10 GHz.

[0086] <Resin sheet> The resin sheet according to one embodiment of the present invention (hereinafter also referred to as "the present resin sheet") is The uncured resin composition is formed into a sheet.

[0087] The thickness of the resin sheet is preferably 10 to 500 μm, more preferably 50 to 400 μm. The thickness is preferably 100 to 350 μm. When the thickness of the present resin sheet is equal to or greater than the above lower limit, the handling properties are good. If the thickness is equal to or less than the upper limit, when the resin sheet is used as a circuit board material, This improves conformability to unevenness in the substrate.

[0088] <Laminate> This resin sheet has a release film on one or both surfaces to improve handling. It is preferable to provide a laminate. Examples of the release film include polyolefins such as polyethylene and polypropylene; Polyesters such as polyethylene terephthalate and polyethylene naphthalate; polyimides A resin film mainly composed of polycarbonate or the like can be used. The peel strength may be adjusted by applying a silicone resin release agent or the like to the surface. The thickness of the release film is preferably 1 to 300 μm, more preferably 5 to 200 μm, It is more preferably 10 to 150 μm, and even more preferably 20 to 120 μm. The release film has matte finish, corona treatment, and anti-static treatment on the surface that comes into contact with the resin sheet. may be applied.

[0089] The laminate may be a wound body wound around a core. In the wound body according to one embodiment of the present invention, the length of the laminate is preferably 10 m or more. The length of the laminate is preferably 10 m or more, and more preferably 20 m or more. For example, the resin sheet can be used as a flexible laminate or a stretchable laminate. In this case, it is possible to continuously produce electronic components, and the continuous film-forming property is excellent. There is no particular upper limit to the length, but it is preferably 1000 m or less. The material of the core is not particularly limited, but examples thereof include paper, resin-impregnated paper, and acrylonitrile / butadiene. Diene / styrene copolymer (ABS resin), fiber reinforced plastic (FRP), phenol Examples of the resin include a resin containing inorganic substances, etc. An adhesive may be used for the core.

[0090] <Method of manufacturing resin sheet> The method for producing the resin sheet will be described below. It is not limited to the law.

[0091] [First manufacturing method] The first method for producing the resin sheet includes a coating liquid preparation step for preparing a coating liquid comprising a resin composition. and a forming step of forming the coating liquid into a sheet.

[0092] (1) Coating liquid preparation process In the coating liquid preparation process, a hydrocarbon polymer compound (A), a fluorine-containing radical polymerizable compound (B), (B), radical polymerizable compound (C), organic peroxide (D) as needed, solvent (E) and other ingredients are stirred to mix uniformly to obtain a coating liquid. For mixing, for example, a mixer, a blender, a three-roll kneading device, a ball mill, a kneader A general mixing and stirring device such as a single-screw kneader or a twin-screw kneader can be used for mixing. In this case, heating may be carried out as necessary.

[0093] (2) Molding process In the molding step, the coating liquid is molded into a sheet to obtain a resin sheet. The coating liquid can be formed into a sheet by any known method. For example, the doctor blade method, the solvent casting method, the extrusion film forming method, etc. may be used. A new molding method includes the following steps (2-1) coating and (2-2) drying. Examples include the law.

[0094] (2-1) Coating process In the coating step, a coating liquid is applied to the surface of a release film to form a coating film. The coating method is a common method such as dipping, spin coating, spray coating, blade coating, etc. The coating may be carried out by any of various methods, including a spin coater, a slit coater, a die coater, a brush coater, etc. Coating equipment such as a ladle coater or gravure coater can be used, which allows for easy release. It is possible to form a coating film of a predetermined thickness uniformly on the film.

[0095] (2-2) Drying process In the drying step, the solvent is removed from the coating film formed above. The drying temperature is not particularly limited, but is usually 10 to 150°C, preferably 25 to 120°C, more preferably The drying temperature is more preferably 30 to 110° C. When the drying temperature is equal to or lower than the upper limit, the The crosslinking reaction of the fluorine-containing radical polymerizable compound (B) is suppressed. By ensuring that the content is equal to or greater than the lower limit, foaming of the resin sheet can be suppressed and the solvent can be removed effectively. This increases productivity. The drying time can be adjusted appropriately depending on the state of the coating film, the drying environment, etc. Preferably, the time is 30 seconds or more, more preferably 1 minute or more, and even more preferably 2 minutes or more. On the other hand, the drying time is preferably 1 hour or less, and more preferably 30 minutes or less. and more preferably 15 minutes or less. When the drying time is equal to or longer than the lower limit, the solvent can be sufficiently removed. By satisfying the above condition, productivity can be improved and manufacturing costs can be reduced. The solvent in the resin composition can be easily removed by using a hot plate, a hot air oven, an IR heating oven, a vacuum dryer, or a high-frequency oven. It can be removed by a known heating method such as a heating machine.

[0096] In addition, from the viewpoint of preventing contamination of the resin sheet surface and ease of handling, after the drying process, A release film may be laminated on the resin sheet.

[0097] [Second manufacturing method] The second method for producing the resin sheet includes a film-forming step of extruding a resin composition onto a release film. include.

[0098] In the film-forming process, a hydrocarbon polymer compound (A) and a fluorine-containing radical polymerizable compound (B) are mixed. ), a radical polymerizable compound (C), an organic peroxide (D) if necessary, and other components are simply The mixture is kneaded in a screw extruder or a twin-screw extruder, and heated to a temperature equal to or higher than the melting point of the hydrocarbon polymer compound (A) and The fluorine-containing radical polymerizable compound (B) is polymerized by using an extruder or the like under a temperature condition lower than the crosslinking temperature. The resin composition is extruded onto a release film to form a film. The extrusion method is not particularly limited, but A specific example is T-die molding.

[0099] The curing temperature of the present resin composition is set at a temperature at which the hydrocarbon polymer compound (A) does not flow and the fluorine The temperature may be any temperature at which the crosslinking reaction of the radical polymerizable compound (B) contained proceeds. The temperature is preferably 120 to 300°C, more preferably 140 to 250°C, and particularly preferably 150 to 220°C. Even more preferable. The curing time of the present resin composition is not particularly limited, but is preferably 10 minutes to 2 hours.

[0100] <Applications of resin composition and resin sheet> The resin composition and the resin sheet according to one embodiment of the present invention can be used, for example, for copper foil. Laminates, stretchable boards, flexible printed circuit boards, multilayer printed wiring boards, Circuit board materials for electrical and electronic equipment such as capacitors, underfill materials, and 3D-LSI interconnects Turbine filler, insulating sheet, vibration damping material, adhesive, solder resist, semiconductor encapsulation material, hole Examples of suitable resins include potting resins and component potting resins, but are not limited to these.

[0101] The resin composition of the present invention can be used as a circuit board material by laminating it with a conductor. When used as a circuit board material for electric and electronic devices, the resin composition is formed into a resin sheet. The thickness of the resin sheet is preferably 10 μm or more and 500 μm or less. The thickness of the conductor is preferably 0.2 μm or more and 70 μm or less.

[0102] Conductors are made of conductive metals such as copper and aluminum, or alloys containing these metals. A metal foil or a metal layer formed by plating or sputtering can be used.

[0103] <Circuit board materials> The circuit board material of the present invention can be produced, for example, by the following method. After placing the resin sheet according to one embodiment of the present invention on a conductor, the resin sheet is thermally cured. An insulating layer is formed, and a conductor is layered on top of the insulating layer, and the required number of such layers are stacked. The curing temperature of the resin sheet is set at a temperature at which the hydrocarbon polymer compound (A) does not flow and the fluorine The temperature may be any temperature at which the crosslinking reaction of the radical polymerizable compound (B) contained proceeds. The curing temperature of the present resin sheet is preferably 120 to 300°C, more preferably 140 to 250°C. The temperature is preferably 150 to 220°C. The curing time of the resin sheet is not particularly limited, but is preferably 10 minutes to 2 hours. The resin sheet and conductor are laminated by directly overlaying a conductive metal foil on the resin sheet. Alternatively, a method of bonding a resin sheet and a conductive metal foil using an adhesive may be used. Alternatively, a method of forming a conductive metal layer by plating or sputtering may be used. These methods may also be combined. In addition, there are processes for drilling holes in the insulating layer to form via holes, and for roughening the surface of the insulating layer. The method may include a step of: [Example]

[0104] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, various materials were prepared by the following methods. Sex was measured.

[0105] <Raw materials> [Hydrocarbon polymer compound (A)] a-1: Styrene-ethylene-butadiene-styrene block copolymer (SEBS: Asahi Kasei Co., Ltd., "Tuftec M1943"), styrene content 20% by mass, storage modulus (24 ℃)=6.8MPa, density=0.900g / cm 3 a-2: Styrene-ethylene-butadiene-styrene block copolymer (SEBS: Asahi Kasei Co., Ltd., "Tuftec H1052"), styrene content 20% by mass, storage modulus (24 ℃)=6.2MPa, density=0.890g / cm 3

[0106] [Fluorine-containing radical polymerizable compound (B)] b-1: 1,6-bis(acryloyloxy)-2,2,3,3,4,4,5,5-o Trifluorohexane (Tokyo Chemical Industry Co., Ltd.), mass average molecular weight (Mw): 370 b-2: 1H,1H,2H,2H-heptadecafluorodecyl acrylate (Tokyo Chemical Industry Co., Ltd.) (manufactured by Kogyo), mass average molecular weight (Mw): 532

[0107] [Radical polymerizable compound (C)] c-1: Triallyl isocyanurate (TAIC: manufactured by Shinryo Corporation), mass average molecular weight (Mw ):250

[0108] [Organic peroxide (D)] d-1: α,α-di(tert-butylperoxyisopropyl)benzene (NOF) (manufactured by the company, "Perbutyl P")

[0109] [Solvent (E)] e-1: Toluene (content: >99.0% by mass)

[0110] <Evaluation> The resulting resin composition was evaluated as follows, and the results are shown in Table 1.

[0111] (1) Dielectric properties The resin sheets with release films each having a resin thickness of 100 μm produced in the examples and comparative examples were The resin sheet was then completely pressed in a heat press at 00°C for 30 minutes under a pressure of approximately 2 MPa. The release films on both sides were peeled off to obtain a cured resin composition. The dielectric constant and dielectric loss tangent in the in-plane direction of the cured resin sheet were measured using a cavity resonator (manufactured by AET Co., Ltd.). ) and network analyzer MS46 122B (manufactured by Anritsu) in TE mode. The measurement frequency was set to 10 GHz.

[0112] (2) Copper foil adhesion The resin sheets with release films having a resin thickness of 25 μm produced in the examples and comparative examples were The release film was peeled off from the resin sheet and a 18μm thick film was applied to both surfaces. The matte surface of a 100mm thick copper foil (Fukuda Metal Foil & Powder Co., Ltd., "CF-T4X-SV") was laminated and heated at 200°C. The resin sheet is then completely hardened by applying a pressure of approximately 2 MPa to the heat press for 30 minutes. The resulting laminate was cut into a 1.5 cm width to prepare a measurement sample. The obtained measurement samples were subjected to a universal testing machine (Shimadzu Corporation) with a chuck distance of 25 mm. A T-peel test was conducted at a peel rate of 50 mm / min in an environment of 23°C to measure the peel strength. did.

[0113] (3)PTFE adhesiveness The resin sheets with release films having a resin thickness of 25 μm produced in the examples and comparative examples were The release film was peeled off from the resin sheet and a 127 mm thick film was applied to both surfaces. μm PTFE substrate (Rogers, "RT5880", etched) The resin sheet is then heated at 200°C for 30 minutes under a pressure of approximately 2 MPa. The laminate was then completely cured to obtain a laminate. The obtained laminate was cut into a width of 1.5 cm and used as a measurement test piece. The obtained measurement samples were subjected to a universal testing machine (Shimadzu Corporation). A T-peel test was conducted at a distance of 25 mm between the blocks, at a temperature of 23°C, and at a peel speed of 50 mm / min. The peel strength was measured.

[0114] Example 1 The raw materials are mixed in the proportions shown in Table 1, heated to approximately 80°C, and completely dissolved to form a resin composite. The prepared resin composition was applied to a 50 μm thick release film treated with silicone release agent. The resin sheet is spread on the release-treated surface of a film (PET film manufactured by Mitsubishi Chemical Corporation). The thickness of the resin sheet was adjusted so that the thickness of the sheet after curing was about 100 μm. The thickness of the sheet after curing was adjusted to 25 μm. Successful. The resin sheet spread on the release film was dried in an oven at 100°C for 1 hour, and then the resin A 50 μm thick release film (Mitsubishi Chemical Corporation) with silicone release treatment was placed on top of the sheet. PET film) is laminated so that the release-treated surface faces the resin sheet to form a laminate. The laminate was held in a heat press at 200°C for 30 minutes under a pressure of approximately 0.2 MPa. The resin sheet was then completely cured, and the release films on both sides were peeled off to obtain a cured sheet. The dielectric properties and adhesion to copper foil and PTFE substrates were evaluated for the cured sheets. .

[0115] <Examples 2 to 5, Comparative Example 1> The sheet was cured in the same manner as in Example 1, except that the raw materials were mixed according to the ratios shown in Table 1. The obtained cured sheet was subjected to the dielectric properties test and the comparison with the copper foil and PTFE substrates. The adhesion was evaluated.

[0116] [Table 1]

[0117] From Examples 1 to 5, the hydrocarbon polymer compound (A), the fluorine-containing radical polymerizable compound By including (B), it is possible to achieve close contact with the copper foil and PTFE substrate while maintaining low dielectric properties. A cured sheet product with an excellent balance of adhesion properties was obtained. The polymerizable composition does not contain the fluorine-containing radical polymerizable compound (B) and contains only the radical polymerizable compound (C). In Comparative Example 1, the interaction with the adherend was reduced, and the copper foil and PTFE substrate The adhesion was poor.

[0118] In the above examples, a styrene-based thermoplastic elastomer was used as the hydrocarbon-based polymer compound (A). Although there are no examples of using other than olefins, hydrocarbon polymer compounds (A), fluorine-containing radical polymers, The molecular chains of the synthetic compound (B) are entangled with each other, and while maintaining low dielectric properties, they function as conductors and The mechanism by which adhesion to the substrate can be improved is that styrene-based thermoplastic elastomers The same effect can be expected.

Claims

1. A hydrocarbon polymer compound (A) containing no oxygen atoms in the main chain and a fluorine-containing radical polymer A resin composition comprising a synthetic compound (B).

2. The resin composition according to claim 1, wherein the hydrocarbon-based polymer compound (A) is a thermoplastic resin. thing.

3. The hydrocarbon-based polymer compound (A) is a styrene-based thermoplastic elastomer, an olefin At least one selected from the group consisting of thermoplastic elastomers and ethylene polymers The resin composition according to claim 1 .

4. The hydrocarbon-based polymer compound (A) includes a styrene-based thermoplastic elastomer. The resin composition according to claim 1.

5. The styrene content of the styrene-based thermoplastic elastomer is 10% by mass or more and 70% by mass or less. The resin composition according to claim 4, wherein:

6. The hydrocarbon polymer compound (A) has a mass average molecular weight (Mw) of 30,000 or more. The resin composition according to claim 1 .

7. The fluorine-containing radical polymerization 2. The method according to claim 1, wherein the content of the reactive compound (B) is 0.01 parts by mass or more and 50 parts by mass or less. A resin composition.

8. The fluorine-containing radical polymerizable compound (B) has a mass average molecular weight (Mw) of 100 or more and The resin composition according to claim 1, wherein the viscosity is 1,000 or less.

9. The resin composition according to claim 1 , further comprising a radical polymerizable compound (C) other than the component (B).

10. The fluorine-containing radical polymerization the sum of the contents of the radically polymerizable compound (B) and the radically polymerizable compound (C) is 2 parts by mass or more and 10 parts by mass or less; The resin composition according to claim 9, wherein the content of the hydroxybenzoates is 0% by mass or less.

11. The resin composition was heat-pressed at 200°C and 2 MPa for 30 minutes to obtain a cured product.

2. The resin composition according to claim 1, wherein the dielectric loss tangent at a frequency of 10 GHz is 0.002 or less. Finished product.

12. A resin sheet comprising the resin composition according to any one of claims 1 to 11.

13. A laminate comprising the resin sheet according to claim 12 and a release film on one or both surfaces thereof. 。

14. A cured sheet obtained by curing the resin sheet according to claim 12.

15. A circuit board material obtained by laminating an insulating layer made of the resin sheet according to claim 12 and a conductor. Fee.

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