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 which have low dielectric properties and heat resistance.SOLUTION: There is provided a resin composition which comprises at least one thermoplastic resin (A) selected from the group consisting of a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, an ethylene-based polymer and a cyclic polyolefin resin copolymer and an alicyclic polyfunctional (meth)acrylate compound (B) represented by the following general formula (I). (In the formula, R1 represents a hydrogen atom or a methyl group, R2 represents a hydroxyl group or a monovalent organic group, X represents an alicyclic hydrocarbon group. However, when R2 is a monovalent organic group, two or more R2 groups may be bonded together to form a condensed ring comprising a ring X. l represents an integer of 1 or 2, m represents an integer of 2 to 10, n represents an integer of 0 to 10. When the number of carbon atoms constituting the ring X is defined as x, 2x≥m+n.)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. On the other hand, as the circuits in electrical and electronic equipment become more highly integrated, the amount of heat generated inside the equipment also increases. As a result, circuit board materials are also required to be heat resistant.

[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.

[0006] Therefore, the present invention provides the above-mentioned sheet cured product and precursor having low dielectric properties and heat resistance. The object of the present invention is to provide a resin composition, a resin sheet, and a laminate that can be used to produce the circuit board material. do. [Means for solving the problem]

[0007] As a result of extensive research into solving the above problems, the present inventors have found that styrene-based thermoplastic elastomers , olefin-based thermoplastic elastomers, ethylene-based polymers, and cyclic polyolefin resins At least one thermoplastic resin (A) selected from the group consisting of alicyclic poly(ethylene glycol) copolymers The resin composition containing the functional (meth)acrylate compound (B) provides low dielectric properties and heat resistance. I discovered that it is possible to achieve both gender.

[0008] The gist of the present invention is as follows. [1] Styrenic thermoplastic elastomer, olefinic thermoplastic elastomer, ethylene At least one selected from the group consisting of a cyclic polyolefin resin copolymer and a cyclic polyolefin resin copolymer. and a thermoplastic resin (A) represented by the following general formula (I): A resin composition containing a late compound (B). [ka] (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents a hydroxyl group or a monovalent organic group, X represents an alicyclic hydrocarbon group. 2 When R is a monovalent organic group, two or more R 2 But each other may be bonded to form a fused ring containing ring X. l represents an integer of 1 or 2, and m represents an integer of 2 to 1. 0, and n represents an integer of 0 to 10. However, when the number of carbon atoms constituting ring X is If m+n, then 2x≧m+n.) [2] The thermoplastic resin (A) contains a styrene-based thermoplastic elastomer. 1] The resin composition according to claim 1. [3] The styrene content of the styrene-based thermoplastic elastomer is 10% by mass or more and 70% by mass or less. % or less. [4] The mass average molecular weight (Mw) of the thermoplastic resin (A) is 30,000 or more. The resin composition according to any one of [1] to [3] above. [5] The alicyclic polyfunctional (meth)acrylate relative to 100 parts by mass of the thermoplastic resin (A). Any of [1] to [4], wherein the content of the carboxylate compound (B) is 1 part by mass or more and 50 parts by mass or less. The resin composition according to any one of the above. [6] The mass average molecular weight (Mw) of the alicyclic polyfunctional (meth)acrylate compound (B) is The resin composition according to any one of [1] to [5], wherein the molecular weight is 100 or more and 5,000 or less. [7] Any of [1] to [6] containing a radical polymerizable compound (C) other than component (B). The resin composition according to claim 1. [8] The alicyclic polyfunctional (meth)acrylate relative to 100 parts by mass of the thermoplastic resin (A). The sum of the contents of the carboxylate compound (B) and the radical polymerizable compound (C) is 2 parts by mass or more and 1 part by mass or less. 00% by mass or less of the resin composition according to [7]. [9] The resin composition is heat-pressed at 200°C and 2 MPa for 30 minutes to obtain a cured product. [1] to [8], in which the dielectric loss tangent at a frequency of 10 GHz is 0.003 or less. The resin composition according to any one of the above.

[10] A resin sheet comprising the resin composition according to any one of [1] to [9].

[11] A laminate comprising the resin sheet according to

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

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

[10] above.

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

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

[0009] According to the present invention, a resin composition having low dielectric properties and heat resistance, 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. In the present invention, the numerical ranges described in stages are not necessarily the upper limit of the numerical range of a certain stage. The upper or lower limit may be arbitrarily combined with the upper or lower limit of a numerical range of another stage. In addition, in the numerical ranges described in the present invention, the upper or lower values ​​of the numerical ranges can be The limit values ​​may be replaced with values ​​shown in the Examples or Production Examples. 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") is a olefin-based thermoplastic elastomers, olefin-based thermoplastic elastomers, ethylene-based polymers, and at least one thermoplastic resin selected from the group consisting of cyclic polyolefin resin copolymers Resin (A) and an alicyclic polyfunctional (meth)acrylate having two or more ethylenically unsaturated bonds in the molecule p) Contains an acrylate compound (B). The cured sheet and circuit board material made from this resin composition have good low dielectric properties and heat resistance. The reason for this is unclear, but the following points are considered: When the resin composition is cured, the alicyclic polyfunctional (meth)aryl group is reacted with the thermoplastic resin (A). The molecular chains of the acrylate compound (B) are partially and physically entangled with each other, forming a thermoplastic resin. It is believed that heat resistance can be imparted while maintaining the low dielectric properties of the fat (A). Each component of the resin composition will now be described.

[0013] 1. Thermoplastic resin (A) The thermoplastic resin (A) in the resin composition is a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, or the like. Fin-based thermoplastic elastomers, ethylene polymers and cyclic polyolefin resin copolymers The resin composition has excellent low dielectric properties. The thermoplastic resin (A) may be used alone or in combination of two or more kinds. The above may be used in combination.

[0014] 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.

[0015] 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.

[0016] 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.

[0017] 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.

[0018] 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) 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.

[0019] 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.

[0020] 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.

[0021] 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."

[0022] 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] (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).

[0029] [ka]

[0030] 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.

[0031] 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.

[0032] 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.

[0033] (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.

[0034] 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.

[0035] (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.

[0036] 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.

[0037] 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.

[0038] (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.

[0039] 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.

[0040] Among the thermoplastic resins (A) exemplified above, the thermoplastic resin (A) itself is particularly preferably an alicyclic polyolefin. When a combination that does not easily react with the functional (meth)acrylate compound (B) is selected The polymers are made of a thermoplastic resin (A) and an alicyclic polyfunctional (meth)acrylate compound (B) with the same molecular chain structure. Since the resins are partially and physically intertwined with each other, it is more flexible than the thermoplastic resin (A) alone. Therefore, it is thought that the elastic modulus improves and the heat resistance improves. From this viewpoint, the thermoplastic resin (A) and the aromatic heterocyclic compound (B) are mutually Among the above thermoplastic resins (A), it is preferable to use a combination that does not react with the above. Styrene-based thermoplastic elastomers are preferred, and styrene-isobutylene-styrene-block Styrene-ethylene-butadiene-styrene block copolymer (SIBS) Styrene-ethylene-butadiene-styrene block copolymer (SEBS) is more preferred, The polymer (SEBS) is more preferred.

[0041] When a styrene-based thermoplastic elastomer is used as the thermoplastic resin (A), the styrene-containing The content is preferably 10% by mass or more, more preferably 15% by mass or more. The content is preferably 70% by mass or less, more preferably 60% by mass or less, and most preferably 50% by mass or less. It is more preferable, and even more preferable that it is 40 mass % or less. When the styrene content is within the above range, the thermoplastic resin (A) has a low dielectric tangent and a low modulus of elasticity. Since the dielectric constant is also moderate, low dielectric properties and heat resistance can be achieved at the same time, and handling properties are also good.

[0042] In addition, from the viewpoint of improving adhesiveness, improving heat resistance, reducing the coefficient of thermal expansion, and reducing tackiness, As the thermoplastic resin (A), styrene-based thermoplastic elastomer, olefin-based thermoplastic At least one selected from the group consisting of elastomers and ethylene polymers (hereinafter referred to as "A1") ) and a cyclic polyolefin resin copolymer (hereinafter also referred to as (A2)) It is preferable to do so. 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.

[0043] When the resin composition contains the thermoplastic resin (A) as described above (A1) and (A2), It is preferable that 1) is used as the main component. The "main component" of the thermoplastic resin (A) refers to the thermoplastic resin contained in the resin composition. This refers to the resin with the highest content of resin (A), and more specifically, the total content of thermoplastic resin (A). When the amount is taken as 100% by mass, the upper limit is 100% by mass, and preferably 50% by mass or more. More preferably, the resin accounts for 55% by mass or more, and even more preferably 60% by mass or more. .

[0044] In addition, when the resin composition contains (A1) and (A2) as the thermoplastic resin (A), ( The content of A2) is determined based on the total mass of the resin composition from the viewpoint of reducing the linear thermal expansion coefficient and reducing tackiness. As a standard, it is preferably 2% by mass or more, and more preferably 4% by mass or more. On the other hand, the upper limit is determined depending on the flexibility and adhesion to the substrate. From this viewpoint, the content is preferably 40% by mass or less, and more preferably 35% by mass or less. It is preferable that the content is 30 mass % or less.

[0045] The mass average molecular weight (Mw) of the thermoplastic resin (A) is such that tackiness occurs in the resulting resin sheet. From the viewpoint of preventing the occurrence of such a problem, a value of 30,000 or more is preferable, and a value of 40,000 or more is even more preferable. On the other hand, from the viewpoint of handling during film formation, , 300,000 or less is preferable, 250,000 or less is more preferable, 200,000 or less is more preferable The following is even more preferred: The mass average molecular weight (Mw) in the present invention is measured by gel permeation chromatography. This is a polystyrene equivalent value determined.

[0046] The thermoplastic resin (A) may be modified by a known method. Examples of the modified resin include For example, the above-mentioned thermoplastic resin (A) and at least one of an unsaturated carboxylic acid and its anhydride may be used. One example is a reaction product with By modifying the thermoplastic resin (A), the polarity of the polymer increases, so it is possible to Improved adhesion to metal layers can be expected.

[0047] 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:

[0048] 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.

[0049] The content of the thermoplastic resin (A) in the composition is 5 to 100 parts by mass based on the total mass of the resin composition. It is preferable that the content of the thermoplastic resin (A) is in the above range. This provides the benefits of low dielectric properties and copper foil adhesion. From the viewpoint of low dielectric properties and copper foil adhesion, the content of the thermoplastic resin (A) is It is more preferably 50% by mass or more, and more preferably 55% by mass or more, based on the total mass. It is more preferable that the content is 60% by mass or more, and particularly preferable that the content is 60% by mass or more. % or less, more preferably 90% by mass or less, and even more preferably 90% by mass or less.

[0050] The storage modulus of the thermoplastic resin (A) at 24°C is preferably 0.1 MPa or more, and more preferably 1 The storage modulus is preferably less than 2000 MPa, and more preferably less than 2000 MPa. Less than 1500 MPa is more preferable, less than 1000 MPa is even more preferable, and less than 500 MPa is even more preferable. More preferably, it is less than a, even more preferably less than 300 MPa, and even more preferably less than 100 MPa. is more preferred, and less than 50 MPa is even more preferred. By setting the storage modulus to less than the above upper limit, the flexibility of the obtained cured sheet 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.

[0051] The storage modulus was measured by molding the thermoplastic resin (A) into a sheet having a thickness of 300 μm. This is a value obtained by measuring the dynamic viscoelasticity using a viscoelasticity spectrometer.

[0052] The density of thermoplastic resin (A) is 0.98 g / cm 3 Preferably less than 0.95 g / cm 3 Less than 0.91 g / cm is more preferable. 3 On the other hand, the density is more preferably below the above range. The limit is not particularly limited, but is 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.

[0053] The density was measured by molding the thermoplastic resin (A) into a sheet having a thickness of 300 μm to prepare a test piece. It can be measured in accordance with ASTM D792.

[0054] The dielectric loss tangent of the thermoplastic resin (A) is preferably less than 0.002 at 10 GHz, and more preferably 0.002. It is more preferably less than 0.0015, and even more preferably less than 0.001. It is not fixed and can be 0 or more. The smaller the dielectric loss tangent, the smaller the dielectric loss. When this is done, the transmission efficiency and speed of electrical signals can be increased.

[0055] The above dielectric loss tangent was measured by molding the thermoplastic resin (A) into a sheet with a thickness of 300 μm and using it as a test piece. The measurements were made in accordance with JIS C2565:1992 at a temperature of 23°C and a frequency of 10 GHz. This is the value obtained by determining

[0056] 2. Alicyclic polyfunctional (meth)acrylate compound (B) The alicyclic polyfunctional (meth)acrylate compound (B) in the present resin composition is represented by the following general formula: (I) which has an alicyclic skeleton in the molecule and has two or more (meth)acryloyloxy groups The resin composition is a compound having an alicyclic polyfunctional (meth)acrylate compound (B By including alicyclic polyfunctional (meth) groups, low dielectric properties and excellent heat resistance can be obtained. p) The acrylate compound (B) may be either bifunctional or trifunctional or higher. These can be used alone or in combination of two or more.

[0057] [ka]

[0058] (In the formula, R 1 represents a hydrogen atom or a methyl group, and R 2 represents a hydroxyl group or a monovalent organic group, X represents an alicyclic hydrocarbon group. 2 When R is a monovalent organic group, two or more R 2 But each other may be bonded to form a fused ring containing ring X. l represents an integer of 1 or 2, and m represents an integer of 2 to 1. 0, and n represents an integer of 0 to 10. However, when the number of carbon atoms constituting ring X is If m+n, then 2x≧m+n.)

[0059] In the above general formula (I), m CH2=CR 1 COO-(CH2) l -Group( Hereinafter, this may be referred to as a "(meth)acryloyloxy(methyl / ethyl) group." 1 may be the same or different. l -As A methylene group (l=1) and an ethylene group (l=2) may be mixed, and either one In addition, when n is 2 or more, n R 2 Regarding They may be the same or different.

[0060] In the above general formula (I), CH2=CR 1 COO-R 1 If is a hydrogen atom, acryloyl It becomes an oxy group, R 1 If the methyl group is used, it becomes a methacryloyloxy group. Alternatively, these groups may be mixed in one molecule.

[0061] In the above general formula (I), R 2 is a hydroxyl group or a monovalent organic group, preferably a monovalent organic represents a group, and R 2 is directly single-bonded to a carbon atom constituting the alicyclic hydrocarbon group of X However, R 2 When R is a monovalent organic group, two or more R 2 are bonded to each other to form a condensed ring containing ring X. A ring may be formed.

[0062] R 2 The monovalent organic group in the formula (I) is preferably a monovalent organic group having 1 to 25 carbon atoms, for example, For example, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, acyloxy groups, and allo The number of carbon atoms in the alkoxy group or alkyl group is preferably 1 to 24, more preferably The number of carbon atoms in the acyloxy group and alkoxycarbonyl group is 2 to 12. It is preferably 25, more preferably 2 to 13. The number of carbon atoms in the silyl group is preferably 6 to 24, more preferably 6 to 12. The number of carbon atoms in the aroyloxy group or aryloxycarbonyl group is preferably 7 to 25. It is preferable that the number of carbon atoms is 1 or more, and more preferably 7 to 13. R 2 is a monovalent organic group, and two or more R 2 are bonded to each other to form a fused ring containing ring X. In this case, R is 2 or more. 2 The number of ring members formed by the ring X is equal to or less than that of the ring X. Preferably, the ring is a 6-membered ring including two or three adjacent carbon atoms on ring X. 10-24 membered rings and the like.

[0063] The monovalent organic group may have a substituent, and the substituent may be, for example, a fluorine atom. Examples of the alkyl group include a hydrogen atom, a chlorine atom, an alkyl group, an aryl group, an alkoxy group, and an aryloxy group. When a monovalent organic group has a substituent, the monovalent organic group includes the substituent. The total number of carbon atoms is preferably 1 to 25, and each group preferably has the above number of carbon atoms.

[0064] In the above general formula (I), X represents an alicyclic hydrocarbon group. The number of carbon atoms forming the alicyclic structure of X is not particularly limited, but from the viewpoint of heat resistance and solubility, The ring is preferably a 9- to 40-membered ring, more preferably a 9- to 20-membered ring, and particularly preferably a 9- to 16-membered ring. is more preferred, a 9- to 12-membered ring is particularly preferred, and a 10- to 12-membered ring is most preferred. The hydrocarbons of formula (I) may have a substituent. The structure of the alicyclic hydrocarbon group of X may be a monocyclic structure or a multicyclic structure. The alicyclic hydrocarbon group of X may have a monocyclic structure, but preferably has a monocyclic structure. This is preferable in terms of the development of low dielectric properties.

[0065] Examples of the monocyclic structure include cyclononane, cyclodecane, cycloundecane, and cyclopentane. Rhododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexene Sadecane, cycloheptadecane, cyclooctadecane, cyclononadecane, cycloicosapentaenoic acid Cyclohexanone, cyclohexanone, cyclodocosane, cyclotricosane, cyclotetracosane, Clopentacosane, cyclohexacosane, cycloheptacosane, cyclooctacosane, Chrononacosane, cyclotriacontane, cyclohentriacontane, cyclodotriacontane cyclopentatriacontane, cyclotritriacontane, cyclotetratriacontane, cyclopentatriacontane contane, cyclohexatriacontane, cyclotetracontane, and the like.

[0066] Among these, cyclononane, cyclodecane, cycloundecane, cyclododecane, Cyclotetradecane, cyclopentadecane, cyclohexadecane, cyclooctadecane, Cycloicosane is preferred. Cyclononane, cyclodecane, Cyclododecane, cyclotetradecane, cyclopentadecane, and cyclohexadecane More preferred are cyclononane, cyclodecane, and cyclododecane. are cyclodecane and cyclododecane.

[0067] In the above general formula (I), m is an integer of 2 to 10. For example, when m=2, The alicyclic polyfunctional (meth)acrylate compound is a di(meth)acrylate, and m=3 In this case, the alicyclic polyfunctional (meth)acrylate compound of the present invention becomes a tri(meth)acrylate. m is preferably 2 to 8, more preferably 2 to 6, and further preferably 3 to 8. It is 6.

[0068] In addition, the number of carbon atoms constituting the ring portion of X in the above general formula (I) is a (=9 to 40). In this case, the number of carbon atoms in the alicyclic skeleton is a and the number of (meth)acryloyloxy (methyl / ethyl) groups is The value m / a obtained by dividing the number m by the number m is preferably 1 / 4 or less, and curability and hydrophobicity (low moisture absorption) are important. In view of both excellent properties and durability, the ratio is preferably 1 / 12 to 1 / 4, and more preferably 1 / 6 to 1 / 4, more preferably 1 / 4. In addition, (meth)acryloyloxy (methyl / ethyl) It is preferred that only one ) group is bonded to each carbon atom constituting the ring portion of X.

[0069] In the above general formula (I), n is an integer of 0 to 10, preferably an integer of 0 to 8. n is preferably 0 to 7, and more preferably 0 to 3. When the compound is prepared by a manufacturing method that uses a raw material or intermediate, the compound has multiple functional groups. In the functional group, or the organic group converted by the reaction of the functional group, or the organic group derived from the raw material It is preferable that R represents the remaining number of organic groups. 2 The type and number n of the alicyclic polycyclic The performance of the (meth)acrylate compound should be appropriately determined according to the intended use and other factors. For example, if you want to improve weather resistance, 2 as an alkyl group or an alkoxy group When flame retardancy, low dielectric properties, and adhesion to fluororesin substrates are desired, simply introduce In order to achieve this, a fluoroalkyl group or a fluoroalkoxy group may be introduced. If it is desired to improve adhesion, a functional group having a high affinity with the resin may be introduced.

[0070] In the alicyclic polyfunctional (meth)acrylate compound of the present invention, when n=0, CH2=CR 1 m groups represented by COO- are attached to the carbon atoms constituting the alicyclic hydrocarbon group of X, and m groups are attached to the carbon atoms constituting the alicyclic hydrocarbon group of X. is bonded via an ethylene group, and when n is 1 to 10, CH2=CR 1 COO m (meth)acryloyloxy groups represented by - each constitute an alicyclic hydrocarbon group of X and R 2 n pieces of Each of these has a structure in which it is single-bonded to a carbon atom constituting the alicyclic hydrocarbon group of X. Two or more (meth)acryloyloxy (methyl / ethyl) groups may be present in the alicyclic hydrocarbon of X. Preferably, one bond is bonded to each carbon atom constituting the group, and R 2 There are multiple In case of multiple R 2 is 1 or 2 per carbon atom constituting the alicyclic hydrocarbon group of X The two will be combined. Also, (meth)acryloyloxy (methyl / ethyl) groups and R 2 The alicyclic carbonization of X The hydrogen atoms may be bonded to the same carbon atom that constitutes the hydrogen group, or to different carbon atoms. In a preferred embodiment, 1 carbon atom constituting the alicyclic hydrocarbon group of X is one (meth)acryloyloxy(methyl / ethyl) group or one R 2 A form in which It is an attitude.

[0071] In addition, the (meth)acryloyloxy (methyl / ethyl) in the alicyclic hydrocarbon group of X (R) group and R 2 When prepared by a preferred method, the bonding position of It is preferable that the position of the functional group in the intermediate alicyclic compound having multiple functional groups is the position of the functional group. stomach.

[0072] The mass average molecular weight (Mw) of the alicyclic polyfunctional (meth)acrylate compound (B) is 100 Preferably, 200 or more is more preferred, 220 or more is even more preferred, and 250 or more is even more preferred. The weight average molecular weight (Mw) is preferably 5,000 or less, and more preferably 4 ,000 or less is more preferable, 3,000 or less is even more preferable, and 1,000 or less is particularly preferable. preferable. The mass average molecular weight (Mw) of the alicyclic polyfunctional (meth)acrylate compound (B) is within the above range. By being within the range of 1000 ppm, the decomposition of the alicyclic polyfunctional (meth)acrylate compound (B) during curing is prevented. The thermoplastic resin (A) and the alicyclic polyfunctional (meth)acrylate compound (B) are ) molecular chains become easily entangled with each other, which makes it easier to increase the cross-linking density. The heat resistance and dimensional stability of the cured sheet are improved. In addition, if the crosslinking agent is not partially crosslinked or polymerized, it is called "alicyclic polyfunctional (meth)acrylate." The mass average molecular weight (Mw) of the acrylate compound (B) is an alicyclic polyfunctional (meth)acrylate It means the molecular weight of the compound used as compound (B).

[0073] Examples of bifunctional alicyclic polyfunctional (meth)acrylate compounds include cyclononanedimethyldiacrylate. (Meth)acrylate, Cyclodecane dimethyl di(meth)acrylate, Cycloundeca cyclododecane dimethyl di(meth)acrylate, cyclododecane dimethyl di(meth)acrylate, Cyclotridecane dimethyl di(meth)acrylate, Cyclotetradecane dimethyl di(meth)acrylate meth)acrylate, cyclopentadecane dimethyl di(meth)acrylate, cyclohexa Decane dimethyl di(meth)acrylate, cycloheptadecane dimethyl di(meth)acrylate acrylate, cyclooctadecane dimethyl di(meth)acrylate, cyclononadecanedimethic Dimethyl di(meth)acrylate, cycloicosane dimethyl di(meth)acrylate, cyclohe Cyclodocosan dimethyl di(meth)acrylate, cyclodocosane dimethyl di(meth)acrylate acrylate, cyclotricosane dimethyl di(meth)acrylate, cyclotetracosane dimethyl Dimethyl di(meth)acrylate, Cyclopentacosane dimethyl di(meth)acrylate, Cyclopentacosane Cycloheptacosane dimethyl di(meth)acrylate, Cycloheptacosane dimethyl di(meth)acrylate ) acrylate, cyclooctacosane dimethyl di(meth)acrylate, cyclononacosa Cyclotriacontane dimethyl di(meth)acrylate, cyclotriacontane dimethyl di(meth)acrylate acrylate, cyclohentriacontane dimethyl di(meth)acrylate, cyclodotriacontane Tanethyl di(meth)acrylate, cyclotritriacontane dimethyl di(meth)acrylate Acrylate, cyclotetratriacontane dimethyl di(meth)acrylate, cyclopentane Triacontane dimethyl di(meth)acrylate, cyclohexatriacontane dimethyl dimethyl di(meth)acrylate, cyclotetracontane dimethyl di(meth)acrylate, etc. Examples include:

[0074] As the trifunctional or more alicyclic polyfunctional (meth)acrylate compound, cyclononanetrimethyl Trimethyl tri(meth)acrylate, cyclodecane trimethyl tri(meth)acrylate, Chlorodecane trimethyl tri(meth)acrylate, cyclododecane trimethyl tri( meth)acrylate, cyclotridecane trimethyl tri(meth)acrylate, cyclotetradecane Toradecan trimethyl tri(meth)acrylate, cyclopentadecane trimethyl tri( meth)acrylate, cyclohexadecane trimethyl tri(meth)acrylate, cyclo Heptadecane trimethyl tri(meth)acrylate, cyclooctadecane trimethyl tri (Meth)acrylate, cyclononadecane trimethyl tri(meth)acrylate, cyclo Eicosane trimethyl tri(meth)acrylate, cyclohenicosane trimethyl tri(meth)acrylate meth)acrylate, cyclodocosane trimethyltri(meth)acrylate, cyclotricho Trimethyl tri(meth)acrylate, cyclotetracosane trimethyl tri(meth)acrylate Acrylate, Cyclopentacosane Trimethyltri(meth)acrylate, Cyclohexa Cosane trimethyl tri(meth)acrylate, cycloheptacosane trimethyl tri(meth)acrylate ) acrylate, cyclooctacosane trimethyl tri(meth)acrylate, cyclonona Cosane trimethyl tri(meth)acrylate, cyclotriacontane trimethyl tri(meth)acrylate p) acrylates.

[0075] As the alicyclic polyfunctional (meth)acrylate compound having 4 or more functional groups, cyclododecanethate tetramethyl tetra(meth)acrylate, cyclotridecane tetramethyl tetra(meth)acrylate Acrylate, cyclotetramethyltetra(meth)acrylate, cyclopentadecantetrate Tetramethyl tetra(meth)acrylate, cyclohexadecane tetramethyl tetra(meth)acrylate Acrylate, cycloheptadecane tetramethyl tetra(meth)acrylate, cyclooctadecane octadecane tetramethyl tetra(meth)acrylate, cyclononadecane tetramethyl tetra tetra(meth)acrylate, cycloicosane tetramethyl tetra(meth)acrylate, Cyclohexamethyltetra(meth)acrylate, Cyclodocosane tetramethyl acrylate Tetramethyltetra(meth)acrylate, Cyclotricosane tetramethyl tetra(meth)acrylate Acrylate, cyclotetracosane tetramethyl tetra(meth)acrylate, cyclopentaerythritol Cyclohexacosane tetramethyl tetra(meth)acrylate, Cyclohexacosane tetramethyl Tetra(meth)acrylate, Cycloheptacosane tetramethyl tetra(meth)acrylate acrylate, cyclooctacosane tetramethyl tetra(meth)acrylate, cyclononacosane Tetramethyl tetra(meth)acrylate, cyclotriacontane tetramethyl tetra( meth)acrylate, cyclohentriacontane tetramethyl tetra(meth)acrylate tetramethyl tetra(meth)acrylate, cyclodotriacontane tetramethyl tetra(meth)acrylate, cyclotrimethyl Acontane tetramethyl tetra(meth)acrylate, cyclotetratriacontane Tetramethyl tetra(meth)acrylate, Cyclopentriacontane tetramethyl tetra (Meth)acrylate, Cyclohexatriacontane tetramethyl tetra(meth)acrylate acrylate, cycloheptatriacontane tetramethyl tetra(meth)acrylate, cyclo Octatriacontane tetramethyl tetra(meth)acrylate, cyclononatriacontane Tantalum tetramethyl tetra(meth)acrylate, cyclotetracontane tetramethyl tetra (meth)acrylate, etc.

[0076] As an alicyclic polyfunctional (meth)acrylate compound having five or more functional groups, cyclopentadecane Pentamethyl penta(meth)acrylate, cyclohexadecane pentamethyl penta(meth)acrylate meth)acrylate, cycloheptadecane pentamethyl penta(meth)acrylate, cyclo Cyclononadecane pentamethyl penta(meth)acrylate, Cyclononadecane pentamethyl Cyclohexyl penta(meth)acrylate, cyclohexyl pentamethyl penta(meth)acrylate , cyclohexyl benzoate pentamethyl penta(meth)acrylate, cyclohexyl benzoate pentamethyl penta(meth)acrylate Trimethyl penta(meth)acrylate, cyclotricosane pentamethyl penta(meth)acrylate Acrylate, cyclotetracosane pentamethyl penta(meth)acrylate, cyclopenta Cyclohexacosane pentamethyl penta(meth)acrylate, cyclohexacosane pentamethyl penta(meth)acrylate Penta(meth)acrylate, Cycloheptacosane Pentamethyl Penta(meth)acrylate , cyclooctacosan pentamethyl penta(meth)acrylate, cyclononacosane pentamethyl penta(meth)acrylate Pentamethyl penta(meth)acrylate, cyclotriacontane pentamethyl penta(meth)acrylate meth)acrylate, cyclohentriacontane pentamethyl penta(meth)acrylate , cyclodotriacontane pentamethyl penta(meth)acrylate, cyclotritria Contane pentamethyl penta(meth)acrylate, cyclotetratriacontane penta Methyl penta(meth)acrylate, cyclopentatriacontane pentamethyl penta( meth)acrylate, cyclohexatriacontane pentamethyl penta(meth)acrylate acrylate, cycloheptatriacontane pentamethyl penta(meth)acrylate, cyclooctyl Triacontane pentamethyl penta(meth)acrylate, cyclononatriacontane Pentamethyl penta(meth)acrylate, cyclotetracontane pentamethyl penta (meth)acrylates, and the like.

[0077] As an alicyclic polyfunctional (meth)acrylate compound having six or more functional groups, cyclooctadecane Hexamethylhexa(meth)acrylate, Cyclononadecane hexamethylhexa(meth)acrylate ) acrylate, cycloicosane hexamethyl hexa(meth)acrylate, cyclohen Eicosane hexamethyl hexa(meth)acrylate, cyclodocosane hexamethyl hexa (Meth)acrylate, cyclotricosane hexamethyl hexa(meth)acrylate, Chlotetracosane hexamethyl hexa(meth)acrylate, Cyclopentacosane hexa Methyl hexa(meth)acrylate, cyclohexacosane hexamethyl hexa(meth)acrylate Acrylate, cycloheptacosane hexamethyl hexa(meth)acrylate, cyclooctadecanoate Cyclonacosan hexamethyl hexa(meth)acrylate, Cyclononacosan hexamethyl hexa Hexa(meth)acrylate, cyclotriacontane hexamethylhexa(meth)acrylate , cyclohentriacontane hexamethylhexa(meth)acrylate, cyclodotri Acontane hexamethyl hexa(meth)acrylate, cyclotritriacontane hexa Methylhexa(meth)acrylate, cyclotetratriacontane hexamethylhexa( meth)acrylate, cyclopentatriacontane hexamethylhexa(meth)acrylate acrylate, cyclohexatriacontane hexamethylhexa(meth)acrylate, cyclohexamethyl Putatriacontane hexamethylhexa(meth)acrylate, cyclooctatriacontane Tanhexamethyl hexa(meth)acrylate, cyclononatriacontane hexamethyl Hexa(meth)acrylate, cyclotetracontane hexamethyl hexa(meth)acrylate Rates, etc.

[0078] As an alicyclic polyfunctional (meth)acrylate compound with 7 or more functional groups, cyclohenicosane Heptamethylhepta(meth)acrylate, Cyclodocosan heptamethylhepta(meth)acrylate Acrylate, Cyclotricosane Heptamethylhepta(meth)acrylate, Cycloteto Lacosane heptamethyl hepta(meth)acrylate, cyclopentacosane heptamethyl hepta(meth)acrylate Hepta(meth)acrylate, Cyclohexacosane Heptamethylhepta(meth)acrylate , cycloheptacosane heptamethylhepta(meth)acrylate, cyclooctacosane Heptamethylhepta(meth)acrylate, cyclononacosan heptamethylhepta(meth)acrylate ) acrylate, cyclotriacontane heptamethylhepta(meth)acrylate, cyclo Hexantriacontane heptamethylhepta(meth)acrylate, Cyclodotriacontane Heptamethylhepta(meth)acrylate, cyclotritriacontane heptamethylhepta Hepta(meth)acrylate, Cyclotetratriacontane Heptamethylhepta(meth)acrylate Acrylate, cyclopentatriacontane heptamethylhepta(meth)acrylate, Cyclohexatriacontane heptamethylhepta(meth)acrylate, cycloheptatri Acontanheptamethylhepta(meth)acrylate, cyclooctatriacontanhepta methylhepta(meth)acrylate, cyclononatriacontane heptamethylhepta( meth)acrylate, cyclotetracontane heptamethylhepta(meth)acrylate, etc.

[0079] As an alicyclic polyfunctional (meth)acrylate compound having 8 or more functional groups, cyclotetracosane Octamethyl octa(meth)acrylate, cyclopentacosane octamethyl octa(meth)acrylate octa(meth)acrylate, cyclohexacosane octamethyl octa(meth)acrylate, cyclohexacosane octamethyl octa(meth)acrylate Rheptacosane octamethyl octa(meth)acrylate, Cyclononacosan octamethy Cycloocta(meth)acrylate, cyclooctacosan octamethylocta(meth)acrylate acrylate, cyclotriacontane octamethylocta(meth)acrylate, cyclophent Triacontane octamethyl octa(meth)acrylate, cyclodotriacontane octa Methyl octa(meth)acrylate, cyclotritriacontane octamethyl octa(meth)acrylate octa(meth)acrylate, cyclotetratriacontane octamethylocta(meth)acrylate , cyclopentatriacontane octamethylocta(meth)acrylate, cyclohexyl Satriacontane octamethylocta(meth)acrylate, cycloheptatriacontane Cyclooctamethylocta(meth)acrylate, Cyclooctatriacontane octamethyl Octa(meth)acrylate, Cyclononatriacontane Octamethylocta(meth)acrylate acrylate, cyclotetracontane octamethylocta(meth)acrylate, etc. can be done.

[0080] Among the above, from the viewpoint of imparting heat resistance, the above-mentioned bifunctional, trifunctional and tetrafunctional alicyclic At least one compound selected from the group consisting of polyfunctional (meth)acrylate compounds of the formula Furthermore, from the viewpoint of easy availability of the compound and excellent reactivity, cyclononanedimethicone is preferred. Tir di(meth)acrylate, cyclodecane dimethyl di(meth)acrylate, cyclodecane Decane dimethyl di(meth)acrylate, cyclododecane trimethyl tri(meth)acrylate acrylate, cyclopentadecane trimethyl tri(meth)acrylate, cyclooctadecane Trimethyl tri(meth)acrylate, cycloicosane pentamethyl penta(meth)acrylate Related is preferred.

[0081] The content of the alicyclic polyfunctional (meth)acrylate compound (B) in the resin composition is The content is preferably 0.01 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the thermoplastic resin (A). The amount is preferably 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 preferable that the amount is 0.5 parts by mass or more and 25 parts by mass or less, and particularly preferable that the amount is 0.5 parts by mass or more and 25 parts by mass or less. When the content of the alicyclic polyfunctional (meth)acrylate compound (B) is within the above range, the thermoplastic resin composition can be easily obtained. It is easy to increase the crosslink density artificially without deteriorating the low dielectric properties of the plastic resin (A). Therefore, the resulting cured sheet has good dielectric properties and heat resistance.

[0082] The thermoplastic resin (A) and the alicyclic polyfunctional (meth)acrylate compound (B) are contained in the thermoplastic resin (A). The sum of the contents is preferably 30% by mass or more relative to the total mass of the resin composition, and 50% by mass or more. It is more preferable that the content is 70% by mass or more, and even more preferable that the content is 70% by mass or more. The sum of the contents of the plastic resin (A) and the alicyclic polyfunctional (meth)acrylate compound (B) By ensuring that the above range, a cured product having excellent adhesiveness and a low dielectric tangent can be obtained. The upper limit of the sum of the above contents is not particularly limited, but from the viewpoint of improving adhesiveness, It is preferably 98% by mass or less, more preferably 97% by mass or less, and even more preferably 96% by mass or less. Desirable.

[0083] 3. Radical polymerizable compound (C) The radical polymerizable compound (C) is the above-mentioned alicyclic polyfunctional (meth)acrylate compound ( It may contain a compound having two or more ethylenically unsaturated bonds in the molecule other than B). By including the radical polymerizable compound (C), the crosslink density can be easily increased. This is expected to have the effect of further improving the heat resistance of the resulting cured sheet. (C) may be either bifunctional or trifunctional or higher. The radical polymerizable compound (C) does not include an alicyclic polyfunctional (meth)acrylate compound. .

[0084] 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, and ethoxylated 2- Difunctional aliphatic (meth)acrylates such as methyl-1,3-propanediol di(meth)acrylate Acrylate compounds; ethoxylated hydrogenated bisphenol A di(meth)acrylate, propoxylated Hydrogenated bisphenol A di(meth)acrylate, ethoxylated propoxylated hydrogenated bisphenol Bisphenol A di(meth)acrylate, ethoxylated hydrogenated bisphenol F di(meth)acrylate Bifunctional alicyclic (meth)acrylate compounds such as acrylate; ethoxylated bisphenol A di( meth)acrylate, propoxylated bisphenol A di(meth)acrylate, ethoxy Propoxylated Bisphenol A Di(meth)acrylate Ethoxylated Propoxylated Bisphenol Enol F di(meth)acrylate, ethoxylated fluorene di(meth)acrylate, Propoxylated fluorene-type di(meth)acrylates and ethoxylated propoxylated fluorenes Difunctional aromatic (meth)acrylate compounds such as olefin-type di(meth)acrylates; ethoxy Propoxylated isocyanuric acid di(meth)acrylate, propoxylated isocyanuric acid di(meth)acrylate difunctional copolymers such as acrylate, ethoxylated propoxylated isocyanuric acid di(meth)acrylate, etc. Examples thereof include acyclic (meth)acrylate compounds.

[0085] 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 acrylate tri(meth)acrylate, ethoxylated pentaerythritol Tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate acrylate, ethoxylated propoxylated pentaerythritol tetra(meth)acrylate, di Trimethylolpropane tetraacrylate and dipentaerythritol hexa(meth)acrylate ) acrylate and other polyfunctional aliphatic (meth)acrylate compounds; ethoxylated isocyanuric acid Acid tri(meth)acrylate, propoxylated isocyanuric acid tri(meth)acrylate, and polyfunctional heterocycles such as ethoxylated propoxylated isocyanuric acid tri(meth)acrylate (meth)acrylate compounds of the formula:

[0086] Among the above, when a styrene-based thermoplastic elastomer is used as the thermoplastic resin (A), In this case, bifunctional aromatic polyolefins are used from the viewpoint of showing appropriate compatibility with styrene-based thermoplastic elastomers. aromatic vinyl compounds, and trialkenyl isocyanurate compounds At least one of these is preferred, and among these, divinylbenzene or triallyl isocyanurate is particularly preferred. From the viewpoint of low dielectric properties, trialkenyl isocyanurate is even more preferred. Desirable.

[0087] 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. When the number of polar functional groups is small, the compatibility with the thermoplastic resin (A) is good, and the resulting The dielectric loss tangent of the cured product also becomes lower. 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.

[0088] 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 thermoplastic resin (A), the alicyclic polyfunctional (meth)acrylate compound (B) and the radical The molecular chains of the polymerizable compound (C) are easily entangled with each other, and the crosslink density is easily increased. 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.

[0089] When the resin composition contains the radical polymerizable compound (C), the content thereof is (A) is preferably 1 part by mass or more and 50 parts by mass or less, and more preferably 3 parts by mass or more and 40 parts by mass or less, per 100 parts by mass. It is more preferably 5 parts by mass or less, and even more preferably 5 parts by mass or more and 30 parts by mass or less. When the content of the radical polymerizable compound (C) is within the above range, the derivative of the thermoplastic resin (A) is It is easy to increase the cross-link density artificially without deteriorating the electrical properties, so the resulting sheet The cured product has good dielectric properties and heat resistance.

[0090] In addition, when the present resin composition contains a radical polymerizable compound (C), the thermoplastic resin (A) 1 00 parts by mass of an alicyclic polyfunctional (meth)acrylate compound (B) and radical polymerization The total content of the reactive compounds (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. The amount is more preferably at most 50 parts by mass, and even more preferably at least 5 parts by mass and at most 30 parts by mass. The composition contains an alicyclic polyfunctional (meth)acrylate compound (B) and a radical polymerizable compound (C). When the sum of the contents is within the above range, the dielectric properties of the thermoplastic resin (A) are not deteriorated, This makes it easier to increase the crosslink density artificially, improving the dielectric properties and heat resistance of the resulting cured sheet. It will be good.

[0091] 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.

[0092] The content of the organic peroxide (D) in the resin composition is 100 mass % of the thermoplastic resin (A). 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. More preferably, the amount is 0.1 part 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.

[0093] 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.

[0094] The content of the solvent (E) in the resin composition is determined based on the amount of the thermoplastic resin (A) from the viewpoint of film-forming properties. Preferably, the amount is 100 parts by mass or more and 500 parts by mass or less, and more preferably 200 parts by mass or more, per 100 parts by mass. More preferably, it is 400 parts by mass or less.

[0095] 6. Other Ingredients The resin composition may contain, as components other than those described above, a thermoplastic resin other than the thermoplastic resin (A), a crosslinking agent, a Crosslinking agent (alicyclic polyfunctional (meth)acrylate compound (B) and radical polymerizable compound (C) ), monofunctional vinyl compounds, ultraviolet absorbers, antistatic agents, antioxidants, coupling agents Agents, plasticizers, flame retardants, colorants, dispersants, emulsifiers, elasticity reducing agents, diluents, antifoaming agents, iontophoresis agents, It may also contain lapping agents, thickeners, leveling agents, inorganic particles, organic particles, etc.

[0096] Examples of the crosslinking agent include bismaleimide compounds, isocyanate compounds, epoxy compounds, and the like. Examples include silicon compounds.

[0097] 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% of the resin component of the present resin composition. The amount is preferably 1 part by mass or more and 200 parts by mass or less, more preferably 5 parts by mass or more and 150 parts by mass or less. The amount of inorganic particles or organic particles is more preferably 10 parts by mass or more and 100 parts by mass or less. When the content of organic particles is equal to or greater than the above lower limit, the dielectric properties of the cured sheet can be further reduced. In addition, the linear thermal expansion coefficient 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 from the surface of the adhesive layer is unlikely to occur. When this is the case, the formability of the cured sheet product is improved.

[0098] <Physical properties of the present resin composition> The present resin composition can have the following physical properties.

[0099] The resin composition has a relative dielectric constant of preferably 4 or less, more preferably 3 or less after curing. 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.

[0100] The curing temperature of the resin composition is set at a temperature at which the thermoplastic resin (A) does not flow and the alicyclic polyfunctional The temperature may be any temperature at which the crosslinking reaction of the (meth)acrylate compound (B) proceeds. The heating temperature is preferably 120 to 300°C, more preferably 140 to 250°C, and more preferably 150 to 220°C. °C is more preferred. The curing time of the present resin composition is not particularly limited, but is preferably 10 minutes to 2 hours.

[0101] <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.

[0102] 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.

[0103] The storage modulus (130°C) of the resin sheet after curing is preferably 0.01 MPa or more. It is preferable that the pressure is 0.1 MPa or more, and more preferable that the pressure is 1.0 MPa or more, and 1.2 MPa or more. When the storage modulus at 130°C is equal to or greater than the above lower limit, On the other hand, the upper limit of the storage modulus (130°C) is not particularly limited. However, it is preferably 100 MPa or less, and more preferably 50 MPa or less. The storage modulus was measured by heat pressing the resin sheet at 200°C and 2 MPa for 30 minutes. The cured product obtained by the curing was used as a test piece, and the dynamic viscoelasticity was measured. .

[0104] <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.

[0105] 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, electronic components can be continuously produced, 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.

[0106] <Method of manufacturing resin sheet> The method for producing the resin sheet will be described below. It is not limited to the law.

[0107] [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.

[0108] (1) Coating liquid preparation process In the coating liquid preparation process, a thermoplastic resin (A), an alicyclic polyfunctional (meth)acrylate compound (B), a radical polymerizable compound (C), an organic peroxide (D) if necessary, a solvent (E) and The coating liquid is obtained by stirring and uniformly mixing the above ingredients and other components. 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.

[0109] (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.

[0110] (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.

[0111] (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 alicyclic polyfunctional (meth)acrylate compound (B) is suppressed. By ensuring that the viscosity is equal to or greater than the lower limit, foaming of the resin sheet during curing can be suppressed, and the solvent can be effectively removed. This can be eliminated, improving 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.

[0112] 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.

[0113] [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.

[0114] In the film-forming process, a thermoplastic resin (A) and an alicyclic polyfunctional (meth)acrylate compound (B) are mixed. If necessary, the radical polymerizable compound (C), the organic peroxide (D) and other components may be mixed together. The mixture is kneaded in a screw extruder or a twin screw extruder, and the temperature is higher than the melting point of the thermoplastic resin (A) and the alicyclic polyfunctional The (meth)acrylate compound (B) is subjected to a temperature condition lower than the crosslinking temperature using an extruder or the like. The resin composition is extruded onto a mold film to form a film. The extrusion method of the resin composition is not particularly limited, but more preferably A specific example is T-die molding.

[0115] <Cured sheet> The sheet cured product according to one embodiment of the present invention (hereinafter also referred to as the "cured product") is a resin having the above-mentioned properties. It is made by hardening a grease sheet.

[0116] The curing temperature of the resin sheet is set at a temperature at which the thermoplastic resin (A) does not flow and the alicyclic polyfunctional ( The crosslinking reaction between the methacrylate compound (B) and the radical polymerizable compound (C) proceeds. Specifically, the temperature is preferably 120 to 300°C, and more preferably 140 to 250°C. A temperature range of 150°C to 220°C is more preferable. The curing time for the resin sheet is not particularly limited, but is preferably 10 minutes to 1 hour.

[0117] <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.

[0118] <Circuit board materials> 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.

[0119] 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.

[0120] 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 thermoplastic resin (A) does not flow and the alicyclic polyfunctional (meth)acrylate is (p) The temperature may be any temperature at which the crosslinking reaction of the acrylate compound (B) proceeds. The curing temperature of the 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]

[0121] 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.

[0122] <Raw materials> [Thermoplastic resin (A)] a-1: 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

[0123] [Alicyclic polyfunctional (meth)acrylate compound (B)] b-1: Cyclododecane trimethyl triacrylate, mass average molecular weight (Mw): 42 1 b-2: Cyclododecane trimethyl trimethacrylate, mass average molecular weight (Mw): 4 63 b-3: Tricyclodecane dimethanol dimethacrylate, mass average molecular weight (Mw): 332 b'-1:1,12-dodecanediol dimethacrylate, mass average molecular weight (Mw): 339 b'-2: 2-Methyl-1,8-octanediol dimethacrylate and 1,9-nonane Mixture of diol dimethacrylates, weight average molecular weight (Mw): 296

[0124] [Radical polymerizable compound (C)] c-1: Triallyl isocyanurate (TAIC: manufactured by Shinryo Corporation), mass average molecular weight (Mw ):250

[0125] [Organic peroxide (D)] d-1: α,α-di(tert-butylperoxyisopropyl)benzene (NOF) (manufactured by the company, "Perbutyl P")

[0126] [Solvent (E)] e-1: Toluene (content: >99.0% by mass)

[0127] <Evaluation> The resulting resin composition was evaluated as follows, and the results are shown in Table 1.

[0128] (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 (Anritsu Corporation) in TE mode. The measurement frequency was set to 10 GHz.

[0129] (2) Storage modulus The dynamic viscoelasticity of the cured sheet was measured using a viscoelasticity spectrometer DVA-200 (IT Measurements were performed under the following conditions using a measuring instrument manufactured by Keisoku Seigyo Co., Ltd. The results showed that the storage temperature at 130°C The elastic modulus value was taken as the storage modulus of each sheet cured product. [Measurement conditions] Vibration frequency: 10Hz Measurement mode: Tensile Heating rate: 3°C / min Measurement temperature: -100℃~130℃ Distortion: 0.03%

[0130] 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 resin composition was applied to a release film (three-layer film) with a thickness of 50 μm that had been treated for release. The resin was spread in a sheet form on the release-treated surface of a PET film (manufactured by Ryo Chemical Co., Ltd.) to obtain a resin sheet. The thickness of the resin sheet was adjusted so that the thickness of the sheet after hardening was about 100 μm. was created. 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 2 MPa. The resin sheet was completely cured, and the release films on both sides were peeled off to obtain a cured sheet. The dielectric properties and storage modulus of the cured sheet were evaluated.

[0131] <Examples 2 to 5, Comparative Examples 1 and 2> 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 dielectric properties and storage modulus of the obtained cured sheets were evaluated.

[0132] [Table 1]

[0133] From Examples 1 to 5, it can be seen that the thermoplastic resin (A), the alicyclic polyfunctional (meth)acrylate compound ( By including B), it is possible to maintain low dielectric properties while achieving a high storage modulus and heat resistance. A cured sheet with excellent performance was obtained. Instead of the alicyclic polyfunctional (meth)acrylate compound (B), In Comparative Examples 1 and 2, which used a polyfunctional (meth)acrylate compound, the low dielectric properties were significantly deteriorated. In addition, the heat resistance was poor. In the above examples, the thermoplastic resin (A) was not limited to a styrene-based thermoplastic elastomer. Although there is no example using a thermoplastic resin (A), an alicyclic polyfunctional (meth)acrylate compound ( B) The molecular chains of the polymer are intertwined, which improves heat resistance while maintaining low dielectric properties. Considering the mechanism, it is expected that the same effect as that of styrene-based thermoplastic elastomers can be expected. can.

Claims

1. Styrene-based thermoplastic elastomer, olefin-based thermoplastic elastomer, ethylene-based polymer and at least one heat-resistant polymer selected from the group consisting of a copolymer of olefin and a cyclic polyolefin resin copolymer. A plastic resin (A) and an alicyclic polyfunctional (meth)acrylate represented by the following general formula (I): A resin composition containing a compound (B). 【Chemical 1】 (In the formula, R １ represents a hydrogen atom or a methyl group, R ２ represents a hydroxyl group or a monovalent organic group, X represents an alicyclic hydrocarbon group. ２ is a monovalent organic group, two or more R ２ But each other may be bonded to form a fused ring containing ring X. l represents an integer of 1 or 2, and m represents an integer of 2 to 1. 0, and n is an integer from 0 to 10. However, the number of carbon atoms constituting ring X is If m+n, then 2x≧m+n. thermoplastic resin

2. The thermoplastic resin (A) according to claim 1, wherein the thermoplastic resin (A) contains a styrene-based thermoplastic elastomer. The resin composition described above.

3. 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 2, wherein

4. The mass average molecular weight (Mw) of the thermoplastic resin (A) is 30,000 or more.

2. The resin composition according to claim 1.

5. The alicyclic polyfunctional (meth)acrylate relative to 100 parts by mass of the thermoplastic resin (A). The composition according to claim 1, wherein the content of the compound (B) is 0.01 parts by mass or more and 50 parts by mass or less. Resin composition.

6. The mass average molecular weight (Mw) of the alicyclic polyfunctional (meth)acrylate compound (B) is 10 The resin composition according to claim 1, wherein the molecular weight is 0 or more and 5,000 or less.

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

8. The alicyclic polyfunctional (meth)acrylate relative to 100 parts by mass of the thermoplastic resin (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 and 10 parts by mass or less; The resin composition according to claim 7, wherein the content of the hydroxybenzoates is 0% by mass or less.

9. 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 0.003 or less. Finished product.

10. A resin sheet comprising the resin composition according to any one of claims 1 to 9.

11. A laminate comprising the resin sheet according to claim 10 and a release film on one or both surfaces thereof. 。

12. A cured sheet obtained by curing the resin sheet according to claim 10.

13. A circuit board material obtained by laminating an insulating layer made of the resin sheet according to claim 10 and a conductor. Fee.

Images