Thermosetting resin composition and application thereof

Abstract

The present invention provides a thermosetting resin composition and its application. The thermosetting resin composition can obtain a cured product having excellent relative dielectric constant and heat resistance and useful for high-frequency applications. It includes: (1) a thermosetting resin composition comprising the following (A), (C) and (D); (2) a thermosetting resin composition comprising the following (A) and (B). Wherein: (A) is a cyclopentadiene compound and / or its oligomer represented by the following formula (1); #imgabs0# (in formula (1), R represents a group selected from alkyl, alkenyl and aryl groups, n is an integer of 1 to 4, and x1 and x2 are independently 0, 1 or 2) (B) a cyclic imide compound; (C) a curing accelerator; and (D) an inorganic filler.

Description

Technical Field

[0001] The present invention relates to a thermosetting resin composition containing a cyclopentadiene compound and application thereof. Background Art

[0002] In recent years, with the advancement of miniaturization and higher performance in electronic devices, demands have been placed on miniaturized and higher-density wiring in multilayer printed wiring boards. Furthermore, next-generation products require materials that operate in high-frequency bands, and as a measure to reduce noise, transmission loss must be reduced. Consequently, insulating materials with excellent dielectric properties are required for the insulating layers of multilayer printed wiring boards.

[0003] As insulating materials used for multilayer printed wiring boards, epoxy resin compositions disclosed in Patent Documents 1 to 3 are known.

[0004] In this patent document 1, it is disclosed that an epoxy resin composition containing an epoxy resin, an active ester compound and a triazine novolac resin is effective for low dielectric loss tangent. In addition, in patent documents 2 and patent documents 3, it is disclosed that a resin composition using an epoxy resin and an active ester compound as essential components is a cured product with low dielectric loss tangent and can be used as an insulating material. However, these known epoxy resin compositions are epoxy resin compositions that cannot meet the requirements for high-frequency band applications.

[0005] On the other hand, Patent Document 4 discloses that a resin film composed of a bismaleimide resin having a long-chain alkyl group and a resin composition containing a curing agent, as a non-epoxy material, has excellent dielectric properties (low relative dielectric constant and low dielectric loss tangent). However, since the long-chain alkyl group in the bismaleimide resin has low heat resistance, there is a problem that the resin film itself also has low heat resistance.

[0006] Prior art literature

[0007] Patent Literature

[0008] [Patent Document 1]: Japanese Patent Application Laid-Open No. 2011-132507

[0009] [Patent Document 2]: Japanese Patent Application Laid-Open No. 2015-101626

[0010] [Patent Document 3]: Japanese Patent Application Laid-Open No. 2017-210527

[0011] [Patent Document 4]: International Publication No. 2016 / 114287 Summary of the Invention

[0012] Problems to be solved by the invention

[0013] An object of the present invention is to provide a thermosetting resin composition capable of producing a cured product having a high glass transition temperature, excellent dielectric properties and heat resistance, and low water absorption, and useful for high-frequency applications, as well as electronic components, thermosetting adhesives, adhesive films, prepregs, and multilayer printed wiring boards produced using the thermosetting resin composition.

[0014] Another object of the present invention is to provide a thermosetting resin composition capable of producing a cured product having excellent dielectric properties and heat resistance and useful for high-frequency applications, and to provide an encapsulating material for electronic components, a thermosetting adhesive, an adhesive film, a prepreg, and a multilayer printed wiring board produced using the thermosetting resin composition.

[0015] Solutions to the problem

[0016] To address the aforementioned issues, the present inventors have conducted extensive research and have discovered that the following thermosetting resin composition can achieve the aforementioned objectives, thereby completing the present invention. Specifically, the present invention provides the following thermosetting resin composition, as well as an encapsulating material for an electronic component, a thermosetting adhesive, an adhesive film, a prepreg, and a multilayer printed wiring board manufactured using the thermosetting resin composition.

[0017] <1>

[0018] A thermosetting resin composition comprising:

[0019] (A) a cyclopentadiene compound represented by the following formula (1) and / or an oligomer thereof,

[0020]

[0021] In formula (1), R represents a group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms, n is an integer of 1 to 4, and x1 and x2 are independently 0, 1, or 2. However, when R represents an alkyl group or an aryl group, x1 is 1 or 2, and 1≤x1+x2≤4;

[0022] (C) a curing accelerator; and

[0023] (D) Inorganic filling materials.

[0024] <2>

[0025] The thermosetting resin composition as described in <1>,

[0026] The oligomer of the compound represented by the formula (1) as the component (A) includes a dimer and / or trimer of the compound represented by the formula (1).

[0027] <3>

[0028] The thermosetting resin composition as described in <1> or <2>,

[0029] Among them, the oligomer of the compound represented by formula (1) as the component (A) has a dicyclopentadiene ring.

[0030] <4>

[0031] The thermosetting resin composition according to any one of <1> to <3>,

[0032] However, the ratio of the oligomer of the compound represented by formula (1) in the component (A) is 10 to 90% by mass.

[0033] <5>

[0034] The thermosetting resin composition according to any one of <1> to <4>,

[0035] The component (D) is surface-treated with a silane coupling agent having an amino group, a methacryloyl group, a vinyl group, or a styrene group.

[0036] <6>

[0037] The thermosetting resin composition according to any one of <1> to <5>,

[0038] The thermosetting resin composition further contains an adhesion promoter as the component (E), and the adhesion promoter has one or more epoxy groups in one molecule.

[0039] <7>

[0040] A thermosetting resin composition comprising:

[0041] (A) a cyclopentadiene compound represented by the following formula (1) and / or an oligomer thereof,

[0042]

[0043] In formula (1), R represents a group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms, n is an integer of 1 to 4, and x1 and x2 are independently 0, 1, or 2. However, when R represents an alkyl group or an aryl group, x1 is 1 or 2, and 1≤x1+x2≤4;

[0044] (B) a cyclic imide compound containing, in one molecule, at least one dimer acid skeleton, at least one linear alkylene group having 6 or more carbon atoms, and at least two unsaturated cyclic imide groups,

[0045] The amount of the component (B) is 5 to 95 parts by mass relative to 100 parts by mass of the total of the component (A) and the component (B).

[0046] <8>

[0047] The thermosetting resin composition as described in <7>,

[0048] The oligomer of the compound represented by the formula (1) as the component (A) includes a dimer and / or trimer of the compound represented by the formula (1).

[0049] <9>

[0050] The thermosetting resin composition as described in <7> or <8>,

[0051] Among them, the oligomer of the compound represented by formula (1) as the component (A) has a dicyclopentadiene ring.

[0052] <10>

[0053] The thermosetting resin composition according to any one of <7> to <9>,

[0054] However, the ratio of the oligomer of the compound represented by formula (1) in the component (A) is 10 to 90% by mass.

[0055] <11>

[0056] The thermosetting resin composition according to any one of <7> to <10>,

[0057] Among them, (B) the cyclic imide compound is represented by the following formula (2):

[0058]

[0059] In formula (2), A independently represents a tetravalent organic group containing an aromatic ring or an aliphatic ring, B is an alkylene group having a divalent aliphatic ring which may contain a heteroatom and having 6 to 18 carbon atoms, Q independently represents a straight-chain alkylene group having 6 or more carbon atoms, R independently represents a straight-chain or branched alkyl group having 6 or more carbon atoms, n represents a number from 1 to 10, and m represents a number from 0 to 10.

[0060] <12>

[0061] The thermosetting resin composition as described in <11>,

[0062] The organic group represented by A in formula (2) is any one of the following structural formulas:

[0063]

[0064] The bonding end of the non-bonded substituent in the above structural formula is bonded to the carbonyl carbon forming the cyclic imide structure in formula (2).

[0065] <13>

[0066] The thermosetting resin composition according to any one of <7> to <12>,

[0067] The thermosetting resin composition further contains a curing accelerator as the component (C).

[0068] <14>

[0069] The thermosetting resin composition according to any one of <7> to <13>,

[0070] The thermosetting resin composition further contains an inorganic filler as the component (D).

[0071] <15>

[0072] The thermosetting resin composition as described in <14>,

[0073] The component (D) is surface-treated with a silane coupling agent having an amino group, a methacryloyl group, a vinyl group, or a styrene group.

[0074] <16>

[0075] The thermosetting resin composition according to any one of <7> to <15>,

[0076] The thermosetting resin composition further contains an adhesion promoter as the component (E), and the adhesion promoter has one or more epoxy groups in one molecule.

[0077] <17>

[0078] A packaging material for electronic components,

[0079] It is formed from the thermosetting resin composition described in any one of <1> to <16>.

[0080] <18>

[0081] The packaging material as described in <17>,

[0082] Wherein, the electronic component is a semiconductor device.

[0083] <19>

[0084] The packaging material as described in <17>,

[0085] Wherein, the electronic component is a coil component.

[0086] <20>

[0087] A thermosetting adhesive,

[0088] It is formed from the thermosetting resin composition described in any one of <1> to <16>.

[0089] <21>

[0090] An adhesive film,

[0091] However, the thermosetting resin composition according to any one of <1> to <16> is formed as a layer on a support film.

[0092] <22>

[0093] A prepreg,

[0094] The thermosetting resin composition according to any one of <1> to <16> is impregnated in a sheet-like fiber base material.

[0095] <23>

[0096] A multilayer printed wiring board,

[0097] The multilayer printed wiring board includes an insulating layer formed of a cured product of the thermosetting resin composition according to any one of <1> to <16>.

[0098] Effects of the Invention

[0099] The cured product of the thermosetting resin composition of the present invention has a high glass transition temperature and exhibits excellent dielectric properties, heat resistance, and low water absorption, making it useful for high-frequency applications. In particular, electronic component encapsulating materials, thermosetting adhesives, adhesive films, prepregs, and multilayer printed wiring boards produced using the thermosetting resin composition are useful for high-frequency applications.

[0100] In addition, the cured product of the thermosetting resin composition of the present invention has excellent dielectric properties and heat resistance and is therefore useful for high-frequency applications (e.g., electronic components, thermosetting adhesives, adhesive films, prepregs, and multilayer printed wiring boards). Furthermore, the cured product of the thermosetting resin composition also has excellent tracking resistance and is useful for power device applications (e.g., inverter motors for hybrid vehicles and electric vehicles). DETAILED DESCRIPTION

[0101] Hereinafter, the present invention will be described in further detail.

[0102] The composition of the present invention is a composition comprising (A) a cyclopentadiene compound and / or an oligomer thereof.

[0103] One embodiment of the composition of the present invention is a composition comprising components (A), (C), and (D) (hereinafter, the composition of this embodiment may be referred to as composition 1). In this embodiment, in addition to components (A), (C), and (D), component (E) may be further contained.

[0104] Another embodiment of the composition of the present invention is a composition comprising component (A) and component (B) (hereinafter, the composition of this embodiment may be referred to as composition 2). In this embodiment, in addition to components (A) and (B), component (C), component (D), and / or component (E) may be further contained.

[0105] Hereinafter, each component will be described.

[0106] [(A) Cyclopentadiene compound and / or its oligomer]

[0107] The component (A) contained in the thermosetting resin composition of the present invention is a cyclopentadiene compound represented by the following formula (1) and / or an oligomer containing a cyclopentadiene compound represented by the following formula (1) as a monomer.

[0108]

[0109] In formula (1), R represents a group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. n is an integer of 1 to 4, and x1 and x2 are independently 0, 1, or 2. However, when R represents an alkyl group or an aryl group, x1 is 1 or 2, and 1 ≤ x1 + x2 ≤ 4.

[0110] In the formula (1), n ​​is an integer of 1 to 4, preferably 1 to 2, and particularly preferably 1. x1 is 0, 1, or 2, preferably 0 or 1. x2 is 0, 1, or 2, preferably 1 or 2.

[0111] Furthermore, R represents a group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an n-hexyl group, an isohexyl group, a cyclopentyl group, and a cyclohexyl group.

[0112] Examples of the alkenyl group include vinyl, allyl, isopropenyl, butenyl, pentenyl, and hexenyl.

[0113] Furthermore, examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a benzyl group, a biphenyl group, and a naphthyl group.

[0114] Among them, R is preferably an alkenyl group, and particularly preferably a vinyl group and an allyl group.

[0115] When R represents an alkyl group or an aryl group, x1 is 1 or 2, preferably 1, and 1≤x1+x2≤4, preferably 1≤x1+x2≤2.

[0116] Since the cyclopentadiene ring of the compound represented by formula (1) is highly reactive, the compound represented by formula (1) is easily dimerized and / or trimerized by the Diels-Alder reaction to generate a dimer and / or trimer. It should be noted that the dimerization or trimerization reaction may be a reaction of cyclopentadiene compounds having the same structure or a reaction of cyclopentadiene compounds having different structures.

[0117] The component (A) preferably contains an oligomer of the compound represented by formula (1) in an amount of 10 to 90% by mass, more preferably 15 to 85% by mass.

[0118] Furthermore, the component (A) preferably contains 3 to 80% by mass, more preferably 5 to 70% by mass, of a dimer of the compound represented by formula (1).

[0119] The dimer ratio and oligomer ratio of the compound represented by formula (1) are calculated from the area ratio of the peaks measured by gel permeation chromatography (GPC).

[0120] Furthermore, the oligomer of the compound represented by formula (1) is preferably an oligomer having a dicyclopentadiene ring structure.

[0121] The cyclopentadiene ring of the compound of formula (1) is reacted to form a dicyclopentadiene ring. That is, since the Diels-Alder reaction between the cyclopentadiene rings in two molecules of the compound of formula (1) occurs more easily than the reaction between the cyclopentadiene ring and other carbon-carbon double bonds capable of undergoing the Diels-Alder reaction, it is believed that a large amount of the compound having the dicyclopentadiene ring is contained in the (A) component.

[0122] Furthermore, since the compound represented by the formula (1) has a reactive double bond other than the cyclopentadiene ring, the reactive double bonds react with each other and / or with the cyclopentadiene ring to generate oligomers.

[0123] The structure of the oligomer can be exemplified by the following formula.

[0124]

[0125] (In the formula, R, n, x1, and x2 are the same as above.)

[0126]

[0127] (In the formula, R, n, x1, and x2 are the same as above.)

[0128]

[0129] (In the formula, R, n, x1, and x2 are the same as above.)

[0130] The oligomer can be obtained by heating the compound represented by formula (1) at 50 to 200° C., preferably 60 to 180° C., more preferably 70 to 160° C., for 20 to 180 minutes, preferably 40 to 150 minutes, more preferably 60 to 120 minutes. The reaction is preferably carried out under vacuum.

[0131] The compound represented by formula (1) may be heated without a solvent, or in a high-boiling-point solvent such as toluene, xylene, or anisole, as needed.

[0132] In order to form 3% by mass or more of the dimer of the cyclopentadiene compound represented by formula (1) in component (A), it is preferred to heat the compound represented by formula (1) at 70 to 160° C. under vacuum conditions for 1 to 2 hours.

[0133] The weight average molecular weight (Mw) of the cyclopentadiene compound of component (A) is not particularly limited, including its properties at room temperature (25°C). However, the weight average molecular weight, as measured by gel permeation chromatography (GPC) and converted to polystyrene standards, is more preferably 10,000 or less, and particularly preferably 100 or more and 5,000 or less. If the molecular weight is 10,000 or less, there is no concern that the resulting composition will have excessively high viscosity and reduced fluidity, and its moldability for lamination molding, etc., will be improved. Furthermore, if the molecular weight is 10,000 or less, compatibility with the cyclic imide compound in the composition containing component (B) will be improved.

[0134] In addition, the molecular weight (Mw) mentioned in this specification refers to the weight average molecular weight measured by GPC under the following conditions using polystyrene as a standard substance.

[0135] [Measurement conditions]

[0136] Developing solvent: tetrahydrofuran

[0137] Flow rate: 0.35mL / min

[0138] Detector: RI

[0139] Column: TSK-GEL Super HZ type (manufactured by TOSOH CORPORATION)

[0140] SuperHZ4000(4.6mm ID×15cm×1)

[0141] SuperHZ3000(4.6mm ID×15cm×1)

[0142] SuperHZ2000(4.6mm ID×15cm×1)

[0143] Column temperature: 40°C

[0144] Sample injection volume: 5 μL (0.1 wt% THF solution)

[0145] The cyclopentadiene compound and / or its oligomer as the component (A) may be used alone or in combination of two or more.

[0146] [(B) Cyclic imide compound]

[0147] The (B) component used in the present invention is a cyclic imide compound, and it has at least one dimer acid skeleton, at least one straight-chain alkylene group with a carbon number of 6 or more, and at least two unsaturated cyclic imide groups in one molecule. (B) component can impart properties such as low dielectric properties, resistance to leakage current tracking, and low elasticity to the composition of the present invention. The cyclic imide compound of component (B) has a straight-chain alkylene group with a carbon number of 6 or more, and the cured product of the composition containing the cyclic imide compound not only has excellent dielectric properties, but also can reduce the content of phenyl groups and improve resistance to leakage current tracking. In addition, the cyclic imide compound of component (B) has a straight-chain alkylene group, so that the cured product of the composition containing the cyclic imide compound can be made low-elastic, and has the effect of reducing the stress on the semiconductor device caused by the cured product.

[0148] Among them, the cyclic imide compound as the component (B) is preferably a maleimide compound, and more preferably a maleimide compound represented by the following formula (2).

[0149]

[0150] In formula (2), A independently represents a tetravalent organic group containing an aromatic ring or an aliphatic ring. B is an alkylene group having 6 to 18 carbon atoms and having a divalent aliphatic ring which may contain a heteroatom. Q independently represents a linear alkylene group having 6 or more carbon atoms. R independently represents a linear or branched alkyl group having 6 or more carbon atoms. n represents a number from 1 to 10. m represents a number from 0 to 10.

[0151] In formula (2), Q is a linear alkylene group having 6 or more carbon atoms, preferably 6 or more and 20 or less carbon atoms, and more preferably 7 or more and 15 or less carbon atoms.

[0152] In formula (2), R is an alkyl group, which may be a linear or branched alkyl group. The number of carbon atoms in these alkyl groups is 6 or more, preferably 6 or more and 12 or less.

[0153] A in formula (2) represents a tetravalent organic group containing an aromatic ring or an aliphatic ring, and is particularly preferably any of the tetravalent organic groups represented by the following structural formulas.

[0154]

[0155] (The end bonded to the non-substituent group in the above structural formula is the end bonded to the carbonyl carbon forming the cyclic imide structure in formula (2).)

[0156] In formula (2), B is an alkylene group having 6 to 18 carbon atoms and having a divalent aliphatic ring which may contain a heteroatom, and the alkylene group preferably has 8 or more and 15 or less carbon atoms. B in formula (2) is preferably any of the alkylene groups having an aliphatic ring represented by the following structural formula.

[0157]

[0158] (The bonding end of the non-bonded substituent in the above structural formula is the bonding end to the nitrogen bonding end forming the cyclic imide structure in formula (2).)

[0159] In the formula (2), n is a number of 1 to 10, preferably a number of 2 to 7. In the formula (2), m is a number of 0 to 10, preferably a number of 0 to 7.

[0160] The weight-average molecular weight (Mw) of the cyclic imide compound of component (B) is not particularly limited, including its properties at room temperature (25°C). However, the weight-average molecular weight, as measured by gel permeation chromatography (GPC), is preferably 70,000 or less, and particularly preferably 500 or more and 50,000 or less, as measured in terms of polystyrene standards. When the weight-average molecular weight is 70,000 or less, there is no concern that the resulting composition will have excessively high viscosity and thus reduce fluidity. Furthermore, not only is moldability in lamination molding improved, but compatibility with component (A) is also improved.

[0161] As the cyclic imide compound of component (B), commercially available products such as BMI-1500, BMI-3000, and BMI-5000 (all manufactured by Designer Molecules Inc.) can be used. Alternatively, compounds synthesized by, for example, reacting a carboxylic acid anhydride having a dimer acid skeleton with a diamine having a linear alkylene group having 6 or more carbon atoms can be used. The cyclic imide compound may be used alone or in combination of two or more.

[0162] [(C) Curing accelerator]

[0163] The curing accelerator used in the present invention is a curing accelerator that promotes the reaction between the (A) components or between the (A) component and other components (for example, with the (B) component). Generally speaking, in order to promote the reaction of reactive double bonds, a free radical reaction initiator is often used. Examples of free radical reaction initiators include free radical initiators such as photoradical initiators and thermal free radical initiators. The free radical reaction initiator is preferably a thermal free radical initiator. A more preferred thermal free radical initiator is an organic peroxide. Among organic peroxides, an organic peroxide with a 10-hour half-life temperature of 100 to 170°C is more preferred. Specific examples of the curing accelerator as component (C) include dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, tert-butylperoxycumyl, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and isopropylbenzene hydroperoxide.

[0164] These curing accelerators may be used alone, regardless of their type, or two or more types may be used in combination.

[0165] [(D) Inorganic filler]

[0166] In order to reduce the thermal expansion coefficient and improve the mechanical properties of the cured product of the thermosetting resin composition of the present invention, an inorganic filler as component (D) is added. Examples of inorganic fillers include silicas such as spherical silica, fused silica, crystalline silica, and cristobalite; aluminum oxide; silicon nitride; aluminum nitride; boron nitride; titanium oxide; glass fiber; magnesium oxide, and the like. Furthermore, to improve dielectric properties, fluororesin fillers or coated fluororesin fillers may be used. The average particle size and shape of these inorganic fillers can be selected according to the intended use.

[0167] In order to enhance the bonding strength between the resin component and the inorganic filler, an inorganic filler that has been surface-treated in advance with a coupling agent such as a silane coupling agent or a titanate coupling agent may be used as the inorganic filler. Examples of such coupling agents include epoxy silanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; amino silanes such as N-2(aminoethyl)-3-aminopropyltrimethoxysilane, a reaction product of imidazole and 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; 3-mercaptosilane, 3-epoxythiopropyltrimethoxysilane, and the like. Mercaptosilanes such as methoxysilane; vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane; styrylsilanes such as p-styryltrimethoxysilane; and methacrylsilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane, among others, containing epoxy, amino, mercapto, vinyl, styryl, or methacryl groups. From the perspective of improving strength, silane coupling agents containing amino, methacryl, vinyl, or styryl groups are particularly preferred. It should be noted that there are no particular restrictions on the amount of coupling agent used for surface treatment or the surface treatment method.

[0168] [(E) Adhesion aid having one or more epoxy groups in one molecule]

[0169] As needed, the thermosetting resin composition of the present invention can be matched with (E) an adhesive agent having more than one epoxy group in one molecule. The adhesive agent with epoxy group of (E) component is used to improve the bonding strength between the thermosetting resin composition of the present invention and Si, Cu, Ni, etc. Component (E) is not particularly limited, as long as it has more than one epoxy group in one molecule. Specifically, silane coupling agents with epoxy group such as isocyanuric acid type epoxy resins such as triglycidyl isocyanurate, aromatic amine type epoxy resins such as p-aminophenol triglycidyl, bisphenol A type bisglycidyl ether, dicyclopentadiene type epoxy resins such as dicyclopentadiene / phenol addition type glycidyl ether, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. can be listed. These adhesion promoters having one or more epoxy groups in one molecule may be used alone or in combination of two or more, regardless of their type.

[0170] When the component (E) is added, a curing accelerator that accelerates the reaction of epoxy groups may be added as a component (C') different from the curing accelerator (C). The curing accelerator (C') is not particularly limited as long as it can accelerate the curing reaction of a general epoxy resin composition. Examples include amine compounds such as 1,8-diazabicyclo[5.4.0]-7-undecene, organic phosphine compounds such as triphenylphosphine and tetraphenylphosphine / tetraborate, and imidazole compounds such as 2-methylimidazole.

[0171] These (C') curing accelerators may be used alone or in combination of two or more, regardless of their type.

[0172] [Other additives]

[0173] As needed, various additives may be further incorporated into the thermosetting resin composition of the present invention. As such additives, to improve resin properties, other thermosetting resins such as organopolysiloxanes, silicone oils, and epoxy resins and cyanate resins other than component (E); thermoplastic resins; thermoplastic elastomers; organic synthetic rubbers; light stabilizers; polymerization inhibitors; pigments; dyes, etc. may be incorporated. Coupling agents for improving wettability with fillers and adhesion to substrates, ion traps for improving electrical properties, and non-halogen flame retardants such as phosphorus compounds and metal hydrates for imparting flame retardancy may also be incorporated. Furthermore, fluorine-containing materials such as PTFE powder for improving dielectric properties may also be incorporated.

[0174] The blending amounts of the respective components in the composition 1 containing the component (A), the component (C), and the component (D) are as follows.

[0175] The amount of the curing accelerator (C) in composition 1 is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 4 parts by mass, and even more preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of component (A). When the amount of the curing accelerator is 0.1 parts by mass or greater, the curing reaction proceeds sufficiently. When the amount of the curing accelerator is 5 parts by mass or less, the storage stability of the thermosetting resin composition is excellent.

[0176] The amount of the inorganic filler (D) in composition 1 is preferably 10 to 2000 parts by mass, more preferably 20 to 1200 parts by mass, and even more preferably 40 to 1000 parts by mass, relative to 100 parts by mass of component (A). Furthermore, based on the total composition being 100 parts by mass, the amount of the inorganic filler in composition 1 is preferably 30 to 95% by mass, more preferably 40 to 90% by mass, and even more preferably 50 to 85%. By including a specific amount of the inorganic filler in the composition, composition 1 can be formed into a sheet for use as a substrate or used as a packaging material.

[0177] When composition 1 contains (E) an adhesion promoter having one or more epoxy groups per molecule, the amount thereof is 0.1 to 20 parts by mass, preferably 0.3 to 15 parts by mass, and more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of component (A).

[0178] When the composition 1 contains the component (E) and further contains a curing accelerator (C') that accelerates the reaction of epoxy groups in addition to the curing accelerator (C), the amount of the component (C') is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 4 parts by mass, and even more preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of the total of the components (A) and (E). If the amount of the curing accelerator (C') is 0.1 parts by mass or more, the curing reaction proceeds sufficiently. If the amount of the curing accelerator (C') is 5 parts by mass or less, the storage stability of the thermosetting resin composition is excellent.

[0179] The blending amounts of the respective components in the composition 2 containing the component (A) and the component (B) are as follows.

[0180] The amount of the cyclic imide compound (B) in composition 2 is preferably 5 to 95% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass, relative to the total of the components (A) and (B).

[0181] When composition 2 contains a curing accelerator (C), the amount thereof is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 4 parts by mass, and even more preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of the total of components (A) and (B). When the amount of the curing accelerator is 0.1 parts by mass or greater, the curing reaction proceeds sufficiently; when the amount of the curing accelerator is 5 parts by mass or less, the storage stability of the thermosetting resin composition is excellent.

[0182] When composition 2 contains an inorganic filler (D), the amount thereof is preferably 10 to 2000 parts by mass, more preferably 20 to 1200 parts by mass, and even more preferably 40 to 1000 parts by mass relative to 100 parts by mass of the total of components (A) to (C) and component (E). Furthermore, based on the total composition being 100% by mass, the amount of the inorganic filler in composition 2 is preferably 30 to 95% by mass, more preferably 40 to 92% by mass, and even more preferably 50 to 90% by mass.

[0183] When composition 2 contains (E) an adhesion promoter having one or more epoxy groups in one molecule, the amount thereof is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass, and even more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the total of component (A) and component (B).

[0184] In addition, when composition 2 contains component (E) and further contains a curing accelerator (C') that accelerates the reaction of epoxy groups in addition to the curing accelerator (C), the amount of the curing accelerator (C') is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 4 parts by mass, and even more preferably 0.5 to 3 parts by mass, relative to 100 parts by mass of the total of components (A) and (B). If the amount of the curing accelerator (C') is 0.1 parts by mass or more, the curing reaction can proceed sufficiently. If the amount of the curing accelerator (C') is 5 parts by mass or less, the storage stability of the thermosetting resin composition is good.

[0185] [Method for producing thermosetting resin composition]

[0186] The method for producing the thermosetting resin composition of the present invention is not particularly limited. Examples include methods in which the aforementioned components are blended at a predetermined ratio and then thoroughly and uniformly mixed, stirred, dissolved, dispersed, and / or melt-kneaded using a mixer or the like. The components may be blended simultaneously or separately, and mixing may be performed while heating, as required.

[0187] The device that is used for mixing etc. is not particularly limited, specifically, can be enumerated as the crusher that is equipped with stirring and heating device, double-roll mill, 3-roll mill, ball mill, planetary mixer and attritor etc. Also these devices can be suitably combined and used.

[0188] By curing the thermosetting resin composition of the present invention at a temperature of 120-250°C for 1-24 hours, a cured product having high heat resistance, a low relative dielectric constant, and a low dielectric loss tangent is formed. Alternatively, the composition can be cured by any of the methods described below, depending on the intended use or application of the composition.

[0189] The thermosetting resin composition of the present invention can be widely used in packaging materials for electronic components, thermosetting adhesives, adhesive films, prepregs, circuit substrates for multilayer printed wiring boards, solder resists, underfill materials, and die bonding agents, and is particularly suitable for packaging materials for electronic components.

[0190] Depending on the application, the thermosetting resin composition of the present invention can be used directly as a varnish, or it can be formed into a film (i.e., as a film-like laminate) for use. In the case of a film-like laminate, the softening point of the thermosetting resin composition is preferably 40 to 140°C from the perspective of lamination.

[0191] [Varnish]

[0192] The varnish comprises the thermosetting resin composition of the present invention and an organic solvent, and can be produced by mixing the above-mentioned components and the organic solvent, for example, in a predetermined combination ratio, and kneading them using a three-roll mill, a ball mill, a sand mill, a sand mill, or the like, or stirring them using a planetary mixer or the like, as needed.

[0193] Examples of organic solvents used when the thermosetting resin composition of the present invention is used as a varnish include acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. These organic solvents may be used alone or in combination.

[0194] Furthermore, the solid content concentration (non-volatile content concentration) of the thermosetting resin composition of the present invention in the varnish can be appropriately adjusted depending on the intended use or form. For example, the organic solvent is preferably added so that the solid content concentration is 30 to 90% by mass, and more preferably 40 to 80% by mass.

[0195] [Electronic components]

[0196] The thermosetting resin composition of the present invention is particularly suitable for use as an encapsulating resin material for semiconductor devices such as transistor-type, module-type, DIP-type, SO-type, flat pack-type, and ball grid array-type devices. Furthermore, in embodiment 2, composition 2 is particularly suitable for use as an encapsulating resin material for coils used in automotive parts and the like. The method for encapsulating electronic components using the thermosetting resin composition of the present invention is not particularly limited, and conventional molding methods such as transfer molding, injection molding, and casting can be used.

[0197] [Thermosetting adhesive]

[0198] The thermosetting resin of the present invention can be used as a thermosetting adhesive, for example, as an adhesive for flexible printed circuit boards, an adhesive for semiconductor elements, and an adhesive for housings.

[0199] [Film-like laminated materials]

[0200] The film-like laminate is a film-like laminate having a resin composition layer formed from the thermosetting resin composition of the present invention on a support. The film-like laminate can be manufactured by directly coating the thermosetting resin composition on the support, or by forming a varnish and then applying the varnish using a die coater or the like. When the varnish is applied, the organic solvent can be dried by heating or blowing hot air, thereby forming a resin composition layer on the support.

[0201] Examples of the support (support film) include polyolefin films such as polyethylene, polypropylene, and polyvinyl chloride; polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate; various plastic films such as polycarbonate and polyimide films; release paper; and metal foils such as copper and aluminum foils. Among these, plastic films are preferred for their versatility, with PET films being more preferred. The support and the protective film described below may also be subjected to surface treatments such as MAD treatment and corona treatment. Mold release treatments may also be performed using release agents such as silicone resin release agents, alkyd resin release agents, and fluororesin release agents.

[0202] [Adhesive film]

[0203] As a specific embodiment of the film-like laminated material, an adhesive film may be mentioned.

[0204] As a method for producing an adhesive film, there can be mentioned a method in which a varnish is prepared by the above-mentioned method, the varnish is then applied to a support using a die coater, and the organic solvent is dried by heating or blowing hot air, thereby forming a resin composition layer. The drying conditions are not particularly limited, but it is preferred that the resin composition layer be dried so that the organic solvent content is 10% by mass or less, preferably 5% by mass or less. Although the drying conditions vary depending on the amount of organic solvent in the varnish and the boiling point of the organic solvent, for example, in the case of a varnish containing 30-60% by mass of an organic solvent, a resin composition layer can be formed by drying at 50-150°C for approximately 3-10 minutes. It should be noted that if drying is carried out for a long time at a higher temperature, the curing reaction of the composition may be accelerated, thereby causing the composition to solidify.

[0205] Another method for producing an adhesive film is a method using an extruder equipped with a T-die, in which a thermosetting resin composition prepared by melt-mixing the components is used instead of a varnish.

[0206] The thickness of the resin composition layer of the adhesive film is preferably in the range of 10 to 120 μm. In particular, when the adhesive film is used for a circuit board described below, the thickness of the resin composition layer of the adhesive film is preferably greater than the thickness of the conductor layer of the circuit board. Since the thickness of the conductor layer of a circuit board is generally in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably in the range of 10 to 100 μm. From the perspective of reducing the thickness of the layer, the thickness of the resin composition layer is more preferably in the range of 15 to 80 μm.

[0207] Alternatively, a protective film conforming to the support may be further laminated on the surface of the resin composition layer that is not in contact with the support. In this case, the adhesive film comprises a support, a resin composition layer formed on the support, and a protective film formed on the resin composition layer. The thickness of the protective film is not particularly limited and may be, for example, 1 to 40 μm. By laminating the protective film, dust and the like can be prevented from adhering to or scratching the surface of the resin composition layer. The adhesive film may be rolled up for storage.

[0208] [Prepreg]

[0209] The prepreg is a prepreg containing the thermosetting resin composition of the present invention, and can be produced by impregnating or coating a reinforcing substrate with the thermosetting resin composition of the present invention and heating to semi-cure the thermosetting resin composition.

[0210] As the reinforcing substrate, for example, glass cloth, quartz glass, aromatic polyamide nonwoven fabric, liquid crystal polymer nonwoven fabric, and the like, which are commonly used as reinforcing substrates for prepregs, can be used.

[0211] Examples of the dipping method or coating method include a hot melt method and a solvent method.

[0212] The hot melt method is a method of directly coating the molten thermosetting resin composition of the present invention on a reinforcing substrate using a die coater, or a method of laminating a film-like laminated material prepared by the above method on the reinforcing substrate.

[0213] The solvent method is a method in which the reinforcing base material is immersed in the varnish prepared by the above method and then dried.

[0214] Furthermore, a prepreg can be prepared by heating the adhesive film prepared by the above method from both sides of the reinforcing substrate and continuously heat-laminating them under pressure. The support and protective film can be the same materials as those mentioned for the adhesive film.

[0215] The reinforcing substrate impregnated or coated with the thermosetting resin composition of the present invention is heated, for example, at 60 to 150°C for 5 to 60 minutes to semi-cure the thermosetting resin composition. The prepreg of the present invention preferably contains 25 to 75% by mass of the thermosetting resin composition of the present invention relative to the reinforcing substrate.

[0216] [Circuit board (multilayer printed wiring board)]

[0217] The circuit substrate of the present invention comprises an insulating layer that is a cured product of the thermosetting resin composition of the present invention. It should be noted that the circuit substrate refers to a circuit substrate having a patterned conductor layer (circuit) formed on one or both surfaces of the substrate, wherein the conductor layer and the insulating layer are alternately laminated, and the circuit substrate comprises a multilayer printed wiring board having a patterned conductor layer (circuit) formed on one or both surfaces of the outermost layer. It should be noted that the surface of the conductor layer may be pre-roughened by blackening, copper etching, or the like.

[0218] An example of a method for forming an insulating layer on a circuit board is to apply the varnish prepared by the above method to the circuit board, followed by drying and heat curing. Specifically, an example of a method is to apply the varnish using a dispenser, dry it at 60-150°C for 0.5-2 hours, and then heat cure it at 120-250°C for 1-12 hours. Alternatively, vacuum drying may be employed as needed.

[0219] In addition, as another method for forming an insulating layer on a circuit substrate, it can be cited as a method (lamination process) in which a film-like laminated material produced by the above method is laminated on one side surface or both sides surface of a circuit substrate using a vacuum laminator. In the case where the film-like laminated material has a protective film, after removing the protective film, the film-like laminated material and the circuit substrate are preheated as needed, and the film-like laminated material is laminated on the circuit substrate while being pressurized and heated. In vacuum lamination, the heating and pressing temperature is preferably 60 to 160°C, the heating and pressing pressure is preferably 0.1 to 1.8 MPa, and the heating and pressing time is preferably 20 to 400 seconds. After lamination, it is preferably at normal pressure, for example, by hot pressing the film-like laminated material to perform a smoothing process on the laminated film-like laminated material. The conditions for the smoothing process can be the same as the heating and pressing conditions for the lamination. Smoothing can also be performed by a commercially available laminator. In addition, the lamination process and the smoothing process can also be continuously performed using the commercially available vacuum laminator.

[0220] After laminating the film-like laminated material on the circuit board, the support can be peeled off after cooling to approximately room temperature. The insulating layer can then be formed by heat-curing the resin composition. However, the order of peeling the support can be appropriately changed. In this way, the insulating layer can be formed on the circuit board. Heat-curing conditions can be appropriately selected based on the type and content of the resin component in the resin composition. The heat-curing conditions are preferably maintained at 150°C to 220°C for 20 to 180 minutes, more preferably at 160°C to 210°C for 30 to 120 minutes.

[0221] Another alternative method for forming an insulating layer on a circuit substrate is to laminate the film-like laminated material produced by the above method onto one or both surfaces of the circuit substrate using a vacuum press. In this method, the film-like laminated material is heated and pressurized under reduced pressure using a conventional vacuum hot press to thermally cure the resin composition on the circuit board, thereby forming the insulating layer.

[0222] Another example is a method for producing a circuit board (multilayer printed wiring board) using the prepreg produced by the above method. This method can be produced by stacking one or more prepregs of the present invention on an interior circuit board, sandwiching a metal plate with a release film, and then pressing them together under pressure and heating conditions.

[0223] After the circuit substrate is manufactured, the insulating layer formed on the circuit substrate may be drilled to form via holes or through-holes, and / or the surface of the insulating layer may be roughened, and / or a plating layer may be formed on the insulating layer to form a conductive layer. These steps may be performed according to conventional methods for manufacturing circuit substrates or multilayer printed wiring boards.

[0224] [Example]

[0225] Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples.

[0226] The components used in Examples and Comparative Examples are shown below. In the following description, the blending amount is expressed as parts by mass.

[0227] The composition ratio of the monomer and oligomer of the component (A) is a value calculated from the area ratio of the peaks measured by GPC.

[0228] (A) Cyclopentadiene compounds

[0229] (A-1) Monosubstituted cyclopentadiene compound

[0230] [Synthesis example 1]

[0231] After adding 17.6g of sodium hydride (1.1 equivalents, 60%, dispersed in liquid paraffin) to a 500mL glass four-necked flask with a stirrer, a cooling condenser, and a thermometer, the liquid paraffin in which sodium hydride is dispersed is removed from the system by washing with hexane. Then, after adding 250mL of tetrahydrofuran to the four-necked flask, a nitrogen atmosphere is formed inside the system. 26.4g (1.0 equivalents) of cyclopentadiene are added dropwise at 0°C while stirring vigorously, and the generated hydrogen is released to the outside of the system. After all the cyclopentadiene has been added dropwise, the temperature inside the system is raised to 60°C, and 54.9g (0.9 equivalents) of 4-(chloromethyl)styrene are added dropwise, and stirred at 60°C for 30 minutes. Then, 50g of water is added to terminate the reaction, and tetrahydrofuran is distilled off under reduced pressure. A mixed solvent of xylene and hexane (50% by volume) was added to dilute the organic layer and washed several times with hydrochloric acid (10% by mass) and water. After separating the aqueous layer, anhydrous sodium sulfate was added to the organic layer and dried, and the solvent was distilled off under reduced pressure to obtain a product (A'-1). The composition of the product (A'-1) is shown in Table 1. Since the monomer (4-(cyclopentadienylmethyl)styrene) contained in the product (A'-1) is easily oligomerized at room temperature, the product (A'-1) contains oligomers (oligomers of 4-(cyclopentadienylmethyl)styrene) using the monomer as a monomer.

[0232] Next, the obtained product (A'-1) was added to a 500 mL glass four-necked flask equipped with a stirrer, a cooling condenser, and a thermometer, and stirred under vacuum at 80°C for 1 hour to carry out oligomerization accompanied by partial dimerization of the cyclopentadienyl groups, thereby obtaining product (A-1). The composition of product (A-1) is shown in Table 1, and the structure of the dimer of the monomer contained in product (A-1) is shown in the following formula. In addition, the weight average molecular weight (Mw) of product (A-1) was 2400.

[0233]

[0234] (A-2) Disubstituted cyclopentadiene compound

[0235] [Synthesis example 2]

[0236] After adding 33.6g of sodium hydride (2.1 equivalents, 60%, dispersed in liquid paraffin) to a 500mL glass four-necked flask with a stirrer, a cooling condenser and a thermometer, the liquid paraffin in which sodium hydride is dispersed is removed from the system by washing with hexane. Then, after adding 250mL of tetrahydrofuran to the four-necked flask, a nitrogen atmosphere is formed inside the system. While adding 26.4g (1.0 equivalents) of cyclopentadiene at 0°C and stirring vigorously, the generated hydrogen is released to the outside of the system. After all the cyclopentadiene has been added, the temperature inside the system is raised to 60°C, and a mixture of 45.8g (0.75 equivalents) of 4-(chloromethyl)styrene and 12.7g (0.25 equivalents) of benzyl chloride is added dropwise, and stirred at 60°C for 30 minutes. Then, 30.6 g (1.0 equivalent) of allyl chloride was added dropwise and stirred at 60° C. for 30 minutes. Then, 50 g of water was added to terminate the reaction, and tetrahydrofuran was distilled off under reduced pressure. A mixed solvent of xylene and hexane (50% by volume) was added to dilute the organic layer, and washed several times with hydrochloric acid (10% by mass) and water. After separating the aqueous layer, anhydrous sodium sulfate was added to the organic layer and dried, and the solvent was distilled off under reduced pressure to obtain a product (A'-2). The composition of the product (A'-2) is shown in Table 1. Since the monomers (4-(allylcyclopentadienylmethyl)styrene and 4-(allylcyclopentadienylmethyl)benzene) contained in the product (A'-2) are easily oligomerized at room temperature, the product (A'-2) contains oligomers containing the monomers as monomers (oligomers of 4-(allylcyclopentadienylmethyl)styrene, oligomers of 4-(allylcyclopentadienylmethyl)benzene, and oligomers of 4-(allylcyclopentadienylmethyl)styrene and 4-(allylcyclopentadienylmethyl)benzene).

[0237] Next, the obtained product (A'-2) was added to a 500 mL glass four-necked flask equipped with a stirrer, a cooling condenser, and a thermometer, and stirred under vacuum at 80°C for 1 hour to carry out oligomerization accompanied by partial dimerization of the cyclopentadienyl groups, thereby obtaining product (A-2). The composition of product (A-2) is shown in Table 1, and the structure of the dimer of the monomer contained in product (A-2) is shown in the following formula. In addition, the weight average molecular weight (Mw) of product (A-2) is 3000.

[0238]

[0239] [Table 1]

[0240] product Monomer (mass %) Oligomers (mass %) (A’-1) 70 30 (A-1) 30 70(20) (A’-2) 80 20 (A-2) 35 65(15)

[0241] In the oligomer ratios of the products (A-1) and (A-2) in Table 1, the values ​​shown in parentheses represent the ratios of dimers in the products.

[0242] (B) Cyclic imide compound

[0243] (B-1): Maleimide compound-1 (BMI-1500, manufactured by Designer Molecules Inc., weight average molecular weight 4000) represented by the following formula:

[0244]

[0245] (B-2): Maleimide compound-2 containing a linear alkylene group represented by the following formula (BMI-3000, manufactured by Designer Molecules Inc., weight average molecular weight 9000)

[0246]

[0247] (B-3): Maleimide compound-3 containing a linear alkylene group represented by the following formula (BMI-5000, manufactured by Designer Molecules Inc., weight average molecular weight 21500)

[0248]

[0249] (B-4): 4,4'-diphenylmethanebismaleimide (BMI, manufactured by K.I. Chemical Industry Co., Ltd.)

[0250] (C) Curing accelerator

[0251] (C-1) Dicumyl peroxide (Park Mill D: manufactured by NOF Corporation)

[0252] (D) Inorganic filling materials

[0253] (D-1) Fused spherical silica (RS-8225 / 53C: manufactured by Ronson Co., Ltd., Japan)

[0254] (D-2) Silica surface-treated by dry method with 0.3 parts of 3-aminopropyltrimethoxysilane (KBM-903: manufactured by Shin-Etsu Chemical Co., Ltd.) relative to 100 parts of (D-1)

[0255] (D-3) Silica surface-treated by dry method with 0.3 parts of N-phenyl-3-aminopropyltrimethoxysilane (KBM-573: manufactured by Shin-Etsu Chemical Co., Ltd.) relative to 100 parts of (D-1)

[0256] (D-4) Silica surface-treated by dry method with 0.3 parts of 3-methacryloxypropyltrimethoxysilane (KBM-503: manufactured by Shin-Etsu Chemical Co., Ltd.) relative to 100 parts of (D-1)

[0257] (D-5) Silica surface-treated by dry method with 0.3 parts of vinyltrimethoxysilane (KBM-1003: manufactured by Shin-Etsu Chemical Co., Ltd.) relative to 100 parts of (D-1)

[0258] (D-6) Silica surface-treated by dry method with 0.3 parts of p-styryltrimethoxysilane (KBM-1403: manufactured by Shin-Etsu Chemical Co., Ltd.) relative to 100 parts of (D-1)

[0259] (E) Adhesion aids having one or more epoxy groups in one molecule

[0260] (E-1) Isocyanuric acid type epoxy resin (TEPIC-S: manufactured by Nissan Chemical Industries, Ltd., Japan)

[0261] (E-2) 3-Glycidoxypropyltrimethoxysilane (KBM-403: manufactured by Shin-Etsu Chemical Co., Ltd.)

[0262] [Examples 1 to 14, Comparative Examples 1 and 2]

[0263] The components in the proportions (parts by mass) shown in Table 2 were mixed with a stirrer and then further mixed with a three-roll mill to obtain a resin composition.

[0264] [Examples 15 to 30, Comparative Examples 3 to 5]

[0265] The components in the proportions (parts by mass) shown in Table 3 were dissolved and dispersed in toluene to adjust the non-volatile content to 70% by mass, thereby obtaining a varnish of a resin composition. The relative dielectric constant and dielectric loss tangent of the varnish were evaluated.

[0266] In addition, the resin composition was obtained by melting, mixing and cooling the components in the ratios (parts by mass) shown in Table 3 using a three-roll mill, and the long-term heat resistance, tracking resistance (CTI) and adhesion of the composition were evaluated.

[0267] <Glass transition temperature>

[0268] The resin composition was cast into a mold and cured by gradual curing at 150°C for 1 hour and further at 180°C for 2 hours to obtain a cured product of 5 mm × 5 mm × 15 mm. These cured products were placed in a thermal dilatometer (TMA8140C, manufactured by Rigaku Co., Ltd.). The heating rate was set at 5°C / minute, and after the test piece of the cured product was set to apply a constant load of 49 mN, the dimensional change of the test piece was measured from -60°C to 300°C. The relationship between the dimensional change and the temperature was plotted in the graph. From the graph of the relationship between the dimensional change and the temperature obtained in this way, the glass transition temperature was obtained.

[0269] <Relative dielectric constant, dielectric loss tangent>

[0270] The resin composition was applied to a 38 μm-thick PET film using a roll coater to a dry thickness of 50 μm. The film was then cured by step-curing at 150°C for 1 hour and then at 180°C for 2 hours. The film's relative dielectric constant and dielectric loss tangent at a frequency of 10 GHz were then measured using a network analyzer (E5063-2D5, manufactured by Keysight Technologies, Inc.) connected to a stripline (manufactured by Keycom Co., Ltd.).

[0271] <Long-term heat resistance test>

[0272] The resin composition was cast into a mold and cured by step-curing at 150°C for 1 hour and then at 180°C for 2 hours, yielding a 50 mm diameter x 3 mm tall cured product. The cured product was stored in a 250°C thermostat for 1000 hours, and its mass after storage was measured. The mass retention rate was calculated as [mass of the cured product after storage / mass of the cured product before storage] × 100 (%).

[0273] <Water absorption>

[0274] The resin composition was cast into a mold and cured by step curing at 150°C for 1 hour and then at 180°C for 2 hours, yielding a 50 mm diameter x 3 mm tall cured product. The cured product was weighed before and after treatment at 121°C and 2.1 atmospheres of saturated steam for 24 hours, and the water absorption was calculated from the weight gain.

[0275] <CTI test>

[0276] The resin composition was cast into a mold and cured by step-curing at 150°C for 1 hour and then at 180°C for 2 hours, resulting in a cured product measuring 50 mm φ x 3 mm t. This cured product was subjected to a tracking resistance test in accordance with JIS C 2134 (IEC 60112). The maximum voltage at which the entire cured product could withstand 50 or more drops of 0.1% ammonium chloride aqueous solution without being damaged was determined in an evaluation with n = 5 samples as the tracking resistance voltage. It should be noted that 600 V was the upper limit of the maximum voltage.

[0277] <Adhesion Test with Silicone>

[0278] With an adhesion area of ​​4mm 2 The resin composition was applied to a 10 mm x 10 mm silicon chip. Another silicon chip was placed on the resin composition coating on the silicon chip. The resin composition was then cured by step-curing at 150°C for 1 hour and then at 180°C for 2 hours to produce a test piece. The shear adhesion of this test piece was measured at room temperature (25°C) using a DAGE-SERIES-4000PXY (DAGE) adhesion tester as an evaluation of adhesion strength.

[0279] <Adhesion Test with Copper>

[0280] With an adhesion area of ​​4mm 2A test piece was prepared by coating the resin composition on a 10 mm x 10 mm copper frame. A silicon chip was placed on the resin composition coating on the copper frame. The resin composition was then cured by step-curing at 150°C for 1 hour and then at 180°C for 2 hours. The shear adhesion of this test piece was measured at room temperature (25°C) using a DAGE-SERIES-4000PXY (DAGE) adhesion tester to evaluate adhesion.

[0281] <Flexural Strength, Flexural Modulus>

[0282] The resin composition was cast into a mold conforming to JIS K 6911:2006 and cured by step curing at 150°C for 1 hour and then at 180°C for 2 hours to produce a test piece. The test piece's flexural strength and flexural modulus were measured at room temperature (25°C) in accordance with JIS K 6911:2006.

[0283] [Table 2]

[0284]

[0285] As shown in Table 2, the cured product of the resin composition of the present invention has a high glass transition temperature (Tg), low relative dielectric constant and dielectric loss tangent, and excellent long-term heat resistance. Furthermore, its water absorption rate is low. Therefore, the resin composition of the present invention is suitable for use as a high-frequency device material.

[0286] [Table 3]

[0287]

[0288] As shown in Table 3, the cured product of the resin composition of the present invention has low relative dielectric constant and dielectric loss tangent values, excellent long-term heat resistance, and high tracking resistance. Therefore, the resin composition of the present invention is suitable for use as a material for high-frequency devices and power devices.

Claims

1. A thermosetting resin composition comprising: (A) a cyclopentadiene compound represented by the following formula (1) and / or an oligomer thereof, in, In formula (1), n ​​is an integer of 1 to 4, x1 and x2 are 1 or 2, or, when x1 is 0, x2 is 1 or 2, and when x2 is 0, x1 is 1 or 2, R represents a group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms; however, when R represents an alkyl group or an aryl group, x1 is 1 or 2, And 1≤x1+x2≤4; (C) a curing accelerator; and (D) Inorganic filling materials.

2. The thermosetting resin composition according to claim 1, in, The oligomer of the compound represented by the formula (1) of the component (A) includes a dimer and / or trimer of the compound represented by the formula (1).

3. The thermosetting resin composition according to claim 1, in, The oligomer of the compound represented by the formula (1) as the component (A) has a dicyclopentadiene ring.

4. The thermosetting resin composition according to claim 1, in, The ratio of the oligomer of the compound represented by formula (1) in the component (A) is 10 to 90% by mass.

5. The thermosetting resin composition according to claim 1, in, The component (D) has been surface-treated with a silane coupling agent having an amino group, a methacryloyl group, a vinyl group, or a styrene group.

6. The thermosetting resin composition according to claim 1, in, The thermosetting resin composition further contains an adhesion promoter as a component (E), and the adhesion promoter has one or more epoxy groups in one molecule.

7. A thermosetting resin composition comprising: (A) a cyclopentadiene compound represented by the following formula (1) and / or an oligomer thereof, in, In formula (1), n ​​is an integer of 1 to 4, x1 and x2 are 1 or 2, or, when x1 is 0, x2 is 1 or 2, and when x2 is 0, x1 is 1 or 2, R represents a group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 10 carbon atoms; however, when R represents an alkyl group or an aryl group, x1 is 1 or 2, And 1≤x1+x2≤4; (B) a cyclic imide compound containing, in one molecule, at least one dimer acid skeleton, at least one linear alkylene group having 6 or more carbon atoms, and at least two unsaturated cyclic imide groups, The amount of the component (B) is 5 to 95 parts by mass relative to 100 parts by mass of the total of the component (A) and the component (B).

8. The thermosetting resin composition according to claim 7, in, The oligomer of the compound represented by the formula (1) of the component (A) includes a dimer and / or trimer of the compound represented by the formula (1).

9. The thermosetting resin composition according to claim 7, in, The oligomer of the compound represented by the formula (1) as the component (A) has a dicyclopentadiene ring.

10. The thermosetting resin composition according to claim 7, in, The ratio of the oligomer of the compound represented by formula (1) in the component (A) is 10 to 90% by mass.

11. The thermosetting resin composition according to claim 7, in, (B) The cyclic imide compound is represented by the following formula (2): In formula (2), A independently represents a tetravalent organic group containing an aromatic ring or an aliphatic ring, B is an alkylene group having a divalent aliphatic ring which may contain a heteroatom and having 6 to 18 carbon atoms, Q independently represents a straight-chain alkylene group having 6 or more carbon atoms, R independently represents a straight-chain or branched alkyl group having 6 or more carbon atoms, n represents a number from 1 to 10, and m represents a number from 0 to 10.

12. The thermosetting resin composition according to claim 11, in, In formula (2), the organic group represented by A is any group represented by the following structural formula, In the above structural formula, the end to which a substituent is not bonded is the end to which the carbonyl carbon forms the cyclic imide structure in formula (2).

13. The thermosetting resin composition according to claim 7, in, The thermosetting resin composition further contains a curing accelerator as the component (C).

14. The thermosetting resin composition according to claim 7, in, The thermosetting resin composition further contains an inorganic filler as the component (D).

15. The thermosetting resin composition according to claim 14, in, The component (D) has been surface-treated with a silane coupling agent having an amino group, a methacryloyl group, a vinyl group, or a styrene group.

16. The thermosetting resin composition according to claim 7, in, The thermosetting resin composition further contains an adhesion promoter as a component (E), and the adhesion promoter has one or more epoxy groups in one molecule.

17. A packaging material for electronic components, It is formed from the thermosetting resin composition according to any one of claims 1 to 16.

18. The packaging material according to claim 17, in, The electronic component is a semiconductor device.

19. The packaging material according to claim 17, in, The electronic component is a coil component.

20. A thermosetting adhesive, It is formed from the thermosetting resin composition according to any one of claims 1 to 16.

21. An adhesive film, in, The thermosetting resin composition according to any one of claims 1 to 16 is formed as a layer on a support film.

22. A prepreg, in, The thermosetting resin composition according to any one of claims 1 to 16 is impregnated in a sheet-like fiber base material.

23. A multilayer printed wiring board, in, The multilayer printed wiring board includes an insulating layer formed of a cured product of the thermosetting resin composition according to any one of claims 1 to 16.

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