Resin composition, and prepreg, resin-coated film, resin-coated metal foil, metal-clad laminate, and wiring board using the same

Abstract

One aspect of the present application relates to a resin composition containing: a compound (A) represented by the following formula (X-Y formula), in which X is 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-yl-10-oxide, and Y is a protecting group; and a thermosetting resin (B) containing at least one selected from the group consisting of an epoxy resin, a polyphenylene ether resin, a cyanate ester resin, a phenol resin, an active ester resin, a benzoxazine resin, a maleimide resin, an acrylic resin, a methacrylic resin, a vinyl resin, an allyl resin, a propenyl resin, and a hydrocarbon-based resin having an unsaturated double bond.

Description

Technical Field

[0001] This invention relates to resin compositions and prepregs using the same, resin-coated films, resin-coated metal foils, metal-clad laminates, and wiring substrates. Background Technology

[0002] In recent years, with the increase in information processing volume, the installation technologies of semiconductor devices in various electronic devices, such as high integration, high-density wiring, and multilayering, have developed rapidly. As the substrate material used to construct the wiring substrates used in various electronic devices, thermosetting resins are usually used. In order to cope with high temperatures such as reflow and multilayering, high heat resistance (glass transition temperature) is required. In order to improve signal transmission speed and reduce signal loss during transmission, low dielectric constant and dielectric loss factor are required.

[0003] For substrate materials used in printed circuit boards and semiconductor packages, high flame retardancy is required. Therefore, flame retardants are typically added to resin compositions used as insulating materials. Halogen-based flame retardants, such as brominated flame retardants, are known as flame retardants. However, cured resin compositions containing halogens raise concerns about the generation of harmful substances such as hydrogen halides during combustion, posing adverse effects on human health and the environment. Against this backdrop, halogen-free materials are also required for use as insulating materials in printed circuit boards and the like.

[0004] It is generally believed that phosphorus-based flame retardants, which are well-known as halogen-free flame retardants, generate a carbonized layer on the surface during combustion by promoting the carbonization of synthetic resins through the effect of phosphorus compounds. This carbonized layer cuts off the heat energy of the fire source or the air necessary for combustion, thereby exerting a flame-retardant effect.

[0005] It has also been previously reported that by adding specified phosphorus compounds to thermosetting resins such as PPE compounds or maleimide compounds, it is possible to maintain the performance of printed circuit boards to a certain extent and ensure flame retardancy (Patent Documents 1-3, etc.).

[0006] However, when using conventional halogen-free flame retardants, a large amount of flame retardant is required to ensure sufficient flame retardancy. As a result, the glass transition temperature (Tg) of the cured resin composition decreases or the dielectric properties are insufficient. Furthermore, there is a need for resin compositions using novel flame retardants with high functionalization suitable for recent substrate materials, different from conventional halogen-free flame retardants, and exhibiting flame-retardant effects.

[0007] The present invention was made in view of the above circumstances, and its object is to provide a resin composition that has the same or higher flame retardancy as a conventional phosphorus-based flame retardant resin composition, and maintains or has higher performance as a wiring board, such as low dielectric properties and high glass transition temperature (Tg).

[0008] Existing technical documents

[0009] Patent documents

[0010] Patent Document 1: Japanese Patent Publication No. 2011-46816

[0011] Patent Document 2: International Patent Publication No. 2020 / 204175

[0012] Patent Document 3: Japanese Patent Publication No. 2011-52165 Summary of the Invention

[0013] One aspect of the present invention relates to a resin composition comprising: compound (A) of the following formula,

[0014] XY

[0015] (In the formula, X is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl-10-oxide, and Y is a protecting group.); and,

[0016] Thermosetting resin (B) contains at least one selected from epoxy resin, polyphenylene ether resin, cyanate ester resin, phenolic resin, reactive ester resin, benzoxazine resin, maleimide resin, acrylic resin, methacrylic resin, vinyl resin, allyl resin, acrylic resin, and hydrocarbon resin having unsaturated double bonds. Attached Figure Description

[0017] Figure 1 This is a schematic cross-sectional view showing the composition of a prepreg according to an embodiment of the present invention.

[0018] Figure 2 This is a schematic cross-sectional view showing the structure of a metal-clad laminate according to an embodiment of the present invention.

[0019] Figure 3 This is a schematic cross-sectional view showing the structure of a wiring substrate according to an embodiment of the present invention.

[0020] Figure 4 This is a schematic cross-sectional view showing the structure of a resin-coated metal foil according to an embodiment of the present invention.

[0021] Figure 5 This is a schematic cross-sectional view showing the structure of a resin film according to an embodiment of the present invention.

[0022] Figure 6 It is the infrared absorption spectrum (IR) of organic compound 1 obtained in manufacturing example 1.

[0023] Figure 7It is the 1H-NMR of organic compound 1 obtained in manufacturing example 1.

[0024] Figure 8 It is the FD-MS of organic compound 1 obtained in manufacturing example 1. Detailed Implementation

[0025] The resin composition (hereinafter, sometimes simply referred to as the resin composition) according to embodiments of the present invention contains:

[0026] The compound (A) shown in the following formula,

[0027] XY

[0028] (In the formula, X is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl-10-oxide, and Y is a protecting group.); and,

[0029] The curable resin (B) contains at least one selected from epoxy resin, polyphenylene ether resin, cyanate ester resin, phenolic resin, reactive ester resin, benzoxazine resin, maleimide resin, acrylic resin, methacrylic resin, vinyl resin, allyl resin, propylene resin, and hydrocarbon resin having unsaturated double bonds.

[0030] Based on the above composition, a resin composition can be provided that exhibits high flame retardancy even without halogen atoms and has properties such as low dielectric properties and high glass transition temperature (Tg).

[0031] It is believed that the protecting group breaks off from the above compound (A) and generates free radicals, thereby the resin composition of this embodiment exerts a flame-retardant effect through the fire-extinguishing effect brought about by the stable free radicals.

[0032] Therefore, according to the present invention, a resin composition can be provided that exhibits high flame retardancy due to the absence of halogen atoms, and whose cured product has properties such as low dielectric properties and high Tg. Furthermore, by using the above-mentioned resin composition, prepregs, resin-coated films, resin-coated metal foils, metal-clad laminates, and wiring substrates possessing properties such as high flame retardancy, low dielectric properties, and high Tg can be provided.

[0033] The components of the resin composition involved in this embodiment will be described in detail below.

[0034] <Compound (A)>

[0035] The compound (A) involved in this embodiment is the compound shown in the following formula.

[0036] XY

[0037] (In the formula, X is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl-10-oxide, and Y is a protecting group.)

[0038] It is generally known that compounds such as organic peroxides, which are prone to homolytic cracking, have low decomposition temperatures, and therefore are unsuitable for addition as flame retardants to various synthetic resins. In contrast, it is believed that, in the case of compound (A) of this embodiment, the decomposition temperature that generates stable free radicals exceeds 200°C, thereby achieving a very high flame retardant effect.

[0039] Furthermore, the resin composition of this embodiment, by containing the above-mentioned compound (A), not only has flame retardancy, but also has the advantages of high Tg and low dielectric properties in its cured product.

[0040] The aforementioned compound (A) is a compound having at least one selected from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl-10-oxide. Compounds having this group possess free radical scavenging effects, therefore it is believed that higher flame retardant properties can be obtained.

[0041] Furthermore, the protecting group in the aforementioned compound (A) refers to a substituent that is temporarily introduced to deactivate a specific functional group of a compound, with the premise of its departure in a subsequent stage, thereby improving the chemical stability of the compound. In this embodiment, the subsequent stage refers to the period during which the resin composition containing the compound undergoes combustion.

[0042] As the protecting group used in this embodiment, any protecting group that can be introduced by a protecting agent can be used without particular problems. Such a protecting agent refers to a commonly available (e.g., commercially available) protecting agent or a substance derived from a synthetic protecting agent.

[0043] Specifically, for example, protecting group Y can be silyl, acyl, allyl, allyloxycarbonyl, benzyl, benzyloxycarbonyl, acetal, thioacetal, 2,2,2-trichloroethoxycarbonyl, alkoxymethyl, tert-butoxycarbonyl, 9-fluorenylmethoxycarbonyl, triphenylmethyl (trityl group), sulfonyl (sulfonyl group), etc. Among these, it is particularly preferred that the total molecular weight of the compound of the above formula (1) is 250 or more, and that when the bond between X and Y is broken, the free radical atom of Y is also stabilized by the resonance of at least one adjacent aromatic ring, just like the free radical atom of X, thereby easily generating a stable free radical.

[0044] Furthermore, the protecting group Y is preferably the group shown in formula (1).

[0045]

[0046] In the above formula (1), R1, R2 and R3 independently represent hydrogen, benzoyloxy, vinylbenzyl, alkoxy with 1 to 6 carbon atoms or alkenyl with 2 to 6 carbon atoms, respectively, and m independently represents an integer from 1 to 5.

[0047] In the case where the protecting group Y in the above compound (A) is the group shown in formula (1), it is considered that: among the free radical atoms generated by the breakage of the above organic compound, one (X side) is stabilized by the resonance of at least one aromatic ring, and the other (protecting group Y side) is stabilized by the resonance of three aromatic rings, so it can break into free radical pairs more smoothly. Therefore, the flame retardant effect as described above can be obtained more reliably.

[0048] More specific examples of the groups represented by the above formula (1) include, for example, triphenylmethyl, 4-methoxytriphenylmethyl, 4,4'-dimethoxytriphenylmethyl, 4,4',4”-tris(benzoyloxy)triphenylmethyl, etc.

[0049] For example, when the protecting group is triphenylmethyl, compound (A) of this embodiment is as follows (wherein, compounds (1-2) to (1-4) other than compound (1-1) are reference compounds):

[0050]

[0051] Additionally, for example, when the protecting group is 4-methoxytriphenylmethyl, compound (A) of this embodiment is as follows (wherein, compounds (2-2) to (2-4) other than compound (2-1) are reference compounds):

[0052]

[0053] Additionally, for example, when the protecting group is 4,4'-dimethoxytriphenylmethyl, compound (A) of this embodiment is as follows (wherein, compounds (3-2) to (3-4) other than compound (3-1) are reference compounds):

[0054]

[0055] Furthermore, when the protecting group is 4,4',4”-tris(benzoyloxy)triphenylmethyl, the compound (A) of this embodiment is as follows (wherein, compounds (4-2) to (4-4) other than compound (4-1) are reference compounds):

[0056]

[0057] Furthermore, the weight-average molecular weight of compound (A) in this embodiment is preferably 250 or more. Therefore, even when added to the synthetic resin at high temperatures, volatility can be suppressed, and the additive effect can be fully utilized. Moreover, the weight-average molecular weight of compound (A) is more preferably 300 or more, and even more preferably 400 or more. The upper limit of the molecular weight is not particularly limited, but from the viewpoint of the number of free radical generation sources per unit molecular weight, it is preferably 1000 or less, and even more preferably 900 or less.

[0058] The synthesis method of compound (A) in this embodiment is not particularly limited. For example, compound (A) can be obtained by condensing compound X (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-yl-10-oxide) and a protecting agent having a group that specifically reacts with the functional group of compound X in the presence or absence of a base. Specific protecting agents that can be used include, for example, triphenylmethyl chloride, 4-methoxytriphenylmethyl chloride, 4,4'-dimethoxytriphenylmethyl chloride, and 4,4',4”-tris(benzoyloxy)triphenylmethyl bromide.

[0059] <Thermosetting Resin (B)>

[0060] The thermosetting resin (B) used in this embodiment is not particularly limited as long as it is a thermosetting resin that can be used as a wiring substrate material. Specifically, examples include epoxy resin, polyphenylene ether resin, cyanate ester resin, phenolic resin, benzoxazine resin, reactive ester resin, and resins having unsaturated groups. Examples of resins having unsaturated groups include acrylic resin, methacrylic resin, vinyl resin, allyl resin, acrylic resin, maleimide resin, and hydrocarbon resins having unsaturated double bonds. Preferably, at least one of these is included.

[0061] Among these, resins that produce cured products with low dielectric constants, low dielectric loss factors, and high Tg are preferred. Specifically, resins preferably contain at least one selected from polyphenylene ether compounds, maleimide compounds, and hydrocarbon resins having unsaturated double bonds.

[0062] (Polyphenylene ether resin)

[0063] As a polyphenylene ether resin, for example, a terminal-modified polyphenylene ether compound that exhibits excellent low dielectric properties after curing is preferred, and a modified polyphenylene ether compound that has been terminally modified with substituents having carbon-carbon unsaturated double bonds is even more preferred.

[0064] As substituents having carbon-carbon unsaturated double bonds, examples include groups that show, for instance, the styrene structure or (meth)acrylate structure shown in formula (2) or (3).

[0065]

[0066] In formula (3), R1 represents a hydrogen atom or an alkyl group. The alkyl group is not particularly limited, but preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms. Specifically, examples include methyl, ethyl, propyl, hexyl, and decyl.

[0067] More specifically, examples of the substituents mentioned above include vinylbenzyl, meta-vinylbenzyl, vinylbenzyl (vinylbenzyl), vinylphenyl, acrylate, and methacrylate.

[0068] It is believed that by using such modified polyphenylene ether compounds, low dielectric constant, low dielectric loss factor and other low dielectric properties and excellent heat resistance can be maintained, and high Tg and tightness can also be improved.

[0069] It should be noted that modified polyphenylene ether compounds can be used alone or in combination of two or more.

[0070] In this embodiment, the weight-average molecular weight (Mw) of the modified polyphenylene ether compound used as a thermosetting resin is not particularly limited, but is preferably 1000 to 5000, and more preferably 1000 to 4000. It should be noted that the weight-average molecular weight can be determined using a general molecular weight determination method; specifically, values ​​obtained using gel permeation chromatography (GPC) can be cited as examples. Furthermore, when the modified polyphenylene ether compound has repeating units (s, m, n) within its molecule, these repeating units are preferably values ​​that bring the weight-average molecular weight of the modified polyphenylene ether compound into this range.

[0071] When the weight-average molecular weight of the modified polyphenylene ether compound is within this range, it not only possesses the excellent low dielectric properties inherent in the polyphenylene ether backbone and exhibits superior heat resistance of the cured product, but also excellent moldability. This is believed to be due to the following reasons: Compared to conventional polyphenylene ethers, when the weight-average molecular weight is within the range described above, the molecular weight is lower, thus tending to decrease the heat resistance of the cured product. Regarding this, it is believed that the modified polyphenylene ether compound according to this embodiment, having a styrene structure or (meth)acrylate structure at the end, exhibits high reactivity, allowing for the production of cured products with sufficiently high heat resistance. Furthermore, it is believed that while the weight-average molecular weight of the modified polyphenylene ether compound is higher than that of styrene or divinylbenzene within this range, it is lower than that of conventional polyphenylene ethers, thus resulting in excellent moldability. Therefore, it is believed that such a modified polyphenylene ether compound can produce cured products with both superior heat resistance and excellent moldability.

[0072] Furthermore, in this embodiment, the average number of the aforementioned substituents (number of terminal functional groups) at the molecular end of each molecule of the modified polyphenylene ether compound used as a thermosetting resin is not particularly limited. Specifically, 1 to 5 is preferred, and 1 to 3 is more preferred. If the number of terminal functional groups is too small, it tends to be difficult to obtain a cured product with sufficient heat resistance. In addition, if the number of terminal functional groups is too large, the reactivity becomes excessively high, which may lead to adverse effects such as decreased shelf life or decreased flowability of the resin composition. That is, if such a modified polyphenylene ether is used, there is a risk of molding problems such as insufficient flowability, which may result in poor molding such as voids during multilayer molding, making it difficult to obtain a printed circuit board with high reliability.

[0073] It should be noted that the number of terminal functional groups in the modified polyphenylene ether compound can be represented by, for example, the average value of the substituents present in each molecule of all the modified polyphenylene ether compounds in 1 mole of the modified polyphenylene ether compound. This number of terminal functional groups can be determined, for example, by measuring the number of residual hydroxyl groups in the obtained modified polyphenylene ether compound and calculating the reduction in the number of hydroxyl groups compared to the polyphenylene ether before modification. This reduction in the number of hydroxyl groups compared to the polyphenylene ether before modification is the number of terminal functional groups. Furthermore, for the method of determining the number of residual hydroxyl groups in the modified polyphenylene ether compound, it can be determined by adding a quaternary ammonium salt (tetraethylammonium hydroxide) associated with hydroxyl groups to a solution of the modified polyphenylene ether compound and measuring the UV absorbance of the mixed solution.

[0074] Furthermore, there is no particular limitation on the intrinsic viscosity of the modified polyphenylene ether compound used in this embodiment. Specifically, it can be 0.03 to 0.12 dl / g, preferably 0.04 to 0.11 dl / g, and more preferably 0.06 to 0.095 dl / g. If the intrinsic viscosity is too low, there is a tendency for a low molecular weight, and it is difficult to obtain low dielectric properties such as low dielectric constant and low dielectric loss factor. On the other hand, if the intrinsic viscosity is too high, the viscosity is high, insufficient flowability is obtained, and the moldability of the cured product tends to decrease. Therefore, if the intrinsic viscosity of the modified polyphenylene ether compound is within the above range, excellent heat resistance and moldability of the cured product can be achieved.

[0075] It should be noted that the intrinsic viscosity here refers to the intrinsic viscosity measured in dichloromethane at 25°C. More specifically, it is, for example, the value obtained by measuring a 0.18 g / 45 ml dichloromethane solution (liquid temperature 25°C) using a viscometer. Examples of such viscometers include, for instance, the AVS500 Visco System manufactured by Schott.

[0076] It should be noted that the polyphenylene ether compound used in the resin composition of this embodiment can be synthesized by known methods or commercially available products can be used. Examples of commercially available products include "OPE-2st1200" and "OPE-2st 2200" manufactured by Mitsubishi Gas Chemical Co., Ltd., and "SA9000" manufactured by SABIC Innovative Plastics Co., Ltd.

[0077] (Maleimide resin)

[0078] As the maleimide resin that can be used in this embodiment, any compound having a maleimide group within its molecule can be used without particular restriction. Specifically, examples of the aforementioned maleimide compounds include: monofunctional maleimide compounds having one maleimide group within their molecule, polyfunctional maleimide compounds having two or more maleimide groups within their molecule, and modified maleimide compounds. Examples of the aforementioned modified maleimide compounds include: modified maleimide compounds in which a portion of the molecule is modified by an amine compound, modified maleimide compounds in which a portion of the molecule is modified by an organosilicon compound, and modified maleimide compounds in which a portion of the molecule is modified by both an amine compound and an organosilicon compound.

[0079] More specifically, examples include maleimide compounds having two or more N-substituted maleimide groups in one molecule, maleimide compounds having an indene structure, maleimide compounds having at least one alkyl group selected from six or more carbon atoms and an alkylene group selected from six or more carbon atoms, and maleimide compounds having a benzene ring in the molecule.

[0080] The maleimide compounds used in this embodiment can be commercially available products, such as BMI-4000, BMI-2300, BMI-TMH, BMI-4000, BMI-5100 manufactured by Daiwa Chemical Industries, Ltd.; MIR-3000-70MT and MIR-5000 manufactured by Nippon Kayaku Co., Ltd.; and BMI-689, BMI-1500, BMI-3000J, and BMI-5000 manufactured by Designer Molecules Inc.

[0081] (Hydrocarbon resins with unsaturated double bonds)

[0082] As for the hydrocarbon resin that can be used in this embodiment, there is no particular limitation as long as it is a hydrocarbon resin with unsaturated double bonds. Examples of preferred examples include, for instance, polyfunctional vinyl aromatic polymers, cyclic polyolefin resins, and hydrocarbon resins that are copolymers of vinyl aromatic compounds and conjugated diene compounds.

[0083] As a polyfunctional vinyl aromatic polymer, it is preferred to be a polymer containing at least a substance obtained by polymerizing a polyfunctional vinyl aromatic compound or / and its derivatives. There is no particular limitation as long as the polymer contains a structure from a polyfunctional vinyl aromatic compound or / and its derivatives, and it can be a polymer containing a structure from one or more polyfunctional vinyl aromatic compounds or / and their derivatives.

[0084] Preferably, multifunctional vinyl aromatic copolymers having structural units derived from monomers containing divinyl aromatic compounds and ethyl vinyl aromatic compounds can be used.

[0085] In the resin composition of this embodiment, as the thermosetting resin (B), in addition to the above, epoxy resin, cyanate ester resin, phenolic resin, reactive ester resin, benzoxazine resin, and resins other than those mentioned above that have unsaturated groups (acrylic resin, methacrylic resin, vinyl resin, allyl resin, acrylic resin, etc.) can also be used.

[0086] As epoxy resins, compounds with intramolecular epoxy groups can be used. Specifically, examples include bixylenol type epoxy resins. Epoxy resins include bisphenol A type, bisphenol F type, bisphenol S type, bisphenol AF type, dicyclopentadiene type, triphenol type, naphthol phenolic varnish type, phenol phenolic varnish type, tert-butyl-catechol type, naphthalene type, naphthol type, anthracene type, glycidylamine type, glycidyl ester type, cresol phenolic varnish type, biphenyl type, linear aliphatic epoxy resin, butadiene-structured epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, spirocyclic epoxy resin, cyclohexane type, cyclohexanediol type, naphthylene ether type, tris(hydroxymethyl) type, and tetraphenylethane type epoxy resin, etc. In addition, the epoxy compounds mentioned above also include the following epoxy resins: polymers of the aforementioned epoxy compounds.

[0087] As cyanate ester resins, compounds with cyanate ester groups in the molecule can be used. Specifically, phenolic varnish-type cyanate ester compounds, naphthol aralkyl-type cyanate ester compounds, biphenyl aralkyl-type cyanate ester compounds, naphthylene ether-type cyanate ester compounds, xylene resin-type cyanate ester compounds, adamantane skeleton-type cyanate ester compounds, etc., can be used.

[0088] As a benzoxazine resin, a benzoxazine compound represented by, for example, the general formula (CI) below can be used.

[0089]

[0090] In formula (C-1), R a The group representing the k-valence, Rb independently represents a halogen atom, alkyl group, or aryl group. K represents an integer from 2 to 4, and l represents an integer from 0 to 4.

[0091] Commercially available products include: "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "Pd", "Fa", and "ALP-d" manufactured by Shikoku Chemical Industry Co., Ltd.; and "HFB2006M" manufactured by Showa Polymer Co., Ltd.

[0092] As acrylic resins, compounds containing an acryloyl group can be used, such as monofunctional acrylate compounds having one acryloyl group and polyfunctional acrylate compounds having two or more acryloyl groups. Examples of the aforementioned monofunctional acrylate compounds include methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate. Examples of the aforementioned polyfunctional acrylate compounds include diacrylate compounds such as tricyclodecanediethanol diacrylate.

[0093] As methacrylic resins, compounds having an intramolecular methacryl group can be used, such as monofunctional methacrylate compounds having one intramolecular methacryl group and polyfunctional methacrylate compounds having two or more intramolecular methacryl groups. Examples of the aforementioned monofunctional methacrylate compounds include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate. Examples of the aforementioned polyfunctional methacrylate compounds include dimethacrylate compounds such as tricyclodecanediethanol dimethacrylate (DCP).

[0094] As vinyl resins, compounds containing vinyl groups within the molecule can be used, such as monofunctional vinyl compounds (monovinyl compounds) having one vinyl group within the molecule and polyfunctional vinyl compounds having two or more vinyl groups within the molecule. Examples of such polyfunctional vinyl compounds include divinylbenzene, cured polybutadiene having carbon-carbon unsaturated double bonds within the molecule, and cured butadiene-styrene copolymers having carbon-carbon unsaturated double bonds within the molecule.

[0095] As the aforementioned active ester resin, compounds with highly reactive ester groups within the molecule can be used, such as phenylcarboxylic acid active ester, phenyl dicarboxylic acid active ester, phenyl tricarboxylic acid active ester, phenyl tetracarboxylic acid active ester, naphthylcarboxylic acid active ester, naphthalene dicarboxylic acid active ester, naphthalene tricarboxylic acid active ester, naphthalene tetracarboxylic acid active ester, fluorene carboxylic acid active ester, fluorene dicarboxylic acid active ester, fluorene tricarboxylic acid active ester, and fluorene tetracarboxylic acid active ester.

[0096] As an allyl resin, compounds containing allyl groups in the molecule can be used, such as triallyl isocyanurate compounds like triallyl isocyanurate (TAIC), diallyl bisphenol compounds, and diallyl phthalate (DAP).

[0097] As phenolic resins, compounds containing hydroxyl groups bonded to an aromatic ring can be used. Examples include bisphenol A type phenolic resin, bisphenol E type phenolic resin, bisphenol F type phenolic resin, bisphenol S type phenolic resin, phenolic resin, bisphenol A phenolic varnish type phenolic resin, glycidyl ester type phenolic resin, aralkyl phenolic varnish type phenolic resin, biphenyl aralkyl type phenolic resin, cresol phenolic varnish type phenolic resin, polyfunctional phenolic resin, naphthol resin, naphthol phenolic varnish resin, polyfunctional naphthol resin, anthracene type phenolic resin, naphthalene skeleton modified phenolic varnish type phenolic resin, phenol aralkyl type phenolic resin, naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin, alicyclic phenolic resin, polyol type phenolic resin, phosphorus-containing phenolic resin, phenolic resin containing polymerizable unsaturated hydrocarbon groups, and organosilicon resins containing hydroxyl groups.

[0098] As a propylene-based resin, for example, propylene-based benzene and BPN manufactured by Gunei Chemical Industry Co., Ltd. can be used.

[0099] (Matching ratio)

[0100] The mixing ratio of compound (A) and thermosetting resin (B) in the resin composition as described above can be appropriately set within an optimal range depending on the type of compound (A) and / or thermosetting resin (B). For example, if the thermosetting resin (B) is set to 100 parts by weight, the content of compound (A) is preferably 1 to 100 parts by weight, more preferably 5 to 60 parts by weight.

[0101] <Thermoplastic Resins>

[0102] Furthermore, in order to more reliably ensure low dielectric properties or adhesive strength, a thermoplastic resin may be added to the resin composition of this embodiment.

[0103] Examples of thermoplastic resins include thermoplastic polyphenylene ether resin, polyphenylene sulfide resin, liquid crystal polymer, polyethylene resin, polystyrene resin, polyurethane resin, polypropylene resin, ABS resin, acrylic resin, polyethylene terephthalate resin, polycarbonate resin, polyacetal resin, polyimide resin, polyamide-imide resin, polytetrafluoroethylene resin, cyclic olefin polymers, cyclic olefin copolymers, and styrene-based elastomers. These resins can be used alone or in combination of two or more.

[0104] Among these, styrene-based elastomers are polymers obtained by polymerizing monomers containing styrene-based monomers, and can be styrene-based copolymers. Furthermore, examples of styrene-based copolymers include copolymers obtained by copolymerizing one or more of the aforementioned styrene-based monomers with one or more other monomers capable of copolymerizing with the aforementioned styrene-based monomers. As long as the molecule contains a structure derived from the aforementioned styrene-based monomer, the aforementioned styrene-based copolymer can be either a random copolymer or a block copolymer. Examples of block copolymers include binary copolymers of the structure (repeating unit) derived from the aforementioned styrene-based monomer and the other monomers (repeating unit) capable of copolymerizing, and ternary copolymers of the structure (repeating unit) derived from the aforementioned styrene-based monomer and the other monomers (repeating unit) capable of copolymerizing, and the structure (repeating unit) derived from the aforementioned styrene-based monomer.

[0105] The aforementioned styrene-based elastomer may be a hydrogenated styrene-based copolymer obtained by hydrogenating the aforementioned styrene-based copolymer.

[0106] The above-mentioned styrene-based elastomers can be made by using one type of styrene-based polymer alone, or by combining two or more types.

[0107] The above-mentioned styrene-based elastomers can be anhydride-modified styrene-based elastomers obtained by modifying a portion of the molecule with anhydrides.

[0108] The weight-average molecular weight of the aforementioned styrene-based elastomer is preferably 1,000 to 300,000, more preferably 1,200 to 200,000. If the molecular weight is too low, the glass transition temperature or heat resistance of the cured resin composition tends to decrease. Conversely, if the molecular weight is too high, the viscosity when the resin composition is made into a varnish or during heat molding tends to increase excessively. It should be noted that the weight-average molecular weight can be determined using conventional molecular weight determination methods; specifically, values ​​obtained using gel permeation chromatography (GPC) can be cited as examples.

[0109] As the aforementioned styrene-based elastomers, commercially available products can also be used, such as V9827, V9461, 2002, 8007, 8076, and 7125F manufactured by Kuraray Co., Ltd., FTR2140 and FTR6125 manufactured by Mitsui Chemicals Co., Ltd., and H1517, H1041, and H1221 manufactured by Asahi Kasei Corporation.

[0110] <Inorganic fillers>

[0111] The resin composition according to this embodiment may also contain an inorganic filler. Examples of inorganic fillers include substances added to improve the heat resistance or flame retardancy of the cured resin composition, and there are no particular limitations. It is believed that by containing an inorganic filler, heat resistance or flame retardancy can be improved, and the coefficient of thermal expansion can be further suppressed.

[0112] Specifically, inorganic fillers that can be used in this embodiment include, for example, metal oxides such as silica, alumina, titanium dioxide, magnesium oxide, and mica; metal hydroxides such as magnesium hydroxide and aluminum hydroxide; talc; aluminum borate; barium sulfate; aluminum nitride; boron nitride; titanium dioxide; barium titanate; strontium titanate; calcium titanate; aluminum titanate; barium zirconate titanate; barium zirconate; calcium zirconate; zirconium phosphate and zirconium phosphotungstenate; magnesium carbonate and calcium carbonate, and their boehmite-treated products. Among these, metal hydroxides such as silica, magnesium hydroxide, and aluminum hydroxide; alumina; boron nitride; barium titanate; and strontium titanate are preferred, with silica being more preferred. The silica used is not particularly limited, and examples include, for instance, fragmented silica, spherical silica, and silica particles.

[0113] These inorganic fillers can be used alone or in combination of two or more. Furthermore, the inorganic fillers described above can be used directly or after surface treatment using silane coupling agents of the epoxy silane, vinyl silane, methacryloxysilane, phenylaminosilane, or aminosilane types. As this silane coupling agent, it can be added via integral blending without pre-treating the filler material.

[0114] When the resin composition of this embodiment contains an inorganic filler, its content is preferably about 10 to 300 parts by mass relative to the total mass of the above-mentioned compound (A), the above-mentioned thermosetting resin (B), and the thermoplastic resin of 100 parts by mass, more preferably about 40 to 250 parts by mass.

[0115] <Other Ingredients>

[0116] The resin composition described in this embodiment may, as needed, contain other components besides those described above, without impairing the effects of the present invention. Other components included in the resin composition described in this embodiment may include, for example, catalysts such as reaction initiators and reaction promoters, silane coupling agents, polymerization inhibitors, polymerization retarders, defoamers, leveling agents, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes, pigments, dispersants, and lubricants.

[0117] The resin composition involved in this embodiment may contain a catalyst as described above. The catalyst is not particularly limited as long as it can promote the curing reaction of the resin composition. Specifically, examples include metal oxides, azo compounds, peroxides, imidazole compounds, phosphorus-based curing accelerators, and amine-based curing accelerators.

[0118] As metal oxides, examples include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0119] Examples of peroxides include α,α'-di(tert-butylperoxide)diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxide)-3-hexyne, benzoyl peroxide, 3,3',5,5'-tetramethyl-1,4-benzophenone, tetrachlorobenzoquinone, 2,4,6-tritert-butylphenoxy, tert-butyl peroxide monocarbonate, and azobisisobutyronitrile.

[0120] As azo compounds, examples include 2,2'-azobis(2,4,4-trimethylpentane), 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(2-methylbutyronitrile).

[0121] As a preferred reaction initiator, α,α'-di(tert-butylperoxide)diisopropylbenzene is preferably used. α,α'-di(tert-butylperoxide)diisopropylbenzene has low volatility, therefore it does not volatilize during drying and storage, exhibiting good stability. Furthermore, α,α'-di(tert-butylperoxide)diisopropylbenzene has a relatively high reaction initiation temperature, thus suppressing the accelerated curing reaction during prepreg drying and other times when curing is not required. By suppressing this curing reaction, the shelf life of the resin composition can be prevented from declining.

[0122] Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphine tetraphenylboron, n-butylphosphonium tetraphenylboron, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylthiocyanate phosphonium, tetraphenylthiocyanate phosphonium, and butyltriphenylthiocyanate phosphonium.

[0123] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyl dimethylamine, 2,4,6'-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene.

[0124] Examples of imidazole compounds include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole ontium trimellitate, 1-cyanoethyl-2-phenylimidazole ontium trimellitate, and 2,4-diamino-6-[2'-methylimidazole]. Imidazole compounds such as 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-triazine isocyanuric acid adduct, 2-phenylimidazolyl isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline.

[0125] The catalysts described above can be used alone or in combination of two or more.

[0126] <Prepregs, resin-coated films, metal-coated laminates, wiring boards, and resin-coated metal foils>

[0127] Next, the prepreg, metal-coated laminate, wiring board, and resin-coated metal foil for wiring substrates using the resin composition of this embodiment will be described. It should be noted that in the following description, each symbol represents the following meanings: 1 prepreg, 2 resin composition or semi-cured resin composition, 3 fibrous substrate, 11 metal-coated laminate, 12 insulating layer, 13 metal foil, 14 wiring, 21 wiring board, 31 resin-coated metal foil, 32 and 42 resin layers, 41 resin-coated film, 43 support film.

[0128] Figure 1 This is a schematic cross-sectional view illustrating an example of the prepreg 1 according to an embodiment of the present invention.

[0129] like Figure 1As shown, the prepreg 1 according to this embodiment includes: the above-described resin composition or the semi-cured product of the above-described resin composition 2; and a fibrous substrate 3. Examples of prepreg 1 include prepregs in which the fibrous substrate 3 is present in the above-described resin composition or its semi-cured product 2. That is, the prepreg 1 includes: the above-described resin composition or its semi-cured product; and a fibrous substrate 3 present in the above-described resin composition or its semi-cured product 2.

[0130] It should be noted that in this embodiment, "semi-cured material" refers to a material that has reached a state where the resin composition can be further cured, even if it is partially cured. In other words, a semi-cured material is a material that allows the resin composition to be in a semi-cured state (a semi-cured state). For example, if the resin composition is heated, its viscosity initially decreases gradually, then begins to cure, and the viscosity gradually increases. In this case, a semi-cured state can be described as the period from when the viscosity begins to increase until complete curing.

[0131] As a prepreg obtained using the resin composition of this embodiment, it may contain a semi-cured product of the resin composition as described above, or it may contain the uncured resin composition itself. That is, it may be a prepreg containing a semi-cured product of the resin composition (the resin composition of stage B) and a fibrous substrate, or it may be a prepreg containing the resin composition before curing (the resin composition of stage A) and a fibrous substrate. Specifically, examples include prepregs containing a fibrous substrate in the resin composition. It should be noted that the resin composition or its semi-cured product may be obtained by heating and drying the resin composition.

[0132] The resin composition involved in this embodiment is typically prepared in a varnish-like form during the manufacture of the aforementioned prepreg, resin-coated metal foil (described later), or metal-clad laminate, and used as a resin varnish. Such a resin varnish can be prepared, for example, as follows.

[0133] First, the resin components, reaction initiator, and other components soluble in the organic solvent are added to the organic solvent and dissolved. Heating may be performed as needed. Then, components insoluble in the organic solvent, such as inorganic fillers, are added, and the mixture is dispersed to a specified dispersion state using a ball mill, bead mill, planetary mixer, roller mill, or similar equipment to prepare a varnish-like resin composition. The organic solvent used here is not particularly limited as long as it can dissolve the aforementioned compound (A), the aforementioned thermosetting resin (B), the aforementioned reactive compound used as needed, and does not inhibit the curing reaction. Specifically, examples include toluene, methyl ethyl ketone, cyclohexanone, cyclopentanone, methylcyclohexane, dimethylformamide, and propylene glycol monomethyl ether acetate. These can be used alone or in combination of two or more.

[0134] As a method for manufacturing the prepreg 1 of this embodiment using the varnish-like resin composition of this embodiment, an example method is to impregnate the resin varnish-like resin composition 2 into the fibrous substrate 3 and then dry it.

[0135] Specifically, examples of fibrous substrates used in the manufacture of prepregs include glass cloth, aramid cloth, polyester cloth, LCP (liquid crystal polymer) nonwoven fabric, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, and lint paper. It should be noted that using glass cloth results in a laminate with excellent mechanical strength, and glass cloth that has undergone a flattening process is particularly preferred. The glass cloth used in this embodiment is not particularly limited, and examples include low-dielectric-constant glass cloths such as E-glass, S-glass, NE-glass, Q-glass, and L-glass. The flattening process can be performed as follows: for example, by continuously applying pressure to the glass cloth with a pressure roller at a suitable pressure, compressing the yarn to a flattened state. It should be noted that the thickness of the fibrous substrate is typically, for example, 0.01 to 0.3 mm.

[0136] The impregnation of the resin varnish (resin composition 2) into the fibrous substrate 3 is carried out by impregnation and coating, etc. This impregnation can be repeated multiple times as needed. In addition, multiple resin varnishes with different compositions and / or concentrations can be used to repeatedly impregnate the substrate, thereby ultimately adjusting to the desired composition (content ratio) and resin amount.

[0137] The fibrous substrate 3 impregnated with resin varnish (resin composition 2) is heated under desired heating conditions, for example, 80°C or higher and 180°C or lower, for 1 minute or more and 10 minutes or less. By heating, the solvent evaporates from the varnish, thereby reducing or removing the solvent, to obtain the prepreg 1 in a state before curing (stage A) or in a semi-cured state (stage B).

[0138] In addition, such as Figure 4 As shown, the resin-coated metal foil 31 of this embodiment has the following configuration: it is formed by laminating a resin layer 32 containing the above-described resin composition or a semi-cured product of the above-described resin composition and a metal foil 13. That is, the resin-coated metal foil of this embodiment may be a resin-coated metal foil having a resin layer containing the above-described resin composition before curing (the above-described resin composition of stage A) and a metal foil, or it may be a resin-coated metal foil having a resin layer containing a semi-cured product of the above-described resin composition (the above-described resin composition of stage B) and a metal foil.

[0139] As a method for manufacturing the resin-coated metal foil 31, examples include the following: coating the surface of the metal foil 13, such as a copper foil, with the resin varnish-like composition described above, and then drying it. Examples of such coating methods include bar coaters, comma coaters, die coaters, roller coaters, and gravure coaters.

[0140] The metal foil 13 described above can be any metal foil used for metal foil laminates, wiring boards, etc., and examples include copper foil and aluminum foil.

[0141] In addition, such as Figure 5 As shown, the resin-bearing membrane 41 of this embodiment has the following configuration: it is formed by laminating a resin layer 42 containing the above-described resin composition or a semi-cured product of the above-described resin composition and a membrane support substrate 43. That is, the resin-bearing membrane of this embodiment may be a resin-bearing membrane having the above-described resin composition before curing (the above-described resin composition of stage A) and a membrane support substrate, or it may be a resin-bearing membrane having a semi-cured product of the above-described resin composition (the above-described resin composition of stage B) and a membrane support substrate.

[0142] As a method for manufacturing the resin-containing membrane 41, for example, after coating the resin varnish-like resin composition as described above onto the surface of the membrane support substrate 43, the solvent is evaporated from the varnish to reduce or remove the solvent, thereby obtaining a resin-containing membrane in a pre-cured (stage A) or semi-cured (stage B) state.

[0143] Examples of electrical insulating films that can be used as the supporting substrate for the aforementioned films include polyimide films, PET (polyethylene terephthalate) films, polyester films, polyurethane films, polyetheretherketone films, polyphenylene sulfide films, aramid films, polycarbonate films, and polyacrylate films.

[0144] It should be noted that, in the resin-coated film and resin-coated metal foil of this embodiment, the resin composition or its semi-cured product can also be, in the same way as the prepreg described above, a resin composition that has been dried or heated and dried.

[0145] The thickness of the metal foil 13 and the film support substrate 43 can be appropriately set according to the desired purpose. For example, the metal foil 13 can be approximately 0.2 to 70 μm thick. When the thickness of the metal foil is, for example, 10 μm or less, a carrier-supported copper foil with a release layer and a carrier can be used to improve operability. The resin varnish is applied to the metal foil 13 and the film support substrate 43 by coating or the like, and this operation can be repeated several times as needed. In addition, multiple resin varnishes with different compositions and / or concentrations can be used for repeated coating to ultimately adjust to the desired composition (content ratio) and resin amount.

[0146] Regarding the drying or heating drying conditions in the manufacturing method of the resin-coated metal foil 31 and resin film 41, there are no particular limitations. After coating the metal foil 13 and film support substrate 43 with a resin varnish-like resin composition, the solvent is evaporated from the varnish under desired heating conditions, such as at 50 to 180°C for about 0.1 to 10 minutes, thereby reducing or removing the solvent. Thus, the resin-coated metal foil 31 and resin film 41 in the pre-cured (stage A) or semi-cured (stage B) state can be obtained.

[0147] The resin-coated metal foil 31 and resin film 41 may be equipped with a cover film as needed. By providing a cover film, the ingress of foreign matter can be prevented. As for the cover film, there are no particular limitations as long as it can be peeled off without damaging the shape of the resin composition. For example, polyolefin film, polyester film, TPX film, or films formed by providing a release agent layer on these films, and paper obtained by pressing these film layers onto a paper substrate, etc., can be used.

[0148] like Figure 2 As shown, the metal foil laminate 11 of this embodiment includes: an insulating layer 12 comprising a cured product of the above-described resin composition or a cured product of the above-described prepreg; and a metal foil 13. It should be noted that the same metal foil as described above can be used as the metal foil 13 for the metal foil laminate 11.

[0149] Alternatively, the resin-coated metal foil 31 or resin film 41 described above can also be used to manufacture the metal foil laminate 11 of this embodiment.

[0150] Regarding the method for producing a metal foil laminate using the prepreg 1, resin-coated metal foil 31, and resin film 41 obtained through the above operations, a double-sided or single-sided metal foil such as copper foil 13 is laminated by overlapping one or more pieces of prepreg 1, resin-coated metal foil 31, and resin film 41, and then heat and press them together to form a laminate. The heating and pressing conditions can be appropriately set according to the thickness of the laminate being manufactured, the type of resin composition, etc. For example, the temperature can be set to 170–230°C, the pressure to 1.5–5.0 MPa, and the time to 60–150 minutes.

[0151] Alternatively, the metal foil laminate 11 can also be manufactured without using prepreg 1, by forming a film-like resin composition on the metal foil 13 and subjecting it to heating and pressure.

[0152] In addition, such as Figure 3 As shown, the wiring board 21 of this embodiment includes: an insulating layer 12 comprising a cured product of the above-described resin composition or a cured product of the above-described prepreg; and wiring 14.

[0153] The resin composition in this embodiment is preferably used as the insulating layer material of the wiring substrate. As a method for manufacturing the wiring substrate 21, for example, a circuit (wiring) is formed by etching the metal foil 13 on the surface of the metal-clad laminate 11 obtained above, thereby obtaining a wiring board 21 with conductor patterns (wiring 14) as circuits provided on the surface of the laminate. As a circuit formation method, in addition to the methods described above, examples include forming the circuit using a semi-additive process (SAP) or a modified semi-additive process (MSAP).

[0154] The prepreg, resin-coated film, and resin-coated metal foil obtained using the resin composition of this embodiment are very useful in industrial applications because their cured products have low dielectric properties, excellent flame retardancy, and high Tg. Furthermore, the metal-clad laminates and wiring substrates formed by curing them also have the advantages of low dielectric properties, excellent flame retardancy, and high Tg.

[0155] The present invention will be further described in detail below through embodiments; however, the scope of protection of the present invention is not limited thereto.

[0156] Example

[0157] <Synthesis of Compound (A)>

[0158] (Manufacturing Example 1)

[0159] Preparation of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-triphenylmethyl-10-oxide (organic compound 1)

[0160] 21.6 g (Mw 216.2 × 0.1 mol) of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 183 g of acetonitrile were added to a 300 ml hard glass four-necked flask equipped with a stirrer, thermometer, reflux condenser and gas inlet.

[0161] Nitrogen gas was blown into the gas inlet while the temperature was increased. When the temperature reached 70°C, triphenylmethyl chloride was added in batches. After the initial addition of 9.3g of triphenylmethyl chloride, the operation of adding 9.3g of triphenylmethyl chloride every 1 hour was repeated, thus adding a total of 27.9g of triphenylmethyl chloride (Mw 278.8 × 0.1 mol) in batches.

[0162] After the batch additions were completed, the temperature of the reactor was set to 80°C for 24 hours of dehydrochlorination and aging, followed by cooling. When the reactor temperature dropped to around 25°C, the precipitated crystals were filtered by suction, and then the filtered crystals were washed with purified water until the pH of the filtrate was almost neutral, after which they were dried.

[0163] Through the above operations, 44.4 g of white crystals of organic compound 1 (Mw458.5) with a melting point of about 250 °C were obtained.

[0164] The purity of organic compound 1 was confirmed to be 99% by liquid chromatography (LC) analysis, and its infrared absorption spectrum (IR) is as follows. Figure 6 As shown, 1H-NMR is as follows Figure 7 As shown, FD-MS Figure 8 As shown, the obtained organic compound 1 was confirmed to be a compound having the following chemical structure.

[0165]

[0166] Other flame retardants

[0167] Flame retardant 1: Aromatic condensed phosphate ester (manufactured by Daihachi Chemical Industry Co., Ltd., "PX-200")

[0168] Flame retardant 2: Phosphazene compound (Fushimi Pharmaceutical Co., Ltd. "FP-100")

[0169] Flame retardant 3: Aluminum phosphonate (Clariant "OP-935")

[0170] Flame retardant 4: Melamine polyphosphate (Melapur 200 / 70 manufactured by BASF Corporation, Japan)

[0171] <Thermosetting Resin Components>

[0172] • Polyphenylene ether compounds: Modified polyphenylene ether compounds obtained by modifying the terminal hydroxyl groups of polyphenylene ether with methacrylamide groups (SA9000 manufactured by SABIC Innovative Plastics, weight average molecular weight Mw2000, number of terminal functional groups 2).

[0173] • Allyl compounds: Triallyl isocyanurate (produced by Nippon Chemical Co., Ltd. as "TALC")

[0174] <Thermoplastic Resin Composition>

[0175] • Styrene-based elastomer resin (Septon V9827 manufactured by Kuraray Co., Ltd.)

[0176] <Other Ingredients>

[0177] Catalyst 1: PBP (1,3-bis(butylperoxyisopropyl)benzene ("perbutyl P(PBP)" manufactured by Nippon Oil Co., Ltd.)

[0178] • Inorganic filler 1: Spherical silica treated with vinylsilane (silica particles "SC2300-SVJ" manufactured by Admatechs Company Limited)

[0179] (Examples 1-2 and Comparative Examples 1-4)

[0180] [Preparation Method]

[0181] (Resin varnish)

[0182] First, all the above-mentioned components, except for compound (A) and the inorganic filler, were added to toluene in the proportions (parts by mass) listed in Table 1 to achieve a solids concentration of 40–65% by mass, and then mixed. The mixture was stirred for 60 minutes. Then, compound (A) and the inorganic filler were added to the resulting liquid. After pre-dispersing with a mixer, the filler was dispersed using a bead mill. This yielded a varnish-like resin composition (varnish).

[0183] (Evaluation Sample)

[0184] Next, the prepreg and evaluation substrate (metal-clad laminate) were obtained in the following manner.

[0185] The obtained varnish was impregnated onto a fibrous substrate (glass cloth: Nitto Boshoku Co., Ltd., type #2116, E glass), and then dried at 120°C for 3 minutes to produce a prepreg. At this point, the content of the components constituting the resin composition relative to the prepreg (resin content) was adjusted to 45% by mass through a curing reaction.

[0186] Then, an evaluation substrate (metal-clad laminate) was obtained as described below.

[0187] Four prepreg sheets were overlapped, and copper foil (3EC-VLP, 12 μm thick, manufactured by Mitsui Metals & Minerals Co., Ltd.) was placed on both sides. This was used as a pressing substrate and heated to 200°C at a heating rate of 2°C / min. The substrate was then subjected to heating and pressurization at 200°C for 120 minutes and a pressure of 2 MPa, resulting in an evaluation substrate (metal-clad laminate) with copper foil bonded to both surfaces, approximately 400 μm thick.

[0188] <Evaluation Experiment>

[0189] Using bare boards obtained by etching away the copper foil from the evaluation substrates described above, flammability (average seconds) was evaluated based on the UL94 flammability test. Specifically, five evaluation substrates were exposed to a flame twice, and the average number of seconds until the flame extinguished was measured over a total of 10 flame exposures, and the average value was calculated. The evaluation standard was less than 25 seconds for acceptance. It should be noted that "complete combustion" in the table refers to the state where the flame covers the entire area of ​​the evaluation substrate from the lower end of the substrate in contact with the flame to the upper end of the substrate being held.

[0190] (Dielectric properties: Dielectric loss factor (Df))

[0191] Using a bare board obtained by etching away the copper foil from the evaluation substrate described above, the dielectric loss factor of the evaluation substrate at 10 GHz was measured using the resonant cavity perturbation method. Specifically, the dielectric loss factor (Df) of the evaluation substrate at 10 GHz was measured using a network analyzer (N5230A manufactured by Agilent Technologies, Inc.). In this test, a Df of 0.006 or less was considered acceptable.

[0192] (glass transition temperature (Tg))

[0193] Using a bare board obtained by etching away the copper foil from the evaluation substrate described above, the Tg was measured using a viscoelastic spectrometer "DMS100" manufactured by Seiko Instruments Inc. Dynamic viscoelasticity (DMA) was performed using the tensile module at a frequency of 10 Hz. The temperature at which tanδ reaches its maximum value when heated from room temperature to 320°C at a heating rate of 5°C / min was defined as Tg. In this test, a Tg of 250°C or higher was considered acceptable.

[0194] The results are shown in Table 1.

[0195]

[0196] (Inspection)

[0197] As shown in Table 1, the evaluation substrate using the resin composition of the examples exhibited good results in terms of flame retardancy, Tg, and low dielectric properties.

[0198] On the other hand, the evaluation substrate using the resin composition of Comparative Example 1 without added flame retardant did not obtain flame retardancy, and Comparative Examples 2 to 4, which used conventional flame retardants other than the compound (A) of the present invention, were unable to obtain sufficiently low dielectric properties. In addition, Comparative Examples 2 to 3 were also unable to obtain high Tg.

[0199] This application is based on Japanese Patent Application No. 2021-81741, filed on May 13, 2021, the contents of which are incorporated herein by reference.

[0200] To illustrate the present invention, it has been appropriately and sufficiently described above with reference to specific embodiments and accompanying drawings. However, it should be recognized that those skilled in the art can readily make changes and / or modifications to the above embodiments. Therefore, any modified or improved embodiments implemented by those skilled in the art that do not depart from the scope of protection of the claims can be interpreted as being included within the scope of protection of the claims.

[0201] Industrial availability

[0202] This invention has broad industrial applicability in the fields of electronic materials, electronic devices, and optical devices.

Claims

1. A resin composition, characterized in that... contain: The compound (A) is shown in the following formula. as well as, The thermosetting resin (B) contains at least one selected from epoxy resin, polyphenylene ether resin, cyanate ester resin, phenolic resin, reactive ester resin, benzoxazine resin, maleimide resin, acrylic resin, methacrylic resin and hydrocarbon resin having unsaturated double bonds.

2. The resin composition according to claim 1, characterized in that, The thermosetting resin (B) contains at least one selected from polyphenylene ether resin, maleimide resin, and hydrocarbon resin having unsaturated double bonds.

3. A resin composition, characterized in that... contain: The compound (A) is shown in the following formula. as well as, Thermosetting resin (B) contains at least one selected from vinyl resins, allyl resins, and acrylic resins. The vinyl resin refers to a compound containing vinyl groups within its molecule.

4. A prepreg, characterized in that... include: The resin composition or the semi-cured product of the resin composition according to any one of claims 1 to 3; and Fiber-based substrate.

5. A resin-coated membrane, characterized in that... include: A resin layer comprising the resin composition of any one of claims 1 to 3 or a semi-cured product of the resin composition; and Support membrane.

6. A resin-coated metal foil, characterized in that... include: A resin layer comprising the resin composition of any one of claims 1 to 3 or a semi-cured product of the resin composition; and Metal foil.

7. A metal-clad laminate, characterized in that... include: An insulating layer comprising a cured resin composition according to any one of claims 1 to 3; and Metal foil.

8. A wiring substrate, characterized in that... include: An insulating layer comprising a cured resin composition according to any one of claims 1 to 3; and wiring.

9. A metal-clad laminate, characterized in that... include: An insulating layer comprising the cured prepreg of claim 4; and Metal foil.

10. A wiring substrate, characterized in that... include: An insulating layer comprising the cured prepreg of claim 4; and wiring.

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