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

Abstract

One aspect of the present invention relates to a resin composition containing: a pre-reaction product (A) obtained by reacting in advance a mixture containing a maleimide compound (a1) having two or more maleimide groups in a molecule, and a phosphorus-containing compound (a2) that is a 9, 9, 10, 10, 10, 10, 10, 11, 12, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, 13, a compound selected from at least one of a 1, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound and a diphenylphosphine oxide compound; and a thermosetting resin (B) having two or more unsaturated double bonds.

Description

Technical Field

[0001] The present invention relates to a resin composition, and a prepreg, a resin-attached film, a resin-attached metal foil, a metal foil-clad laminate, and a wiring board using the same. Background Art

[0002] In recent years, various electronic devices have been developing rapidly in terms of high integration of semiconductor devices, high density and multi-layer wiring, etc., as the amount of information processing increases. The substrate material used to form the base material of the wiring board used in various electronic devices is required to have low electrical properties such as dielectric constant and dielectric loss factor in order to increase the signal transmission speed and reduce the loss during signal transmission.

[0003] Since the substrate materials of printed wiring boards and semiconductor packages are required to have high flame retardancy, flame retardants are usually added to the resin compositions used as their insulating materials. As flame retardants, halogen flame retardants such as bromine flame retardants are also known, but the cured products of such halogen-containing resin compositions may produce harmful substances such as hydrogen halides when burned, and have the disadvantage of causing adverse effects on the human body and the natural environment. In this context, halogen-free is also required as insulating materials for printed wiring boards and the like.

[0004] Phosphorus-based flame retardants, also known as halogen-free flame retardants, are based on the effect of phosphorus compounds in promoting the carbonization of synthetic resins. They utilize the carbonized layer generated on the surface during combustion to block the heat energy of the ignition source or the air required for combustion, thereby exerting a flame retardant effect.

[0005] It has been proposed that flame retardancy can be ensured while maintaining a certain degree of performance of a printed wiring board by adding a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative to a thermosetting resin such as a PPE (polyphenylene ether) compound (Patent Document 1).

[0006] However, although 9,10-dichloro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter also referred to as "DOPO") used in the composition described in Patent Document 1 exhibits excellent flame retardancy, when it is mixed with a resin composition, there is a problem that the thermal expansion coefficient of the cured product becomes high due to unreacted DOPO and the low dielectric properties are also poor.

[0007] Furthermore, wiring boards used in various electronic devices are also required to be less susceptible to changes in the external environment. For example, it is required that the substrate material used to form the insulating layer of the wiring board can produce a cured product with low water absorption so that the wiring board can be used even in a high humidity environment. It is believed that the insulating layer of the wiring board obtained from the substrate material that can produce such a cured product with low water absorption can suppress moisture absorption.

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resin composition whose cured product has excellent flame retardancy, low water absorption, low thermal expansion coefficient, and low dielectric properties (low dielectric loss factor).

[0009] Prior art literature

[0010] Patent Literature

[0011] Patent Document 1: Japanese Patent Publication No. 2014-198780 Summary of the invention

[0012] A resin composition according to one technical solution of the present invention comprises: a pre-reaction product (A) obtained by pre-reacting a mixture containing a maleimide compound (a1) and a phosphorus-containing compound (a2), wherein the maleimide compound (a1) has two or more maleimide groups in the molecule, and the phosphorus-containing compound (a2) is at least one of a 9,10-dihydro-9-oxa-10-phosphatase 10-oxide compound and a diphenylphosphine oxide compound; and a thermosetting resin (B) having two or more unsaturated double bonds. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 This is a schematic cross-sectional view showing the structure of a prepreg according to one embodiment of the present invention.

[0014] Figure 2 This is a schematic cross-sectional view showing the structure of a metal foil-clad laminate according to one embodiment of the present invention.

[0015] Figure 3 This is a schematic cross-sectional view showing the structure of a wiring board according to one embodiment of the present invention.

[0016] Figure 4 This is a schematic cross-sectional view showing the structure of a metal foil with resin according to one embodiment of the present invention.

[0017] Figure 5 This is a schematic cross-sectional view showing the structure of a resin film according to one embodiment of the present invention.

[0018] Figure 6 is the reaction rate of DOPO calculated in Example 1 31 P-NMR spectrum. DETAILED DESCRIPTION

[0019] The resin composition involved in an embodiment of the present invention (hereinafter, also referred to as the resin composition) contains: a pre-reaction product (A) obtained by pre-reacting a mixture containing a maleimide compound (a1) and a phosphorus-containing compound (a2), wherein the maleimide compound (a1) has two or more maleimide groups in the molecule, and the phosphorus-containing compound (a2) is at least one of a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound and a diphenylphosphine oxide compound; and a thermosetting resin (B) having two or more unsaturated double bonds.

[0020] By the above-mentioned constitution, it is possible to provide a resin composition having a high flame retardancy and low water absorption, low thermal expansion coefficient and low dielectric properties (low dielectric loss factor) in a cured product and a laminate, wiring board, etc. comprising the cured product, although not containing halogen atoms. In addition, it is possible to provide a prepreg, a film with resin, a metal foil with resin, a metal foil-clad laminate and a wiring board having excellent flame retardancy and low water absorption, low thermal expansion coefficient and low dielectric properties (low dielectric loss factor) by using the resin composition.

[0021] Hereinafter, each component of the resin composition according to the present embodiment will be described in detail.

[0022] (Pre-reaction product (A))

[0023] The resin composition of the present embodiment contains a pre-reaction product (reaction product) (A) obtained by reacting a mixture containing a maleimide compound (a1) and a phosphorus-containing compound (a2) in advance, wherein the maleimide compound (a1) has two or more maleimide groups in the molecule, and the phosphorus-containing compound (a2) is at least one of a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound and a diphenylphosphine oxide compound. As long as the mixture contains the maleimide compound (a1) component and the phosphorus-containing compound (a2) component, it may also contain other components, and as the third component, for example, a catalyst, a curing accelerator, other resins, etc. can be listed.

[0024] That is, the resin composition of the present embodiment contains a pre-reaction product (A) obtained by pre-reacting at least a part of the maleimide group of the maleimide compound (a1) with a phosphorus-containing compound (a2), wherein the phosphorus-containing compound (a2) is at least one of the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter, also referred to as "DOPO") compound and a diphenylphosphine oxide compound.

[0025] In this way, by reacting the maleimide compound (a1) and the phosphorus-containing compound (a2) in advance, the phosphaphenanthrene skeleton of DOPO and / or the diphenylphosphine oxide skeleton of the diphenylphosphine oxide compound are bonded to a part of the maleimide groups, thereby suppressing the deterioration of low dielectric properties, low thermal expansion coefficient and low water absorption caused by directly mixing DOPO and the like into the resin composition.

[0026] In addition, in this embodiment, the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound and the diphenylphosphine oxide compound include their respective derivatives.

[0027] The pre-reaction product (hereinafter also referred to as "pre-reaction product") (A) obtained by pre-reacting the maleimide compound (a1) and the phosphorus-containing compound (a2) in this embodiment preferably contains a phosphorus-containing maleimide compound (A-1), wherein the phosphorus-containing maleimide compound (A-1) is at least one of a phosphorus-containing maleimide compound having a group represented by the following formula (1) and a phosphorus-containing maleimide compound having a group represented by the following formula (2).

[0028]

[0029] Moreover, the phosphorus-containing maleimide compound (A-1) preferably contains a phosphorus-containing maleimide compound (A-2), and the phosphorus-containing maleimide compound (A-2) is at least one of a phosphorus-containing maleimide compound having a group represented by the following formula (3) and a phosphorus-containing maleimide compound having a group represented by the following formula (4).

[0030]

[0031] It is considered that the phosphorus-containing maleimide compound (A-2) has the advantages of imparting flame retardancy and suppressing deterioration of mechanical properties and electrical characteristics.

[0032] In this embodiment, the pre-reaction product (A) is preferably a reaction product (product) obtained by pre-reacting a maleimide compound (a1) with a phosphorus-containing compound (a2) which is at least one of a DOPO compound and a diphenylphosphine oxide compound at a mass ratio (a1): (a2) = 50:50 to 95:5. It is believed that by reacting at this ratio, a higher flame retardancy can be obtained more reliably. The preferred range of the ratio of (a1): (a2) is 55:45 to 90:10.

[0033] In the pre-reaction product (A) of the present embodiment, the reaction of the maleimide compound (a1) and the phosphorus-containing compound (a2) may not be completely completed, as long as a portion of them has reacted and the remaining portion may be in an unreacted state. That is, the pre-reaction product (A) of the present embodiment may contain a portion of unreacted maleimide compound (a1) and phosphorus-containing compound (a2) in addition to the pre-reaction product containing the (a1) component and the (a2) component.

[0034] The reaction ratio in the preliminary reaction product (A) is not particularly limited, but it is preferred that the reaction be conducted so that the reaction rate of the phosphorus-containing compound (a2) component reaches 30% or more and less than 100%. 31 The reaction rate is determined by the peak area value of the phosphorus-containing compound (a2) component in the P-NMR analysis and the peak area value of the pre-reaction product (A). More specifically, the pre-reaction product (A) contains unreacted phosphorus-containing compound (a2) and phosphorus-containing compound (a2-1) obtained by reacting the phosphorus-containing compound (a2) in advance. In this embodiment, the reaction rate is calculated based on 31 The peak area value of the phosphorus-containing compound (a2-1) in the P-NMR spectrum is calculated by the calculation formula of the peak area value of the phosphorus-containing compound (a2-1) / (peak area value of the component (a2) + peak area value of the phosphorus-containing compound (a2-1)). It is believed that by reacting in a manner such that the reaction rate of the phosphorus-containing compound (a2) component is within the range, the flame retardancy of the cured product of the resin composition can be ensured, and the effects of improving low dielectric properties, low thermal expansion coefficient and low water absorption can be obtained more reliably. The more preferred range of the reaction rate is 50% or more and 100% or less.

[0035] As more specific reaction conditions, for example, when a DOPO compound is used as the phosphorus-containing compound (a2), the maleimide compound (a1) and the DOPO compound (a2) can be added to a solvent such as toluene in the above-mentioned ratio so that the solid content concentration reaches about 50 to 70%, and the reaction is carried out at a temperature of about 90 to 120°C for about 3 to 9 hours.

[0036] Alternatively, when a diphenylphosphine oxide compound is used as the phosphorus-containing compound (a2), the maleimide compound (a1) and the diphenylphosphine oxide compound (a2) can be added to a solvent such as toluene in the above-mentioned ratio so that the solid content concentration reaches about 50 to 70%, and the reaction is carried out at a temperature of about 90 to 120°C for about 1 to 3 hours to obtain a pre-reaction product (A).

[0037] The maleimide compound (a1) that can be used in the pre-reaction product (A) of the present embodiment is not particularly limited as long as it is a multifunctional maleimide compound having two or more maleimide groups in the molecule. Since the maleimide compound (a1) reacts with both DOPO and the thermosetting resin (B), it has the advantage of being able to suppress the degradation of mechanical properties and electrical properties while imparting flame retardancy.

[0038] More specifically, for example, maleimide compounds having two or more N-substituted maleimide groups in the molecule and modified maleimide compounds are mentioned, etc. These may be used alone or in combination of two or more.

[0039] The maleimide compound (a1) used in this embodiment can be a commercially available product, for example: the solid components of MIR-3000-70MT and MIR-5000-60T manufactured by Nippon Kayaku Co., Ltd.; BMI-4000, BMI-2300, BMI-5100, BMI-TMH manufactured by Yamato Chemical Industry Co., Ltd.; and BMI-689, BMI-1500, BMI-3000J, BMI-5000, etc. manufactured by Designer Molecules Inc.

[0040] Alternatively, as the maleimide compound (a1), a maleimide compound containing an indane structure may be used. More specifically, maleimide compounds having a structure represented by the following formula (5) in the molecule may be mentioned.

[0041]

[0042] In formula (5), Ra is independently represented. That is, Ra may be the same group or different groups. For example, when q is 2 to 4, 2 to 4 Ra bonded to the same benzene ring may be the same group or different groups. Ra represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group or a mercapto group. Rb represents an alkyl group having 1 to 10 carbon atoms, an alkyloxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an arylthio group having 6 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a halogen atom, a nitro group, a hydroxyl group or a mercapto group. q represents an integer of 0 to 4. r represents an integer of 0 to 3. n represents an integer of 0.95 to 10.

[0043] In the preliminary reaction product (A) of the present embodiment, at least one of a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound and a diphenylphosphine oxide compound is used as the phosphorus-containing compound (a2) to be reacted in advance with the maleimide compound (a1).

[0044] The 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound is a compound containing a group represented by the above formula (1), and the compound also includes 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and its derivatives.

[0045] Furthermore, the diphenylphosphine oxide compound is a compound containing a group represented by the above formula (2), and the compound also includes a derivative of diphenylphosphine oxide.

[0046] The DOPO and diphenylphosphine oxide compound (a2) are phosphorus-based flame retardants with high flame retardancy. By containing a pre-reaction product (A) of at least one of the phosphorus-containing compound (a2), i.e., these compounds and their derivatives, the resin composition of this embodiment can exhibit high flame retardancy. DOPO and DOPO derivatives can be synthesized by a known method, but commercial products can also be used, for example, "HCA" manufactured by Sanko Co., Ltd. can be used. In addition, as a diphenylphosphine oxide compound, "OX-2" manufactured by Katayama Chemical Industry Co., Ltd. can be used.

[0047] (Thermosetting resin (B))

[0048] The thermosetting resin (B) used in this embodiment is not particularly limited as long as it is a thermosetting resin having two or more unsaturated double bonds and can be used as a wiring board material. By using such a thermosetting resin (B) having two or more unsaturated double bonds, it has the advantage of being able to impart low dielectric properties and high heat resistance.

[0049] Specific examples of thermosetting resins (B) include polyphenylene ether compounds, allyl compounds, acrylate compounds, methacrylate compounds, vinyl compounds, styrene compounds, maleimide compounds (b1) different from the maleimide compound (a1) described above, and benzoxazine having an allyl group in the molecule, and each of them has two or more unsaturated double bonds.

[0050] Among them, it is more preferred to use a resin whose cured product has a low dielectric loss tangent, a low thermal expansion coefficient, and low water absorption. Specifically, it is preferred to contain at least one selected from a polyphenylene ether compound, a maleimide compound (b1), and a styrene-based compound.

[0051] As the polyphenylene ether compound having two or more unsaturated double bonds of the present embodiment, it is preferably a modified polyphenylene ether compound substituted with chloromethylstyrene, methacryloyl chloride, etc. The polyphenylene ether compound can be synthesized by a known method or a commercially available product. As commercially available products, for example, "OPE-2st1200", "OPE-2st 2200" manufactured by Mitsubishi Gas Chemical Co., Ltd., "SA9000", "SA90", "SA120", "Noryl640" manufactured by SABIC Innovative Plastics, etc. can be cited.

[0052] The allyl compound that can be used in the present embodiment is a polyfunctional allyl compound having two or more allyl groups in the molecule, and examples thereof include triallyl isocyanurate compounds such as triallyl isocyanurate (TAIC), diallyl bisphenol compounds, and diallyl phthalate (DAP).

[0053] The acrylate compound that can be used in this embodiment is a compound having an acryloyl group in the molecule, and examples thereof include a multifunctional acrylate compound having two or more acryloyl groups in the molecule, etc. Examples of the multifunctional acrylate compound include diacrylate compounds such as tricyclodecane dimethanol diacrylate, etc.

[0054] The methacrylate compound that can be used in this embodiment is a compound having a methacryloyl group in the molecule, and examples thereof include: a multifunctional methacrylate compound having two or more methacryloyl groups in the molecule, etc. Examples of the multifunctional methacrylate compound include: dimethacrylate compounds such as tricyclodecane dimethanol dimethacrylate (DCP), etc.

[0055] The vinyl compound that can be used in this embodiment is a compound having a vinyl group in the molecule, and examples thereof include a multifunctional vinyl compound having two or more vinyl groups in the molecule. Examples of the multifunctional vinyl compound include divinylbenzene, a curable polybutadiene having a carbon-carbon unsaturated double bond in the molecule, and a curable butadiene-styrene copolymer having a carbon-carbon unsaturated double bond in the molecule.

[0056] The styrene-based compound that can be used in the present embodiment is not particularly limited as long as it is a compound having a styrene group, and examples thereof include styrene-based compounds represented by the following formula (6).

[0057]

[0058] In formula (6), X represents a hydrocarbon group having at least 6 carbon atoms and containing at least one selected from aromatic ring groups and aliphatic ring groups.

[0059] More specifically, for example, a styrene compound represented by the following formula (7) can be mentioned.

[0060]

[0061] In formula (7), n represents an integer of 1 to 10.

[0062] The maleimide compound (b1) is not particularly limited as long as it is different from the maleimide compound (a1) described above, and examples thereof include maleimide compounds such as 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, meta-phenylene bismaleimide, and 4-methyl-1,3-phenylene bismaleimide compounds.

[0063] The benzoxazine compound is not particularly limited as long as it has an allyl group in the molecule, and for example, a benzoxazine compound represented by the following general formula (CI) can be used.

[0064]

[0065] In formula (CI), R 1 Represents a k-valent group, R 2 represents an aryl group. k represents an integer of 2 to 4, and l represents an integer of 0 to 4. Commercially available products can be used for the benzoxazine compound, and specific examples thereof include "ALP-d" manufactured by Shikoku Chemicals Co., Ltd.

[0066] (Content ratio and content)

[0067] In the resin composition of the present embodiment, the content of the pre-reaction product (A) and the thermosetting resin (B) is not particularly limited, and the ratio of the pre-reaction product (A) to the thermosetting resin (B) is preferably 70:30 to 10:90 by mass ratio. It is believed that by making the content ratio of the pre-reaction product (A) and the thermosetting resin (B) in the resin composition within the above range, low dielectric properties (especially low dielectric loss factor) can be obtained more reliably. The preferred range of the content ratio is 65:35 to 25:75 by mass ratio.

[0068] In the resin composition of the present embodiment, if the resin component in the resin composition is set to 100 parts by mass, the content of the pre-reaction product (A) is about 15 to 70 parts by mass, and more preferably about 25 to 65 parts by mass. In addition, if the resin component in the resin composition is set to 100 parts by mass, the content of the thermosetting resin (B) is about 30 to 85 parts by mass, and more preferably about 35 to 75 parts by mass.

[0069] (Inorganic filler)

[0070] The resin composition involved in the present embodiment may further contain an inorganic filler. As the inorganic filler, there may be cited substances added to improve the heat resistance and flame retardancy of the cured product of the resin composition, etc., without particular limitation. It is believed that: by containing an inorganic filler, heat resistance and flame retardancy, etc. can be further improved, and the thermal expansion coefficient can also be suppressed to be lower (to achieve lower thermal expansion).

[0071] As inorganic fillers that can be used in this embodiment, specifically, for example, metal oxides such as silica, alumina, titanium oxide, magnesium oxide, and mica; metal hydroxides such as magnesium hydroxide and aluminum hydroxide; talc; aluminum borate, barium sulfate, aluminum nitride, boron nitride; barium titanate, strontium titanate, calcium titanate, aluminum titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate; magnesium carbonate and calcium carbonate such as anhydrous magnesium carbonate; and their boehmite-treated products. Among them, preferred are metal hydroxides such as silica, magnesium hydroxide and aluminum hydroxide, alumina, boron nitride, and barium titanate, strontium titanate, and the like, and more preferred is silica. The silica is not particularly limited, and for example, crushed silica, spherical silica, and silica particles can be cited.

[0072] These inorganic fillers can be used alone or in combination of two or more. In addition, the inorganic filler as described above can be used directly, or an inorganic filler surface-treated by a silane coupling agent of epoxysilane type, vinylsilane type, methacrylsilane type, phenylaminosilane type or aminosilane type can be used. As the silane coupling agent, a method of adding the filler by an overall blending method can be used instead of a method of surface-treating the filler in advance.

[0073] When the resin composition of the present embodiment contains an inorganic filler, the content thereof is preferably 10 to 300 parts by mass, more preferably 20 to 200 parts by mass, based on 100 parts by mass of the total mass of the preliminary reaction product (A) and the thermosetting resin (B).

[0074] <Other ingredients>

[0075] The resin composition of the present embodiment may contain components (other components) other than the above components as required within the scope of not impairing the effect of the present invention. As other components contained in the resin composition of the present embodiment, for example, resin components other than the above maleimide compound (a1) and the thermosetting resin (B), resin components other than the above 9, 10- Additives other than dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (a2) or its derivatives, such as flame retardants, reaction initiators, catalysts such as reaction accelerators, silane coupling agents, polymerization inhibitors, polymerization retardants, flame retardant aids, defoaming agents, leveling agents, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes or pigments, dispersants and lubricants.

[0076] Examples of the other resins include epoxy resins, phenol resins, and cyanate esters.

[0077] Examples of other flame retardants include phosphorus-based flame retardants such as phosphate ester-based flame retardants, phosphazene-based flame retardants, bisdiphenylphosphine-based flame retardants, and phosphinate-based flame retardants.

[0078] In addition, the resin composition involved in the present embodiment may contain a reaction initiator (catalyst) and a reaction accelerator as described above. The reaction initiator and the reaction accelerator are not particularly limited as long as they can promote the curing reaction of the resin composition. Specifically, for example, metal oxides, azo compounds, peroxides, imidazole compounds, phosphorus-based curing accelerators, amine-based curing accelerators, etc. can be cited.

[0079] Specific examples of the metal oxide include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0080] Examples of the peroxide include α,α′-di(tert-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, benzoyl peroxide, 3,3′,5,5′-tetramethyl-1,4-diphenolquinone, chloranil, 2,4,6-tri-tert-butylphenoxy, tert-butylperoxyisopropyl monocarbonate, and azobisisobutyronitrile.

[0081] Specific examples of the azo compound include 2,2′-azobis(2,4,4-trimethylpentane), 2,2′-azobis(N-butyl-2-methylpropionamide), and 2,2′-azobis(2-methylbutyronitrile).

[0082] Among them, α, α'-di(tert-butylperoxy)diisopropylbenzene is preferably used as a preferred reaction initiator. α, α'-di(tert-butylperoxy)diisopropylbenzene has low volatility, so it does not volatilize during drying and storage, and has good stability. In addition, α, α'-di(tert-butylperoxy)diisopropylbenzene has a relatively high reaction starting temperature, so it can inhibit the promotion of the curing reaction when the prepreg is dried and curing is not required. By inhibiting the curing reaction, the storage property of the resin composition can be inhibited from being reduced.

[0083] Examples of the phosphorus-based curing accelerator include triphenylphosphine, boric acid phosphorus ester compounds, tetraphenylboron tetraphenylphosphine, n-butylboron tetraphenylphosphine, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate.

[0084] Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)undecene.

[0085] Examples of the imidazole compound 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-decylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, and 1-cyanoethyl-2-phenylimidazolium trimellitate. trimellitate), 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')2-ethyl-4-methylimidazolyl]-ethyl-s-triazine ne), 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct (2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct), 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole2-a]benzimidazole), 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds.

[0086] The above-mentioned reaction initiators may be used alone or in combination of two or more.

[0087] When the resin composition of the present embodiment contains the reaction initiator, its content is not particularly limited. For example, it is preferably 0.01 to 5.0 parts by mass, more preferably 0.01 to 3 parts by mass, and further preferably 0.05 to 3.0 parts by mass, relative to 100 parts by mass of the total of the maleimide compound (A) and the hydrocarbon compound (B) (when the reactive compound (C) is contained, relative to 100 parts by mass of the total of the maleimide compound (A), the hydrocarbon compound (B) and the reactive compound (C)).

[0088] (Prepreg, film with resin, metal foil-clad laminate, wiring board, and metal foil with resin)

[0089] Next, a prepreg for a wiring board, a metal foil-clad laminate, a wiring board, and a metal foil with resin using the resin composition of the present embodiment will be described.

[0090] Figure 1 1 is a schematic cross-sectional view showing an example of a prepreg 1 according to an embodiment of the present invention. In addition, each symbol in the figure represents the following: 1 prepreg, 2 resin composition or semi-cured product of resin composition, 3 fibrous substrate, 11 metal foil-clad laminate, 12 insulating layer, 13 metal foil, 14 wiring, 21 wiring board, 31 metal foil with resin, 32, 42 resin layer, 41 film with resin, 43 support film.

[0091] like Figure 1 As shown, the prepreg 1 according to the present embodiment comprises: the resin composition or the semi-cured product 2 of the resin composition; and a fibrous base material 3. Examples of the prepreg 1 include a prepreg in which the fibrous base material 3 is present in the resin composition or the semi-cured product 2. That is, the prepreg 1 comprises: the resin composition or the semi-cured product thereof; and the fibrous base material 3 present in the resin composition or the semi-cured product 2.

[0092] It should be noted that, in the present embodiment, "semi-cured material" is a material that cures the resin composition to a state in which the resin composition can be further cured midway. That is, the semi-cured material is a material that makes the resin composition semi-cured (B-staged). For example, if the resin composition is heated, the viscosity is slowly reduced at first, and then solidification begins, and the viscosity slowly rises. In this case, as semi-cured, the state during the period from when the viscosity begins to rise to before fully solidified can be cited.

[0093] As the prepreg obtained by using the resin composition involved in the present embodiment, it can be a prepreg with a semi-cured product of the resin composition as described above, and it can also be a prepreg with an uncured resin composition. That is, it can be a prepreg with a semi-cured product of the resin composition (the resin composition in the second stage) and a fibrous substrate, and it can also be a prepreg with the resin composition before curing (the resin composition in the first stage) and a fibrous substrate. Specifically, for example, a prepreg with a fibrous substrate in the resin composition can be cited. It should be noted that the resin composition or its semi-cured product can be a substance obtained by heating and drying the resin composition.

[0094] When producing the above-mentioned prepreg, the resin-coated metal foil, the metal foil-clad laminate, etc., which will be described later, the resin composition according to the present embodiment is often prepared into a varnish state and used as a resin varnish. The resin varnish can be prepared, for example, as follows.

[0095] First, a mixture containing maleimide compound (a1) and phosphorus-containing compound (a2) is reacted under the above conditions to obtain a pre-reaction product (A), then, each component soluble in an organic solvent such as the pre-reaction product (A) and thermosetting resin (B), reaction initiator, etc. is put into an organic solvent and dissolved. At this time, heating can be performed as required. Then, an inorganic filler as a component insoluble in an organic solvent is added, and a ball mill, a bead mill, a planetary mixer, a roller mill, etc. are used to disperse to a specified dispersion state, thereby preparing a varnish-like resin composition. As the organic solvent used herein, as long as it is an organic solvent that can dissolve the pre-reaction product (A) and the thermosetting resin (B) and the like and does not hinder the curing reaction, it is not particularly limited. Specifically, for example, toluene, methyl ethyl ketone, cyclohexanone, cyclopentanone, methylcyclohexane, dimethylformamide and propylene glycol monomethyl ether acetate, etc. can be cited. These can be used alone or in combination with more than two kinds.

[0096] As a method of producing the prepreg 1 of the present embodiment using the varnish-like resin composition of the present embodiment, for example, there is a method of impregnating the fibrous base material 3 with the resin varnish-like resin composition 2 and then drying it.

[0097] As the fibrous substrate used in the manufacture of prepreg, specific examples include: glass cloth, aramid cloth, polyester cloth, LCP (liquid crystal polymer) non-woven fabric, glass non-woven fabric, aramid non-woven fabric, polyester non-woven fabric, pulp paper, and cotton linter paper. It should be noted that when glass cloth is used, a laminate with excellent mechanical strength can be obtained, and glass cloth processed by flattening 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. As a flattening process, specifically, for example, the glass cloth can be continuously pressed with a rigid roller at an appropriate pressure to compress the yarn into a flat state. It should be noted that as the thickness of the fibrous substrate, a fibrous substrate of, for example, 0.01 to 0.3 mm can usually be used.

[0098] The impregnation of the resin varnish (resin composition 2) into the fibrous substrate 3 is performed by impregnation and coating. The impregnation may be repeated multiple times as needed. In addition, multiple resin varnishes with different compositions and concentrations may be used to repeatedly impregnate, thereby finally adjusting to the desired composition (content ratio) and resin amount.

[0099] The fibrous substrate 3 impregnated with the resin varnish (resin composition 2) is heated under desired heating conditions, for example, at 80°C or higher and 180°C or lower for 1 minute or longer and 10 minutes or shorter. By heating, the solvent is volatilized from the varnish to reduce or remove the solvent, thereby obtaining a prepreg 1 before curing (A stage) or in a semi-cured state (B stage).

[0100] In addition, if Figure 4 As shown, the metal foil with resin 31 of the present embodiment has the following structure: a structure in which a resin layer 32 containing the resin composition or a semi-cured product of the resin composition and a metal foil 13 are stacked. That is, the metal foil with resin of the present embodiment may be a metal foil with resin including: a resin layer containing the resin composition before curing (the resin composition in the A stage); and a metal foil, or may be a metal foil with resin including: a resin layer containing a semi-cured product of the resin composition (the resin composition in the B stage); and a metal foil.

[0101] As a method for manufacturing the metal foil 31 with resin, for example, the following method can be cited: a method in which the resin composition in the form of resin varnish as described above is applied to the surface of the metal foil 13 such as copper foil and then dried. As the coating method, a bar coater, a comma coater, a die coater, a roll coater, a gravure coater, etc. can be cited.

[0102] As the metal foil 13 , any metal foil used for metal foil-clad laminates, wiring boards, etc. can be used without limitation, and examples thereof include copper foil and aluminum foil.

[0103] In addition, if Figure 5 As shown, the film with resin 41 of the present embodiment has the following structure: a structure in which a resin layer 42 containing the resin composition or a semi-cured product of the resin composition and a film supporting substrate 43 are stacked. That is, the film with resin of the present embodiment may be a film with resin including: the resin composition before curing (the resin composition in the A stage); and a film supporting substrate, or may be a film with resin including: a semi-cured product of the resin composition (the resin composition in the B stage); and a film supporting substrate.

[0104] As a method for manufacturing the resin-bearing film 41, for example, after coating the resin varnish-like resin composition as described above on the surface of the film supporting substrate 43, the solvent is evaporated from the varnish to reduce or remove the solvent, thereby obtaining a resin-bearing film before curing (stage A) or in a semi-cured state (stage B).

[0105] Examples of the film supporting substrate include electrically insulating films such as polyimide films, PET (polyethylene terephthalate) films, polyethylene naphthalate films, polyester films, polyparabanic acid films, polyetheretherketone films, polyphenylene sulfide films, aramid films, polycarbonate films, and polyarylate films.

[0106] In addition, in the film with resin and the metal foil with resin of this embodiment, similarly to the above-mentioned prepreg, the resin composition or its semi-cured product may be a resin composition or its semi-cured product obtained by drying or heat-drying the resin composition.

[0107] The thickness of the metal foil 13 and the film support substrate 43 can be appropriately set according to the desired purpose. For example, as the metal foil 13, a metal foil of about 0.2 to 70 μm can be used. When the thickness of the metal foil is, for example, less than 10 μm, a copper foil with a carrier having a peeling 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, etc., and the operation can be repeated multiple times as needed. In addition, at this time, multiple resin varnishes with different compositions and concentrations can be repeatedly applied, so as to finally adjust to the desired composition (content ratio) and resin amount.

[0108] There is no particular limitation on the drying or heat-drying conditions in the method for manufacturing the metal foil 31 with resin and the resin film 41. After applying a resin varnish-like resin composition to the above-mentioned metal foil 13 and the film supporting substrate 43, heating is performed under desired heating conditions, for example, at 50 to 180°C for about 0.1 to 10 minutes to evaporate the solvent from the varnish and reduce or remove the solvent, thereby obtaining the metal foil 31 with resin and the resin film 41 before curing (stage A) or in a semi-cured state (stage B).

[0109] The metal foil 31 with resin and the resin film 41 may be provided with a covering film etc. as required. By providing the covering film, it is possible to prevent the mixing of foreign matter etc. As the covering film, there is no particular limitation as long as it can be peeled off without damaging the form of the resin composition, and for example, polyolefin film, polyester film, TPX film, a film formed by providing a release agent layer on these films, and paper obtained by laminating these films on a paper substrate etc. can be used.

[0110] like Figure 2 As shown, the metal foil-clad laminate 11 of this embodiment includes: an insulating layer 12 including a cured product of the resin composition or a cured product of the prepreg; and a metal foil 13. It should be noted that as the metal foil 13 used for the metal foil-clad laminate 11, the same metal foil as the metal foil 13 described above can be used.

[0111] In addition, the metal foil-clad laminate 11 of the present embodiment may be produced by using the above-mentioned metal foil 31 with resin or the resin film 41 .

[0112] As for the method of making a metal foil-clad laminate using the prepreg 1, the metal foil 31 with resin, and the resin film 41 obtained by the above operation, a single piece or multiple pieces of the prepreg 1, the metal foil 31 with resin, and the resin film 41 are taken, and a metal foil 13 such as copper foil is further overlapped on both sides or one side of the upper and lower surfaces thereof, and the metal foil 13 is heated and pressed to form and laminated to form a laminated body with metal foil on both sides or one side. The heating and pressing conditions can be appropriately set according to the thickness of the laminate to be manufactured, the type of resin composition, etc., for example, the temperature can be set to 170 to 230°C, the pressure can be set to 1.5 to 5.0 MPa, and the time can be set to 60 to 150 minutes.

[0113] The metal foil-clad laminate 11 may be produced by forming a film-like resin composition on the metal foil 13 and applying heat and pressure without using the prepreg 1 or the like.

[0114] In addition, if Figure 3 As shown, wiring board 21 of the present embodiment includes: insulating layer 12 including a cured product of the above-mentioned resin composition or a cured product of the above-mentioned prepreg; and wiring 14.

[0115] The resin composition of this embodiment is suitable for use as a material for an insulating layer of a wiring board. As a method for manufacturing a wiring board 21, for example, the metal foil 13 on the surface of the metal foil-clad laminate 11 obtained above is etched to form a circuit (wiring), thereby obtaining a wiring board 21 having a conductor pattern (wiring 14) as a circuit on the surface of the laminate. As a method for forming a circuit, in addition to the method described above, for example, a method for forming a circuit by a semi-additive process (SAP: Semi Additive Process) or a modified semi-additive process (MSAP: Modified Semi Additive Process) can be cited.

[0116] The prepreg, film with resin, and metal foil with resin obtained using the resin composition of the present embodiment are very useful in industrial utilization because their cured products have excellent low dielectric properties, low thermal expansion coefficient, and flame retardancy, and their water absorption is also suppressed. In addition, the metal foil-clad laminate and wiring board having an insulating layer containing the cured product of the resin composition of the present embodiment have the advantages of having low dielectric properties, low thermal expansion coefficient, and flame retardancy, and being able to suppress water absorption (moisture absorption).

[0117] As described above, this specification discloses various types of technologies, and the main technologies are summarized as follows.

[0118] The first technical solution of the present invention relates to a resin composition comprising: a pre-reaction product (A) obtained by pre-reacting a mixture containing a maleimide compound (a1) and a phosphorus-containing compound (a2), wherein the maleimide compound (a1) has two or more maleimide groups in the molecule, and the phosphorus-containing compound (a2) is at least one of a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound and a diphenylphosphine oxide compound; and a thermosetting resin (B) having two or more unsaturated double bonds.

[0119] The resin composition according to the second technical solution of the present invention is the resin composition according to the first technical solution, wherein the pre-reaction product (A) is a reaction product obtained by pre-reacting the maleimide compound (a1) and the phosphorus-containing compound (a2) at a mass ratio of 50:50 to 95:5, and the phosphorus-containing compound (a2) is at least one of a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound and a diphenylphosphine oxide compound.

[0120] The resin composition according to the third aspect of the present invention comprises the resin composition according to any one of the first and second aspects, wherein the preliminary reaction product (A) and the thermosetting resin (B) are contained in a mass ratio of 70:30 to 10:90.

[0121] The resin composition involved in the fourth technical solution of the present invention is the resin composition of any one of the first to third technical solutions, wherein the pre-reaction product (A) contains a phosphorus-containing maleimide compound (A-1), and the phosphorus-containing maleimide compound (A-1) is at least one of a phosphorus-containing maleimide compound having a group represented by the above formula (1) and a phosphorus-containing maleimide compound having a group represented by the above formula (2).

[0122] The resin composition involved in the fifth technical solution of the present invention is the resin composition of any one of the first to fourth technical solutions, wherein the phosphorus-containing maleimide compound (A-1) contains a phosphorus-containing maleimide compound (A-2), and the phosphorus-containing maleimide compound (A-2) is at least one of a phosphorus-containing maleimide compound having a group represented by the following formula (3) and a phosphorus-containing maleimide compound having a group represented by the following formula (4).

[0123] The resin composition involved in the sixth technical scheme of the present invention is the resin composition of any one of the first to fifth technical schemes, wherein the pre-reaction product (A) contains unreacted phosphorus-containing compound (a2) and a phosphorus-containing compound (a2-1) obtained by pre-reacting the phosphorus-containing compound (a2), and the reaction rate of the phosphorus-containing compound (a2) is greater than 30% and less than 100%, and the reaction rate is calculated based on the peak area value of the phosphorus-containing compound (a2-1) in the 31P-NMR spectrum / (peak area value of component (a2) + peak area value of the phosphorus-containing compound (a2-1)).

[0124] The resin composition involved in the seventh technical solution of the present invention is the resin composition of any one of the first to sixth technical solutions, wherein the thermosetting resin (B) contains at least one selected from the group consisting of a polyphenylene ether compound, an allyl compound, an acrylate compound, a methacrylate compound, a vinyl compound, a styrene-based compound, a maleimide compound (b1) different from the maleimide compound (a1), and a benzoxazine compound having an allyl group, each of which has two or more unsaturated double bonds.

[0125] The resin composition according to an eighth aspect of the present invention is the resin composition according to any one of the first to seventh aspects, further comprising an inorganic filler.

[0126] A ninth technical aspect of the present invention relates to a prepreg comprising: the resin composition according to any one of the first to eighth technical aspects or a semi-cured product of the resin composition; and a fibrous base material.

[0127] A tenth invention of the present invention relates to a film with a resin, comprising: a resin layer comprising the resin composition according to any one of the first to eighth inventions or a semi-cured product of the resin composition; and a support film.

[0128] An eleventh invention of the present invention relates to a metal foil with resin, comprising: a resin layer comprising the resin composition according to any one of the first to eighth inventions or a semi-cured product of the resin composition; and a metal foil.

[0129] A twelfth invention of the present invention is a metal foil-clad laminate comprising: an insulating layer comprising a cured product of the resin composition of any one of the first to eighth inventions or a cured product of the prepreg of the ninth invention; and a metal foil.

[0130] A thirteenth invention of the present invention is directed to a wiring board comprising: an insulating layer comprising a cured product of the resin composition of any one of the first to eighth inventions or a cured product of the prepreg of the ninth invention; and wiring.

[0131] Hereinafter, the present invention will be further specifically described by way of examples; however, the scope of the present invention is not limited to these examples.

[0132] Example

[0133] First, the components used in preparing the resin composition in this example are described.

[0134] (Maleimide compound (a1))

[0135] · Polyfunctional maleimide compound: MIR-5000 (manufactured by Nippon Kayaku Co., Ltd.)

[0136] (Flame retardant: phosphorus-containing compound (a2))

[0137] 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide: HCA (manufactured by Sanko Co., Ltd.)

[0138] (Thermosetting resin (B))

[0139] Polyphenylene ether compound: OPE-2St-1200 (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

[0140] (Inorganic filler)

[0141] · Silica MEK slurry treated with phenylaminosilane: SC2050-MTX (manufactured by Admatechs Company Limited)

[0142] [Preparation of pre-reaction product]

[0143] In Example 1 and Example 2, each component was added to toluene according to the ratio (mass parts) described in Table 1 below and stirred at 120° C. for 6 hours. Thus, a pre-reaction product was prepared by reacting the maleimide compound (a1) and the phosphorus-containing compound (a2) in advance (pre-reaction). The solid content concentration of the obtained pre-reaction product was adjusted to 60 to 70%, respectively. The pre-reaction product contains unreacted phosphorus-containing compound (a2) and phosphorus-containing compound (a2-1) obtained by reacting the phosphorus-containing compound (a2) in advance.

[0144] Then, the reaction rate of DOPO after the preliminary reaction (preliminary reaction) was measured as follows.

[0145] conduct 31 P-NMR analysis ( Figure 6 The spectrum showing the analysis results of Example 1 is shown as an example in FIG. 1 ), and the reaction rate is calculated based on the peak area value of the obtained DOPO (unreacted phosphorus-containing compound (a2)) and the peak area value of the phosphorus-containing compound (a2-1) obtained by reacting the phosphorus-containing compound (a2) in advance. Specifically, by calculating 31 The reaction rate was determined by calculating the peak area value of the phosphorus-containing compound (a2-1) in the P-NMR spectrum / (peak area value of the component (a2) + peak area value of the phosphorus-containing compound (a2-1)).

[0146] The above results are shown in Table 1.

[0147] Table 1

[0148] Example 1 Example 2 Solvent (Toluene) 41 41 Maleimide compound (a1) 61 61 Flame retardant (a2) 26 13 Solid content concentration (%) 69 64 Reaction temperature (℃) 120 120 Response time (hours) 6 6

[0149] <Examples 1 and 2 and Comparative Examples 1 and 2>

[0150] [Preparation method]

[0151] (resin varnish)

[0152] First, the resin components (pre-reaction product (A), thermosetting resin (B)) were added to a toluene solvent and mixed in a ratio (parts by mass) of each component as shown in Table 2 described later, and in a manner such that the solid content concentration was 40 to 50% by mass. An inorganic filler was added to the mixture, stirred for 30 to 60 minutes, and dispersed with a bead mill to obtain a resin varnish. It should be noted that the P (phosphorus) concentration in the table is a value calculated by the mixed amount of phosphorus-containing compound (a2) × the phosphorus concentration of phosphorus-containing compound (a2) / (the mixed amount of maleimide compound (a1) + the mixed amount of phosphorus-containing compound (a2) + the mixed amount of thermosetting resin (B)). Here, the phosphorus concentration of the phosphorus-containing compound (a2) is 0.143.

[0153] It should be noted that in Comparative Examples 1 and 2, the same method as in Examples 1 and 2 was used except that the maleimide compound (a1) and the phosphorus-containing compound (a2) were not reacted in advance (preliminary reaction) to prepare the resin varnish.

[0154] (Preparation of Evaluation Samples)

[0155] First, the varnish obtained above was impregnated into a fibrous substrate (glass cloth: #2116 type, NE glass manufactured by Nitto Bo Co., Ltd.), and then heated and dried at 120 to 140° C. for 2 to 5 minutes to prepare a prepreg having a thickness of 100 μm. At this time, the content of the components constituting the resin composition by the curing reaction (resin content) relative to the prepreg was adjusted to be about 46% by mass.

[0156] Next, an evaluation substrate (metal foil-clad laminate) was obtained as follows.

[0157] Copper foil ("3EC-LPIII" manufactured by Mitsui Mining & Smelting Co., Ltd., copper foil thickness: 12 μm) was arranged on both sides of each obtained prepreg. It was used as a pressed body, heated to a temperature of 220°C at a heating rate of 3°C / min, and heated and pressed under the conditions of 220°C, 120 minutes, and a pressure of 2 MPa, thereby obtaining an evaluation substrate (metal foil-clad laminate) with a resin layer thickness of about 100 μm bonded to copper foil on both surfaces.

[0158] An evaluation test was performed by the method shown below using the evaluation substrate (metal foil-clad laminate) prepared as described above.

[0159] <Evaluation Test>

[0160] (Dielectric properties: Dielectric loss factor (Df))

[0161] The bare board from which the copper foil was removed from the evaluation substrate (metal foil laminate) by etching was used as a test piece, and the dielectric loss factor at 10 GHz was measured by the resonant cavity perturbation method. Specifically, the relative dielectric constant and dielectric loss factor of the evaluation substrate at 10 GHz were measured using a network analyzer (N5230A manufactured by Keysight Technologies Co., Ltd.). In this test, if Df is less than 0.003, it is considered qualified.

[0162] (Coefficient of Thermal Expansion (CTE))

[0163] The bare board from which the copper foil was removed from the evaluation substrate (metal foil laminate) by etching was used as a test piece, and the thermal expansion coefficient of the cured resin in the substrate surface direction (tensile direction, Y direction) at a temperature below the glass transition temperature was measured by the TMA method (Thermo-mechanical analysis). Specifically, during the measurement, the measurement was performed in the tensile mode using a TMA device ("TMA6000" manufactured by Seiko Nanotech Corporation). In order to remove the influence of the thermal strain of the test piece, the heating-cooling cycle was repeated twice, and the average thermal expansion coefficient from 50°C to 100°C of the second temperature displacement diagram was measured. The smaller the value, the better the result. The unit is ppm / °C.

[0164] [Measurement conditions]

[0165] · First cycle: Temperature rise range 30℃→350℃

[0166] Heating rate: 20℃ / min, load: 10g

[0167] · Second cycle: Temperature rise range 30℃→320℃

[0168] Heating rate: 10℃ / min, load: 10g

[0169] (Water absorption)

[0170] A bare board obtained by removing the copper foil from the evaluation substrate (metal-clad laminate) by etching was used as a test piece, and the water absorption (%) was measured by the method according to IPC-TM-6502.6.2.1. In this test, a water absorption of less than 0.3% was considered acceptable.

[0171] (Flame retardancy)

[0172] After the copper foil on the surface of the evaluation substrate (metal foil-clad laminate) was peeled off, the flammability was evaluated in accordance with the UL94 (0.8 mmt) flammability test.

[0173] The above results are shown in Table 2.

[0174] Table 2

[0175]

[0176] (Inspection)

[0177] It can be seen from the results in Table 2 that the cured products (insulating layers) of the resin compositions of the embodiments of the present invention all have low dielectric loss factor, low thermal expansion coefficient and low water absorption.

[0178] On the other hand, in Comparative Examples 1 and 2, in which the additives were directly added without preliminary reaction, the flame retardancy at the same level as that of the Examples was obtained, but the dielectric loss tangent, thermal expansion coefficient and water absorption rate were higher.

[0179] This application is based on Japanese patent application No. 2022-159545 filed on October 3, 2022, and the contents are included in this application.

[0180] In order to describe the present invention, the present invention has been appropriately and fully described above by referring to specific embodiments and drawings, but it should be recognized that those skilled in the art can easily change and / or improve the above-mentioned embodiments. Therefore, as long as the modified embodiments or improved embodiments implemented by those skilled in the art do not deviate from the protection scope of the claims recorded in the claims, the modified embodiments or improved embodiments can be interpreted as being included in the protection scope of the claims.

[0181] Industrial Applicability

[0182] The present invention has broad industrial applicability in technical fields such as electronic materials, electronic devices, and optical devices.

Claims

1. A resin composition, characterized in that contain: A pre-reaction product (A) obtained by reacting in advance a mixture comprising a maleimide compound (a1) having two or more maleimide groups in a molecule and a phosphorus-containing compound (a2), wherein the phosphorus-containing compound (a2) is at least one of a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound and a diphenylphosphine oxide compound; and The thermosetting resin (B) has two or more unsaturated double bonds.

2. The resin composition according to claim 1, characterized in that The pre-reaction product (A) is a reaction product obtained by preliminarily reacting the maleimide compound (a1) and the phosphorus-containing compound (a2) at a mass ratio of 50:50 to 95:5, and the phosphorus-containing compound (a2) is at least one of a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide compound and a diphenylphosphine oxide compound.

3. The resin composition according to claim 1, characterized in that The preliminary reaction product (A) and the thermosetting resin (B) are contained in a mass ratio of 70:30 to 10:

90.

4. The resin composition according to claim 1, characterized in that The pre-reaction product (A) contains a phosphorus-containing maleimide compound (A-1), wherein the phosphorus-containing maleimide compound (A-1) is at least one of a phosphorus-containing maleimide compound having a group represented by the following formula (1) and a phosphorus-containing maleimide compound having a group represented by the following formula (2), 5. The resin composition according to claim 4, characterized in that The phosphorus-containing maleimide compound (A-1) contains a phosphorus-containing maleimide compound (A-2), wherein the phosphorus-containing maleimide compound (A-2) is at least one of a phosphorus-containing maleimide compound having a group represented by the following formula (3) and a phosphorus-containing maleimide compound having a group represented by the following formula (4), 6. The resin composition according to claim 1, characterized in that The pre-reaction product (A) contains an unreacted phosphorus-containing compound (a2) and a phosphorus-containing compound (a2-1) obtained by reacting the phosphorus-containing compound (a2) in advance. The reaction rate of the phosphorus-containing compound (a2) is 30% or more and 100% or less, and the reaction rate is based on 31 The peak area value of the phosphorus-containing compound (a2-1) in the P-NMR spectrum / (peak area value of the component (a2) + peak area value of the phosphorus-containing compound (a2-1)).

7. The resin composition according to claim 1, characterized in that The thermosetting resin (B) contains at least one selected from the group consisting of a polyphenylene ether compound, an allyl compound, an acrylate compound, a methacrylate compound, a vinyl compound, a styrene-based compound, a maleimide compound (b1) different from the maleimide compound (a1), and a benzoxazine compound having an allyl group, each of which has two or more unsaturated double bonds.

8. The resin composition according to claim 1, characterized in that Also contains: Inorganic fillers.

9. A prepreg, characterized in that include: The resin composition according to any one of claims 1 to 8 or a semi-cured product of the resin composition; as well as Cellulosic substrate.

10. A film with resin, characterized in that include: A resin layer comprising the resin composition according to any one of claims 1 to 8 or a semi-cured product of the resin composition; as well as Support membrane.

11. A metal foil with resin, characterized in that include: A resin layer comprising the resin composition according to any one of claims 1 to 8 or a semi-cured product of the resin composition; as well as Metal foil.

12. A metal foil-clad laminate, characterized in that include: An insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 8; as well as Metal foil.

13. A metal foil-clad laminate, characterized in that include: An insulating layer comprising a cured product of the prepreg according to claim 9; as well as Metal foil.

14. A wiring board, characterized in that include: An insulating layer comprising a cured product of the resin composition according to any one of claims 1 to 8; as well as wiring.

15. A wiring board, characterized in that include: An insulating layer comprising a cured product of the prepreg according to claim 9; as well as wiring.

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