WO2022131151A1 - 熱硬化性樹脂組成物の相容性評価方法、熱硬化性樹脂組成物、プリプレグ、樹脂フィルム、積層板、多層プリント配線板及び半導体パッケージ - Google Patents

熱硬化性樹脂組成物の相容性評価方法、熱硬化性樹脂組成物、プリプレグ、樹脂フィルム、積層板、多層プリント配線板及び半導体パッケージ Download PDF

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WO2022131151A1
WO2022131151A1 PCT/JP2021/045494 JP2021045494W WO2022131151A1 WO 2022131151 A1 WO2022131151 A1 WO 2022131151A1 JP 2021045494 W JP2021045494 W JP 2021045494W WO 2022131151 A1 WO2022131151 A1 WO 2022131151A1
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Prior art keywords
group
resin composition
thermosetting resin
component
compatibility
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Ceased
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PCT/JP2021/045494
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English (en)
French (fr)
Japanese (ja)
Inventor
秀一 石橋
大輔 藤本
智彦 小竹
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Resonac Corp
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Showa Denko Materials Co Ltd
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Priority to US18/257,146 priority Critical patent/US20230392002A1/en
Priority to KR1020237019829A priority patent/KR20230118575A/ko
Priority to CN202180083991.2A priority patent/CN116583562B/zh
Priority to JP2022569944A priority patent/JPWO2022131151A1/ja
Publication of WO2022131151A1 publication Critical patent/WO2022131151A1/ja
Anticipated expiration legal-status Critical
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    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/225—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion
    • G01N23/2251—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion using incident electron beams, e.g. scanning electron microscopy [SEM]
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C—CHEMISTRY; METALLURGY
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
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    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L15/00—Compositions of rubber derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/44—Resins; Plastics; Rubber; Leather
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W70/00—Package substrates; Interposers; Redistribution layers [RDL]
    • H10W70/60—Insulating or insulated package substrates; Interposers; Redistribution layers
    • H10W70/67—Insulating or insulated package substrates; Interposers; Redistribution layers characterised by their insulating layers or insulating parts
    • H10W70/68—Shapes or dispositions thereof
    • H10W70/685—Shapes or dispositions thereof comprising multiple insulating layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W70/00—Package substrates; Interposers; Redistribution layers [RDL]
    • H10W70/60—Insulating or insulated package substrates; Interposers; Redistribution layers
    • H10W70/67—Insulating or insulated package substrates; Interposers; Redistribution layers characterised by their insulating layers or insulating parts
    • H10W70/69—Insulating materials thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2447/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2471/12—Polyphenylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • G01N2223/418—Imaging electron microscope
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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    • G01N2223/60—Specific applications or type of materials
    • G01N2223/611—Specific applications or type of materials patterned objects; electronic devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W70/00—Package substrates; Interposers; Redistribution layers [RDL]
    • H10W70/60—Insulating or insulated package substrates; Interposers; Redistribution layers
    • H10W70/67—Insulating or insulated package substrates; Interposers; Redistribution layers characterised by their insulating layers or insulating parts
    • H10W70/69—Insulating materials thereof
    • H10W70/695—Organic materials

Definitions

  • the present embodiment relates to a method for evaluating compatibility of a thermosetting resin composition, a thermosetting resin composition, a prepreg, a resin film, a laminated board, a multilayer printed wiring board, and a semiconductor package.
  • the speed and capacity of signals used are increasing year by year.
  • the substrate material of the printed wiring board mounted on these electronic devices has a dielectric characteristic that can reduce the transmission loss of a high frequency signal [hereinafter, may be referred to as "high frequency characteristic”. ], That is, a low relative permittivity and a low dielectric loss tangent are required.
  • high frequency characteristic a dielectric characteristic that can reduce the transmission loss of a high frequency signal
  • practical application or practical planning of a new system handling high-frequency radio signals is in progress. Therefore, it is expected that the need for substrate materials having excellent high-frequency characteristics will increase for printed wiring boards used in these fields in the future.
  • thermoplastic polymer having excellent high frequency characteristics has been used for a printed wiring board that requires low transmission loss.
  • a thermoplastic polymer for example, a polymer having no polar group in the molecule such as polyphenylene ether and polybutadiene is effective for low dielectric loss tangent.
  • these thermoplastic polymers have low compatibility with other resins having a polar group, and when they are made into a resin composition, there are problems such as separation from other resins. Separation of the resins may lead to a decrease in workability, a decrease in the homogeneity of the product, and a resulting decrease in physical properties, and is therefore desirable to be suppressed.
  • Patent Document 1 discloses a curable resin composition containing a specific polyphenylene ether and a polyfunctional vinyl aromatic copolymer.
  • the compatibility of the polyfunctional vinyl aromatic copolymer with the epoxy resin is determined by dissolving the polyfunctional vinyl aromatic copolymer, the epoxy resin and the phenol resin in a solvent, and the sample after dissolution. It is evaluated by visually confirming the transparency.
  • the present embodiment uses a method for evaluating compatibility of a thermosetting resin composition, a thermosetting resin composition having improved compatibility, and the thermosetting resin composition.
  • An object of the present invention is to provide a prepreg, a resin film, a laminated board, a multilayer printed wiring board, and a semiconductor package.
  • thermosetting resin composition containing two or more kinds of resins and an inorganic filler, which comprises the following steps 1A and 2A, and is a phase of the thermosetting resin composition.
  • Capacity evaluation method Acquiring a backscattered electron image of a scanning electron microscope with respect to a cross section of a cured product of the thermosetting resin composition at an observation magnification of 50 to 250 times
  • Step 2A A phase-separated resin region in the backscattered electron image.
  • Step [2] A method for evaluating compatibility of a thermosetting resin composition containing two or more kinds of resins and an inorganic filler, which comprises the following steps 1B and 2B. Compatibility evaluation method.
  • Step 1B Acquiring a backscattered electron image of the cured product of the thermosetting resin composition with respect to the cross section of the cured product. Step of acquiring the average domain size DL of the part [3]
  • the reflected electron image of the scanning electron microscope is acquired with respect to the cross section of the cured product of the thermosetting resin composition at an observation magnification of 50 to 200 times.
  • the area ratio R w of the non-separable portion acquired under the condition that the observation magnification of the scanning electron microscope is 100 times or 200 times is 50% or more.
  • the domain size of the separation portion observed in at least three fields of view is large under the condition that the observation magnification of the scanning electron microscope is 65 times.
  • [6] A resin film containing the thermosetting resin composition according to the above [4].
  • thermosetting resin composition a thermosetting resin composition having improved compatibility
  • prepreg and a resin film using the thermosetting resin composition a method for evaluating compatibility of a thermosetting resin composition, a thermosetting resin composition having improved compatibility, and a prepreg and a resin film using the thermosetting resin composition.
  • Laminated boards, multilayer printed wiring boards and semiconductor packages can be provided.
  • the numerical range indicated by using "-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
  • the lower and upper limits of the numerical range described herein are optionally combined with the lower or upper limit of the other numerical ranges, respectively.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
  • each component and material exemplified in the present specification may be used alone or in combination of two or more.
  • the content of each component in the thermosetting resin composition is the thermosetting resin composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the thermosetting resin composition.
  • thermosetting resin composition it means the total amount of the plurality of substances present in the object.
  • An embodiment in which the items described in the present specification are arbitrarily combined is also included in the present embodiment.
  • the mechanism of action described herein is speculative and does not limit the mechanism by which the thermosetting resin composition according to this embodiment is effective.
  • phase in the present specification means that the resins are miscible in nano, micro units, or in appearance, even if they are not necessarily compatible in molecular units.
  • the number average molecular weight in the present specification means a value measured in terms of polystyrene by gel permeation chromatography (GPC), and can be specifically measured by the method described in Examples.
  • thermosetting resin composition may be simply abbreviated as "resin composition”.
  • the compatibility evaluation method of the first aspect of the present embodiment is a method of evaluating the compatibility of a thermosetting resin composition containing two or more kinds of resins and an inorganic filler, and is described in the following steps 1A and It is a compatibility evaluation method of a thermosetting resin composition containing 2A.
  • Step 1A A step of acquiring a reflected electron image of a scanning electron microscope with respect to a cross section of a cured product of the thermosetting resin composition at an observation magnification of 50 to 250 times.
  • Step 2A A phase-separated resin region in the reflected electron image.
  • the area ratio of the region of the non-separable portion of the binarized image (the area of the region of the non-separable portion ⁇ 100 / the area of the entire region of the binarized image) is calculated as the area ratio R w of the non-separable portion.
  • step 1A a backscattered electron image of a thermosetting resin composition containing two or more kinds of resins and an inorganic filler is acquired by a scanning electron microscope (SEM) at an observation magnification of 50 to 250 times. It is a process.
  • the resin composition to be measured by the compatibility evaluation method of the present embodiment is not particularly limited as long as it is a resin composition containing two or more kinds of resins and an inorganic filler.
  • the resin composition may be a measurement target.
  • the curing conditions of the resin composition are not particularly limited, and the resin composition may be cured under conditions suitable for the resin composition to be measured.
  • the conditions described in the examples can be used. Specifically, the resin composition is heated and dried at 170 ° C. for 5 minutes to be in a B stage state, and then cured by heat and pressure molding at a temperature of 230 ° C., a pressure of 2.0 MPa, and a time of 120 minutes. You can get things.
  • the method for forming the cross section of the cured product of the resin composition is not particularly limited, and a conventionally known method can be adopted.
  • a precision cutting machine, an ion milling device, an ultrasonic cutting machine or the like can be used to form the cured product.
  • a method of forming a cross section of the above can be mentioned.
  • the cured product of the resin composition may be embedded in the embedding resin from the viewpoint of processability.
  • polishing treatment or the like may be performed as necessary.
  • After forming the cross section of the cured product it is preferable to carry out a vapor deposition treatment of platinum or the like on the cross section in order to perform SEM observation satisfactorily.
  • the object of SEM observation obtained by the above steps is referred to as a "test piece".
  • the SEM observation in the compatibility evaluation method of the present embodiment is performed in the backscattered electron mode in order to enhance the contrast between the inorganic filler and the resin component.
  • the acceleration voltage during SEM observation may be appropriately adjusted according to the measurement target, but may be adjusted in the range of 0.5 to 20 kV, for example.
  • the observation magnification of the SEM in step 1A is in the range of 50 to 250 times, preferably 60 to 230 times, and more preferably 80 to 210 times.
  • the observation magnification within the above range, measurement variation due to the visual field can be suppressed, and the reproducibility of the calculated area ratio R w of the non-separable portion can be improved.
  • the phase-separated resin region and the other regions are each in the form of a domain having a uniform color. Since it can be observed in the above, it becomes easy to carry out the step 2A described later.
  • the reflected electron image of the test piece can be acquired by the step 1A.
  • step 2A in the backscattered electron image, the phase-separated resin region is set as a separation portion and the other region is set as a non-separation portion, so that the separation portion has one value and the non-separation portion has the other value.
  • Area ratio of the area of the non-separable part of the binarized image to the whole area of the binarized image obtained by quantifying (area of the non-separable part ⁇ 100 / area of the whole area of the binarized image) ) Is a step of calculating the area ratio R w of the non-separable portion.
  • FIG. 1 shows an example of a reflected electron image obtained in step 1A.
  • the reflected electron image obtained in step 1A includes a region 1 that looks relatively bright and a region 2 that looks relatively dark.
  • the region that looks relatively dark is a phase rich in the resin having a low electron density, and corresponds to a phase-separated resin region.
  • the region that looks relatively bright is the phase in which the compatible resin and the inorganic filler having a high electron density are contained.
  • the phase-separated resin region is designated as a “separated portion”, and the other regions are designated as a “non-separated portion”.
  • the separated portion can be clearly and easily identified by visual inspection.
  • the reflected electron image is binarized so that the separated portion has one value and the non-separated portion has the other value, and then the binarized value is obtained for the entire region of the obtained binarized image.
  • the area ratio of the region of the non-separable portion of the image (area of the region of the non-separable portion ⁇ 100 / the area of the entire region of the binarized image) is calculated as the area ratio R w of the non-separable portion.
  • the binarization in this step is, for example, a process of giving a pixel value "1 (white)" to a pixel having a pixel value equal to or higher than a predetermined threshold value and giving a pixel value "0 (black)" to other pixels.
  • the binarization may be performed by a known method, and can be performed, for example, by using commercially available image processing software.
  • the binarization condition may be appropriately adjusted according to the reflected electron image obtained in the step 1A, and the binarization may be performed under the condition that the separated portion has one value and the non-separated portion has the other value.
  • the RGB threshold is appropriately adjusted to the range of 40 to 100 as a processing condition. It can be binarized by this.
  • the area ratio of the region of the non-separated portion of the binarized image to the entire region of the obtained binarized image (area of the region of the non-separated portion ⁇ 100 / area of the entire region of the binarized image) is calculated. , Calculated as the area ratio R w of the non-separable part.
  • the area ratio R w may be calculated, for example, by counting the number of pixels in the entire region of the binarized image and the number of pixels having a value representing the non-separable portion.
  • the area ratio R w of the non-separable portion may be calculated for one visual field, but from the viewpoint of reproducibility, the area ratio R w of the non-separable portion is calculated for a plurality of visual fields. Then, it is preferable to average this.
  • the number of visual fields to be averaged is not particularly limited, and may be, for example, 2, 3, 4, or 5 or more visual fields, and may be appropriately selected depending on the required accuracy.
  • the area ratio R w of the non-separable portion obtained by the above method can be used as an index of compatibility. That is, it can be seen that the larger the area ratio R w of the non-separated portion, the smaller the amount of the phase-separated resin, and the better the compatibility of the resin composition.
  • the compatibility evaluation method of the second aspect of the present embodiment is a method of evaluating the compatibility of a thermosetting resin composition containing two or more kinds of resins and an inorganic filler, and is described in the following steps 1B and It is a compatibility evaluation method of a thermosetting resin composition containing 2B.
  • Step 1B Acquiring a backscattered electron image of the cured product of the thermosetting resin composition
  • Step 2B In the backscattered electron image, the phase-separated resin region is used as a separation portion, and the separation is performed.
  • Step 1B is a step of acquiring a reflected electron image of a scanning electron microscope for a cross section of a cured product of a thermosetting resin composition containing two or more kinds of resins and an inorganic filler.
  • the observation magnification of the scanning electron microscope in the step 1B is not particularly limited, but is preferably 30 to 500 times, more preferably 40 to 200 times, still more preferably 50 to 200 times, particularly, from the viewpoint of workability and reproducibility. It is preferably 50 to 100 times.
  • the description of step 1B other than the observation magnification is the same as the description of step 1A.
  • Step 2B is a step of acquiring the average domain size DL of the separated portion by using the phase-separated resin region as the separating portion in the backscattered electron image.
  • the domain size in this step is defined as the diameter of the maximum perfect circle that can be drawn in the domain of the separation portion.
  • 2 and 3 show a schematic diagram showing a method of measuring the domain size of the separated portion. For example, as shown in FIG. 2A, when a domain is regarded as a perfect circle, its diameter corresponds to the domain size. Further, for example, when the domain is regarded as an ellipse or an amorphous shape as shown in FIG. 2B or FIG. 2C, the diameter of the maximum perfect circle that can be drawn in the ellipse or the amorphous shape corresponds to the domain size. ..
  • the domain of the separation portion may have a shape in which two or more domains are connected.
  • the diameter t is 1/3 or less of the diameter s.
  • the domain is divided by the above-mentioned concatenated part. That is, it is assumed that the domain shown in FIG. 3A has two domains, a domain having a diameter s and a domain having a diameter u.
  • the domain shown in FIG. 3B since the diameter t exceeds 1/3 of the diameter s, it is assumed that the domain is not divided at the connecting portion and has a domain size of the diameter s.
  • the average domain size DL of the separation part in step 2B is obtained by averaging the domain sizes of the domains having the second and subsequent sizes, counting from the domain of the separation part having the largest domain size. Is preferable. As a result, it is possible to eliminate the influence of a large separation portion that is unintentionally generated due to factors other than compatibility during the production of the resin composition, and it is possible to improve the reproducibility.
  • the number of the second and subsequent domains for obtaining the average value is not particularly limited, and may be appropriately determined according to the measurement target. From the viewpoint of workability and reproducibility, the average domain size DL of the separation part is the domain having the size within the 100th, preferably the domain having the size within the 50th, in order from the second and the largest. , More preferably, it is obtained by averaging the domain sizes of domains having a size within the 10th, and more preferably domains having a size of 2nd to 6th.
  • the average domain size DL may be obtained by performing the above step for only one visual field, but from the viewpoint of reproducibility, after observing a plurality of visual fields, the said. It is preferable to obtain the average domain size DL from all the domains included in the plurality of fields of view.
  • the number is preferably 3 visual fields or more, more preferably 5 visual fields or more, and further preferably 6 visual fields or more.
  • the upper limit of the number of visual fields to be observed is not particularly limited, but may be, for example, 20 visual fields or less, 15 visual fields or less, or 10 visual fields or less.
  • the average domain size DL of the separated portion obtained by the above method can be used as an index of compatibility. That is, it can be seen that the smaller the average domain size DL of the separated portion, the more excellent the compatibility of the resin composition.
  • thermosetting resin composition is a thermosetting resin composition containing two or more kinds of resins and an inorganic filler.
  • the area ratio R w of the non-separable portion acquired under the condition that the observation magnification of the scanning electron microscope is 100 times or 200 times is 50% or more
  • the observation magnification of the scanning electron microscope is 65 times, and the domain of the separation part observed in at least three fields of view is counted from the one having the largest domain size.
  • thermosetting resin composition obtained by averaging the domain sizes of the domains having the second to sixth sizes and having an average domain size DL of 120 ⁇ m or less in the separated portion.
  • the area ratio R w and the average domain size DL of the non-separable portion with respect to the thermosetting resin composition of the present embodiment are based on the compatibility evaluation method of the first aspect and the compatibility evaluation method of the second aspect. More specifically, it is a value measured by the method described in Examples.
  • the area ratio R w of the non-separable portion of the resin composition of the present embodiment is not particularly limited, but is preferably 52% or more, more preferably 54% or more, still more preferably 56% or more.
  • the upper limit of the area ratio R w of the non-separable portion is not particularly limited and may be 100%, but from the viewpoint of ease of manufacture and the like, it may be 98% or less, or 95% or less. May be good.
  • the average domain size DL of the separated portion of the resin composition of the present embodiment is not particularly limited, but is preferably 100 ⁇ m or less, more preferably 90 ⁇ m or less, still more preferably 85 ⁇ m or less.
  • the lower limit of the average domain size DL of the separated portion is not particularly limited and may be 0 ⁇ m, but from the viewpoint of ease of manufacture and the like, it may be 10 ⁇ m or more, or 30 ⁇ m or more.
  • the average domain size DL of the separated portion is 0 ⁇ m, which means that the separated portion cannot be substantially observed and the domain size cannot be measured.
  • the area ratio R w of the non-separable portion and the average domain size DL of the separated portion can be appropriately adjusted within the above ranges by, for example, selecting the type of resin contained in the resin composition.
  • the resin composition of the present embodiment contains two or more kinds of resins and an inorganic filler.
  • the resin component is not particularly limited as long as it satisfies the above-mentioned area ratio R w of the non-separable portion and the average domain size DL of the separated portion, but contains at least two types of elastomer and thermosetting resin. Is preferable.
  • the elastomer examples include polyether elastomers, styrene elastomers, conjugated diene elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, acrylic elastomers, silicone elastomers and the like.
  • the elastomer one type may be used alone, or two or more types may be used in combination.
  • a polyether elastomer, a styrene elastomer, and a conjugated diene elastomer are preferable from the viewpoint of dielectric properties.
  • thermosetting resin examples include epoxy resins, cyanate ester compounds, maleimide compounds, bisallyl nadiimide resins, benzoxazine compounds, and derivatives thereof.
  • the thermosetting resin one type may be used alone, or two or more types may be used in combination.
  • the thermosetting resin is preferably a maleimide compound or a derivative thereof from the viewpoint of heat resistance, low thermal expansion property and mechanical properties.
  • the resin composition of the present embodiment preferably contains a polyether elastomer as an elastomer and a maleimide compound or a derivative thereof as a thermosetting resin.
  • the resin composition of the present embodiment may be referred to as a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group [hereinafter, "polyphenylene ether derivative (A)” or “component (A)” as an elastomer.
  • thermosetting resin one or more selected from the group consisting of a maleimide compound having two or more N-substituted maleimide groups and a derivative thereof [hereinafter, "maleimide compound or its derivative (B)” or It may be referred to as "(B) component”. ] Is more preferable.
  • thermoplastic elastomer (D) styrene-based thermoplastic elastomer (D)" or “component (D)".
  • styrene-based thermoplastic elastomer (D) or “component (D)”.
  • the resin composition of the present embodiment may be referred to as (E) an imidazole compound or a modified imidazole compound [hereinafter, "imidazole compound or its modified product (E)" or “(E) component” as a curing accelerator. be. ] Is particularly preferable.
  • the component (A) has an ethylenically unsaturated bond-containing group. That is, it can be said that the component (A) is a polyphenylene ether introduced with an ethylenically unsaturated bond-containing group.
  • the "ethylenically unsaturated bond” means a carbon-carbon double bond capable of an addition reaction, and does not include a double bond of an aromatic ring.
  • the "ethylenically unsaturated bond-containing group” means a substituent containing the ethylenically unsaturated bond.
  • one type may be used alone, or two or more types may be used in combination.
  • the position of the ethylenically unsaturated bond-containing group in the component (A) is not particularly limited, and may be a terminal or a position other than the terminal.
  • the position of the ethylenically unsaturated bond-containing group may be one end or both ends.
  • the "terminal" of the component (A) means not only the atom at the end of the molecule but also the entire organic group bonded to the ether bond existing at the end of the polyphenylene ether chain from the end side.
  • the component (A) having an ethylenically unsaturated bond-containing group at the end means that the organic group bonded to the ether bond existing at the most end of the polyphenylene ether chain from the end side is an ethylenically unsaturated bond-containing group. It is synonymous with having.
  • the component (A) may be a mixture of a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at one end and a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at both ends, but at least, It is preferable to contain a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at one end, and more preferably the polyphenylene ether derivative itself having an ethylenically unsaturated bond-containing group at one end.
  • the content of the polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at one end in the component (A). is preferably 30% by mass or more, more preferably 45% by mass or more, further preferably 55% by mass or more, still more preferably 70% by mass or more, particularly preferably 90% by mass or more, and most preferably substantially 100% by mass. %.
  • Examples of the ethylenically unsaturated bond-containing group contained in the component (A) include unsaturated aliphatic hydrocarbon groups such as vinyl group, isopropenyl group, allyl group, 1-methylallyl group and 3-butenyl group; maleimide group, Examples thereof include a substituent containing a hetero atom such as a (meth) acryloyl group.
  • unsaturated aliphatic hydrocarbon group and a maleimide group are preferable, an allyl group and a maleimide group are more preferable, and an allyl group is further preferable, from the viewpoint of dielectric properties.
  • the unsaturated aliphatic hydrocarbon group described as the ethylenically unsaturated bond-containing group does not contain a hetero atom.
  • the number of unsaturated aliphatic hydrocarbon groups contained in one molecule of the component (A) is not particularly limited, but is preferably 2 or more, more preferably 3 or more, still more preferably 4 from the viewpoint of dielectric properties. That is all.
  • the upper limit of the number of unsaturated aliphatic hydrocarbon groups contained in one molecule of the component (A) is not particularly limited, and may be 8 or less, 7 or less, or 6 It may be less than one.
  • the number of unsaturated aliphatic hydrocarbon groups (A) contained in one end is not particularly limited, but from the viewpoint of dielectric properties, it is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more. Is.
  • (A) There is no particular limitation on the upper limit of the number of unsaturated aliphatic hydrocarbon groups that the component has at one end, and it may be 8 or less, 7 or less, or 6 or less. May be. It is most preferable that the number of unsaturated aliphatic hydrocarbon groups contained in the component (A) and the number of unsaturated aliphatic hydrocarbon groups contained in the component (A) at one end are both four.
  • the component (A) preferably contains a structure represented by the following general formula (a-1) from the viewpoint of dielectric properties.
  • Ra1 is an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms.
  • N1 is 1 or 2
  • n2 is 0 or 1. * Is a bond position to another structure. Shows.
  • unsaturated fats having 2 to 5 carbon atoms from the viewpoint of dielectric properties.
  • Group hydrocarbon groups are preferred, vinyl groups, isopropenyl groups, allyl groups, 1-methylallyl groups and 3-butenyl groups are more preferred, and allyl groups are even more preferred.
  • n1 is 2, the plurality of Ra1s may be the same or different from each other.
  • the component (A) preferably includes a structure represented by the following general formula (a-2).
  • R a2 and R a3 are each independently unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. * Indicates the bond position to another structure.
  • Examples of the unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms represented by Ra 2 and Ra 3 in the general formula (a-2) are the same as those in Ra 1 in the general formula (a-1). , The same is preferred.
  • the component (A) more preferably contains a structure represented by any of the following general formulas (a-3) to (a-5), and the following general formula (a-5) is used. It is more preferred to include the structure represented.
  • Ra4 is an unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms. * Indicates a bond position to another structure.
  • R a5 and R a6 are each independently unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms.
  • X a1 is a divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms. * Indicates the position of connection to other structures.
  • R a7 to R a10 are independently unsaturated aliphatic hydrocarbon groups having 2 to 10 carbon atoms.
  • X a2 is a divalent organic group. * Is a divalent organic group. Indicates the bonding position.
  • the unsaturated aliphatic hydrocarbon group having 2 to 10 carbon atoms represented by R a4 to R a10 in the general formulas (a-3) to (a-5) is R in the general formula (a-1).
  • the same as in the case of a1 can be mentioned, and the preferred one is also the same.
  • Examples of the divalent aliphatic hydrocarbon group having 1 to 6 carbon atoms represented by Xa1 in the general formula (a-4) include an alkylene having 1 to 6 carbon atoms such as a methylene group, an ethylene group and a trimethylene group.
  • An alkylidene group having 2 to 6 carbon atoms such as an isopropyridene group can be mentioned. Among these, a methylene group and an isopropyridene group are preferable, and an isopropyridene group is more preferable.
  • Examples of the divalent organic group represented by Xa2 in the above general formula (a-5) include an aliphatic hydrocarbon group which may contain a hetero atom in a part and a hetero atom in a part. Examples thereof include an alicyclic hydrocarbon group which may be present, an aromatic hydrocarbon group which may partially contain a hetero atom, a group consisting of any combination of these groups, and the like. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom and the like.
  • the divalent organic group represented by X a2 is preferably a group that does not contain a hetero atom, an aliphatic hydrocarbon group that does not contain a hetero atom, and an alicyclic hydrocarbon that does not contain a hetero atom.
  • a hydrogen group is more preferable, and a group consisting of a combination of an aliphatic hydrocarbon group that does not contain a hetero atom and an alicyclic hydrocarbon group that does not contain a hetero atom is further preferable
  • the structures represented by the general formula (a-3), the general formula (a-4), or the general formula (a-5) are described in the following formula (a-3') and the following, respectively, from the viewpoint of dielectric properties. It is preferable that the structure is represented by the formula (a-4') or the following general formula (a-5'). Among these, from the viewpoint of dielectric properties, the structure represented by the following formula (a-4') or the following general formula (a-5') is more preferable, and is represented by the following general formula (a-5'). The structure is more preferred.
  • component (A) is a polyphenylene ether derivative, it also has a phenylene ether bond, and preferably has a structural unit represented by the following general formula (a-10).
  • Ra11 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms.
  • N3 is an integer of 0 to 4.
  • Examples of the aliphatic hydrocarbon group represented by Ra11 in the general formula (a-10) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t-butyl group. , N-pentyl group and the like.
  • an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is further preferable.
  • halogen atom represented by R a11 examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
  • Ra11 an aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferable.
  • N3 in the general formula (a-10) is an integer of 0 to 4, preferably an integer of 1 or 2, and more preferably 2.
  • the substitution position of Ra 11 is preferably the ortho position with respect to the substitution position of the oxygen atom.
  • the plurality of Ra 11s may be the same or different from each other.
  • the structural unit represented by the general formula (a-10) specifically, the structural unit represented by the following general formula (a-10') is preferable.
  • the component (A) preferably contains a polyphenylene ether derivative represented by any of the following general formulas (a-6) to (a-8), and preferably contains the following general formula (a-7) or (a-8). ), It is more preferable to contain the polyphenylene ether derivative represented by the following general formula (a-8), and it is further preferable to contain the polyphenylene ether derivative represented by the following general formula (a-8).
  • X a2 is the same as X a2 in the above general formula (a-5).
  • N4 to n6 are independently integers of 1 to 200.
  • n4 to n6 are independently integers of 1 to 200, and are preferably 1 from the viewpoint of dielectric properties and compatibility with other resins. It is an integer of up to 150, more preferably an integer of 1 to 120, and even more preferably an integer of 1 to 100.
  • a mixture of polyphenylene ether derivatives having different values of n4 to n6 may be used.
  • the number average molecular weight of the component (A) is not particularly limited, but is preferably 1,000 to 25,000, more preferably 2,000 to 20,000, still more preferably 3,000 to 10,000, and particularly preferably. It is 4,000 to 6,000.
  • (A) When the number average molecular weight of the component is at least the above lower limit value, the dielectric property tends to be better. Further, when the number average molecular weight of the component (A) is not more than the above upper limit value, the compatibility of the resin composition becomes good, and it tends to be difficult to separate even if it is left for a long period of time.
  • a phenol compound having a structure represented by any of the above general formulas (a-1) to (a-5) and a polyphenylene ether are redistributed in an organic solvent.
  • the phenolic compound containing the structure represented by any of the above general formulas (a-1) to (a-5) is referred to as "unsaturated aliphatic hydrocarbon group-containing phenolic compound (1)".
  • unsaturated aliphatic hydrocarbon group-containing phenolic compound (1) is sometimes referred to.
  • the polyphenylene ether used as a raw material for the redistribution reaction may be referred to as "raw material polyphenylene ether".
  • the number average molecular weight of the raw material polyphenylene ether is not particularly limited, but is preferably 3,000 to 30,000.
  • the oxy radical of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) attacks the carbon atom to which the oxygen atom in the raw material polyphenylene ether is bonded, so that the OC bond is formed there. It is a reaction that cuts and reduces the molecular weight. At that time, the oxyradical of the attacked unsaturated aliphatic hydrocarbon group-containing phenol compound (1) is bonded to the broken carbon atom and incorporated into the structure of the polyphenylene ether.
  • known methods can be used and applied.
  • the molecular weight of the component (A) can be controlled by the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used, and the larger the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used, the more (A).
  • the components are reduced in molecular weight. That is, the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used may be appropriately adjusted so that the number average molecular weight of the component (A) finally produced is in a suitable range.
  • the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) to be used is not particularly limited, but for example, the raw material polyphenylene ether to be reacted with the unsaturated aliphatic hydrocarbon group-containing phenol compound (1). It may be determined according to the number average molecular weight. For example, when the number average molecular weight of the raw material polyphenylene ether is 3,000 to 30,000, the amount of hydroxyl groups of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) with respect to 1 mol of the raw material polyphenylene ether is preferably 1. It is ⁇ 10 mol, more preferably 1-8 mol, still more preferably 2-6 mol. When the amount of the unsaturated aliphatic hydrocarbon group-containing phenol compound (1) used is within the above range, the component (A) having a number average molecular weight within the above-mentioned preferable range can be obtained.
  • Examples of the organic solvent used in the process for producing the component (A) include alcohol solvents such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone.
  • alcohol solvents such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether and propylene glycol monomethyl ether
  • acetone methyl ethyl ketone
  • methyl isobutyl ketone cyclohexanone
  • Ketone-based solvents such as; aromatic hydrocarbon-based solvents such as toluene, xylene, mesityrene; ester-based solvents such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate; N, N-dimethylformamide, N, N Examples thereof include nitrogen atom-containing solvents such as -dimethylacetamide and N-methyl-2-pyrrolidone.
  • the organic solvent one kind may be used alone, or two or more kinds may be used in combination.
  • a reaction catalyst can be used as needed, as described above.
  • the reaction catalyst for example, from the viewpoint of obtaining the component (A) having a stable number average molecular weight with good reproducibility, an organic peroxide such as t-butylperoxyisopropyl monocarbonate and a carboxylic acid such as manganese naphthenate and manganese octylate are used. It is preferable to use it in combination with an acid metal salt.
  • the organic peroxide and the carboxylic acid metal salt are used in combination, the amount of both used is not particularly limited, but the amount of the organic peroxide used is 0.5 to 5 with respect to 100 parts by mass of the raw material polyphenylene ether.
  • the amount of the carboxylic acid metal salt used is preferably 0.05 to 0.5 parts by mass.
  • the reaction rate and the suppression of gelation in the production of the component (A) tend to be better.
  • An unsaturated aliphatic hydrocarbon group-containing phenol compound (1), a raw material polyphenylene ether, an organic solvent and, if necessary, a reaction catalyst are charged in a reactor, and if necessary, the reaction is carried out while heating, keeping warm and stirring (A). Ingredients are obtained.
  • the reaction temperature of the redistribution reaction is preferably 70 to 110 ° C.
  • the reaction time of the redistribution reaction is preferably 1 to 8 hours. When the reaction temperature and the reaction time are within the above ranges, the workability and the suppression of gelation are excellent, and the component (A) having the above-mentioned number average molecular weight tends to be easily produced.
  • the reaction conditions are not limited to the above conditions, and can be appropriately adjusted according to the type of raw material and the like. Further, as the reaction conditions, known reaction conditions for the redistribution reaction can also be applied.
  • reaction concentration Solid content concentration during the reaction in the manufacturing process of the component
  • reaction concentration Is not particularly limited, but is preferably 10 to 60% by mass, more preferably 15 to 55% by mass, and even more preferably 20 to 50% by mass.
  • reaction concentration is at least the above lower limit value, a good reaction rate is obtained, and the productivity tends to be better.
  • reaction concentration is not more than the above upper limit value, better solubility is obtained, stirring efficiency is improved, and gelation tends to be further suppressed.
  • the solution of the polyphenylene ether derivative (A) produced by the above method may be concentrated to remove a part of the organic solvent, or may be diluted by adding an organic solvent. ..
  • the resin composition of the present embodiment tends to have better dielectric properties than the resin composition containing the above-mentioned raw material polyphenylene ether instead of the component (A).
  • the content thereof is not particularly limited, but is preferable with respect to 100 parts by mass of the total resin components in the resin composition from the viewpoint of dielectric properties. Is 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, still more preferably 0.7 to 5 parts by mass, and particularly preferably 1 to 3 parts by mass.
  • the "resin component” refers to, for example, a component (A), a component (B), a component (C), a component (D), and the like, and when other resins are contained. , The other resin is also included in the resin component.
  • the component (B) is one or more selected from the group consisting of maleimide compounds having two or more N-substituted maleimide groups and derivatives thereof.
  • the above-mentioned "derivative of a maleimide compound having two or more N-substituted maleimide groups” includes, for example, an addition reaction product of the above-mentioned maleimide compound having two or more N-substituted maleimide groups and the diamine compound (b2). And so on.
  • the component (B) one type may be used alone, or two or more types may be used in combination.
  • the component (B) is one or more compounds selected from the group consisting of the following (i) and (ii) from the viewpoint of compatibility with other resins, adhesiveness with conductors, and dielectric properties. Is preferable.
  • Maleimide compound (b1) having two or more N-substituted maleimide groups [hereinafter, may be referred to as “maleimide compound (b1)” or “component (b1)”.
  • the component (b1) is not particularly limited as long as it is a maleimide compound having two or more N-substituted maleimide groups.
  • the component (b1) one type may be used alone, or two or more types may be used in combination.
  • component (b1) examples include bis (4-maleimidephenyl) methane, bis (4-maleimidephenyl) ether, bis (4-maleimidephenyl) sulfone, and 3,3'-dimethyl-5,5'-diethyl-. 2 in molecules such as 4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2-bis [4- (4-maleimidephenoxy) phenyl] propane, etc.
  • Aromatic maleimide compound having two N-substituted maleimide groups Aromatic polymaleimide compound having three or more N-substituted maleimide groups in the molecule such as polyphenylmethane maleimide and biphenyl aralkyl type maleimide; 1,6-bismaleimide -(2,2,4-trimethyl) hexane, aliphatic maleimide compounds such as pyrophosphate binder type long chain alkyl bismaleimide and the like can be mentioned.
  • aromatic maleimide compounds and molecules having two N-substituted maleimide groups in the molecule from the viewpoints of compatibility with other resins, adhesion to conductors, heat resistance, low thermal expansion, and mechanical properties.
  • Aromatic polymaleimide compounds having three or more N-substituted maleimide groups within are preferred, with 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, and biphenylaralkyl-type maleimide being more. preferable.
  • component (b1) a compound represented by the following general formula (b1-1) is preferable.
  • X b1 is a divalent organic group.
  • X b1 in the above general formula (b1-1) is a divalent organic group, and corresponds to a divalent group obtained by removing two N-substituted maleimide groups from the component (b1).
  • Examples of the divalent organic group represented by X b1 include a group represented by the following general formula (b1-2), a group represented by the following general formula (b1-3), and the following general formula (b1-4). Examples thereof include a group represented by the following general formula (b1-5), a group represented by the following general formula (b1-6), and the like.
  • R b1 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms.
  • P1 is an integer of 0 to 4. * Indicates a bond position to another structure.
  • Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b1 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group and an n-pentyl group. Group etc. can be mentioned.
  • an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is further preferable.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
  • p1 is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0, from the viewpoint of availability.
  • p1 is an integer of 2 or more, the plurality of R b1s may be the same or different.
  • R b2 and R b3 are independently aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms.
  • X b2 is an alkylene group having 1 to 5 carbon atoms and 2 to 5 carbon atoms.
  • P2 and p3 are, respectively. Independently, it is an integer from 0 to 4. * indicates the position of connection to other structures.
  • Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R b2 and R b3 are the same as in the case of R b1 .
  • As the aliphatic hydrocarbon group an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, a methyl group and an ethyl group are more preferable, and an ethyl group is further preferable.
  • Examples of the alkylene group having 1 to 5 carbon atoms represented by X b2 include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group and the like. Can be mentioned.
  • an alkylene group having 1 to 3 carbon atoms is preferable, and an alkylene group having 1 or 2 carbon atoms is preferable from the viewpoints of compatibility with other resins, adhesion to conductors, heat resistance, low thermal expansion, and mechanical properties.
  • the alkylene group of the above is more preferable, and the methylene group is further preferable.
  • Examples of the alkylidene group having 2 to 5 carbon atoms represented by X b2 include an ethylidene group, a propyridene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group.
  • an isopropylidene group is preferable from the viewpoint of compatibility with other resins, adhesiveness with a conductor, heat resistance, low thermal expansion property, and mechanical properties.
  • p2 and p3 are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and even more preferably 0 or 2. Is.
  • p2 or p3 is an integer of 2 or more, the plurality of R b2s or R b3s may be the same or different from each other.
  • the divalent group represented by the general formula (b1-3-1) represented by X b2 is as follows.
  • R b4 and R b5 are independently aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms.
  • X b3 is an alkylene group having 1 to 5 carbon atoms and 2 to 5 carbon atoms. It is an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond.
  • P4 and p5 are independently integers of 0 to 4, respectively. * Is a bond position to another structure. Shows.)
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R b4 and R b5 will be described in the same manner as in the case of R b1 .
  • Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X b3 are the same as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X b2 . Be done.
  • an alkylidene group having 2 to 5 carbon atoms is preferable, an alkylidene group having 2 to 4 carbon atoms is more preferable, and an isopropylidene group is further preferable.
  • p4 and p5 are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
  • p4 or p5 is an integer of 2 or more
  • the plurality of R b4s or R b5s may be the same or different from each other.
  • p6 is an integer from 0 to 10. * Indicates the bonding position to other structures.
  • p6 is preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 3.
  • R b6 and R b7 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
  • P8 is an integer of 1 to 8; * is a bond to another structure. Indicates the position.
  • R b6 and R b7 The aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R b6 and R b7 will be described in the same manner as in the case of R b1 .
  • p8 is an integer of 1 to 8, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1.
  • the plurality of R b6s or R b7s may be the same or different from each other.
  • the component (B1) is an aminomaleimide compound having a structural unit derived from the maleimide compound (b1) and a structural unit derived from the diamine compound (b2).
  • the component (B1) one type may be used alone, or two or more types may be used in combination.
  • the structural unit derived from the component (b1) for example, at least one N-substituted maleimide group among the N-substituted maleimide groups of the component (b1) has a Michael addition reaction with the amino group of the diamine compound (b2).
  • the structural unit derived from the component (b1) contained in the component (B1) may be one type alone or two or more types.
  • Examples of the structural unit derived from the component (b1) include a group represented by the following general formula (b1-7), a group represented by the following general formula (b1-8), and the like.
  • X b1 is a divalent organic group, and * indicates the bond position to another structure.
  • the content of the structural unit derived from the component (b1) in the aminomaleimide compound (B1) is not particularly limited, but is preferably 5 to 95% by mass, more preferably 30 to 93% by mass, and further preferably 60 to 90% by mass. %, Especially preferably 75 to 90% by mass. (B1) When the content of the structural unit derived from the component is within the above range, the dielectric property and the film handleability tend to be better.
  • the structural unit derived from the component (b2) for example, of the two amino groups possessed by the component (b2), one or both amino groups are added with the N-substituted maleimide group possessed by the maleimide compound (b1) and Michael addition. Examples thereof include structural units formed by reaction.
  • the structural unit derived from the component (b2) contained in the component (B1) may be one type alone or two or more types.
  • the amino group contained in the component (b2) is preferably a primary amino group.
  • Examples of the structural unit derived from the component (b2) include a group represented by the following general formula (b2-1), a group represented by the following general formula (b2-2), and the like.
  • X b4 is a divalent organic group, and * indicates the bond position to another structure.
  • X b4 in the general formula (b2-1) and the general formula (b2-2) is a divalent organic group, and corresponds to a divalent group obtained by removing two amino groups from the component (b2). ..
  • X b4 in the general formula (b2-1) and the general formula (b2-2) is a divalent group represented by the following general formula (b2-3).
  • R b11 and R b12 are independently aliphatic hydrocarbon groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, hydroxyl groups or halogen atoms.
  • X b5 has 1 carbon atom.
  • P9 and p10 are independently integers of 0 to 4. * Indicates a binding position to another structure.
  • R b13 and R b14 are independently aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms.
  • X b6 is an alkylene group having 1 to 5 carbon atoms and 2 to 5 carbon atoms. Alkylidene group, m-phenylenediisopropyridene group, p-phenylenediisopropyridene group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group or single bond.
  • P11 and p12 are 0 independently. It is an integer of ⁇ 4. * indicates the position of connection to other structures.
  • R b15 is an aliphatic hydrocarbon group or a halogen atom having 1 to 5 carbon atoms.
  • X b7 and X b8 are independently alkylene groups having 1 to 5 carbon atoms and 2 to 5 carbon atoms, respectively. Alkylidene group, ether group, sulfide group, sulfonyl group, carbonyloxy group, keto group or single bond.
  • P13 is an integer of 0 to 4. * Indicates the bond position to other structures.
  • Examples of the aliphatic hydrocarbon group or halogen atom of 1 to 5 include the same as R b1 in the above general formula (b1-2).
  • As the aliphatic hydrocarbon group an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group and an ethyl group are further preferable.
  • the number of carbon atoms represented by X b5 in the general formula (b2-3), X b6 in the general formula (b2-3-1), and X b7 and X b8 in the general formula (b2-3-2) is 1.
  • the alkylene group to 5 and the alkylidene group having 2 to 5 carbon atoms will be described in the same manner as in the case of X b2 in the above general formula (b1-3).
  • P9 and p10 in the above general formula (b2-3) are independently integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 3, more preferably 0 to 3. An integer of 2, more preferably 0 or 2.
  • P11 and p12 in the above general formula (b2-3-1) are independently integers of 0 to 4, and from the viewpoint of availability, both are preferably integers of 0 to 2, more preferably. It is 0 or 1, more preferably 0.
  • R b13s or R b14s may be the same or different from each other.
  • P13 in the above general formula (b2-3-2) is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0 from the viewpoint of availability. be.
  • component (b2) examples include 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4.
  • the component (b2) includes 4,4'-diaminodiphenylmethane and 4,4'-diamino from the viewpoint of excellent solubility in an organic solvent, reactivity with the maleimide compound (b1), and heat resistance.
  • the component (b2) is preferably 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane from the viewpoint of excellent dielectric properties and low water absorption.
  • the component (b2) is preferably 2,2-bis [4- (4-aminophenoxy) phenyl] propane from the viewpoint of excellent mechanical properties such as high adhesiveness to a conductor, elongation, and breaking strength.
  • the component (b2) is excellent in solubility in an organic solvent, reactivity at the time of synthesis, heat resistance, high adhesion to a conductor, and also excellent in dielectric properties and low hygroscopicity.
  • 4,4'-[1,3-phenylenebis (1-methylethylidene)] bisaniline and 4,4'-[1,4-phenylenebis (1-methylethylidene)] bisaniline are preferable.
  • the content of the structural unit derived from the component (b2) in the aminomaleimide compound (B1) is not particularly limited, but is preferably 5 to 95% by mass, more preferably 7 to 70% by mass, and further preferably 10 to 40% by mass. %, Especially preferably 10 to 25% by mass. (B2)
  • the content of the structural unit derived from the component is within the above range, the dielectric properties, heat resistance, flame retardancy and glass transition temperature tend to be better.
  • the equivalent ratio (Tb2 / Tb1) of the group (including the N-substituted maleimide group) to the total equivalent (Tb1) is not particularly limited, but is preferably 0.05 to 10, more preferably 0.5 to 7, and further. It is preferably 1 to 5. When the equivalent ratio (Tb2 / Tb1) is within the above range, the dielectric properties, heat resistance, flame retardancy and glass transition temperature tend to be better.
  • the number average molecular weight of the aminomaleimide compound (B1) is not particularly limited, but is preferably 400 to 10,000, more preferably 500 to 5,000, still more preferably 600 to 2,000, and particularly preferably 700 to 1, It is 500.
  • the aminomaleimide compound (B1) is an aminomaleimide compound represented by the following general formula (b2-4) from the viewpoints of dielectric properties, solubility in an organic solvent, high adhesiveness to a conductor, moldability of a resin film, and the like. Is preferably contained.
  • the component (B1) can be produced, for example, by reacting a maleimide compound (b1) with a diamine compound (b2) in an organic solvent. By reacting the maleimide compound (b1) with the diamine compound (b2), the aminomaleimide compound (B1) obtained by the Michael addition reaction between the maleimide compound (b1) and the diamine compound (b2) is obtained.
  • reaction catalyst When the maleimide compound (b1) and the diamine compound (b2) are reacted, a reaction catalyst may be used if necessary.
  • the reaction catalyst include acidic catalysts such as p-toluenesulfonic acid; amines such as triethylamine, pyridine and tributylamine; imidazoles such as methylimidazole and phenylimidazole; and phosphorus catalysts such as triphenylphosphine. ..
  • One type of reaction catalyst may be used alone, or two or more types may be used in combination.
  • the amount of the reaction catalyst to be blended is not particularly limited, but for example, 0.01 to 5 parts by mass may be used with respect to 100 parts by mass of the total amount of the maleimide compound (b1) and the diamine compound (b2).
  • the reaction temperature of the above reaction is preferably 50 to 160 ° C. from the viewpoint of workability such as reaction rate and suppression of gelation during the reaction. Further, the reaction time of the above reaction is preferably 1 to 10 hours from the same viewpoint. Further, in this step, the solid content concentration and the solution viscosity of the reaction raw material may be adjusted by adding or concentrating the organic solvent.
  • the solid content concentration of the reaction raw material is not particularly limited, but is preferably 10 to 90% by mass, more preferably 15 to 85% by mass, and further preferably 20 to 80% by mass. When the solid content concentration of the reaction raw material is at least the above lower limit value, a good reaction rate is obtained, and the productivity tends to be better. Further, when the solid content concentration of the reaction raw material is not more than the above upper limit value, better solubility is obtained, stirring efficiency is improved, and gelation tends to be further suppressed.
  • the content thereof is not particularly limited, but from the viewpoint of heat resistance and dielectric properties, the total amount of the resin components in the resin composition is 100 parts by mass. It is preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass, still more preferably 30 to 70 parts by mass, and particularly preferably 40 to 60 parts by mass.
  • the component (C) is not particularly limited, but is not particularly limited.
  • (C1) Conjugated diene polymer having a vinyl group in the side chain [hereinafter, may be referred to as "(c1) component”. ]
  • the conjugated diene polymer having (c1) a vinyl group in the side chain may be referred to as (c2) a maleimide compound having two or more N-substituted maleimide groups [hereinafter, “component (c2)”.
  • Modified conjugated diene polymer (C1) [hereinafter, may be referred to as "modified conjugated diene polymer (C1)” or "(C1) component”. ] Is preferable.
  • the component (C) one type may be used alone, or two or more types may be used in combination.
  • the component (c1) is not particularly limited as long as it is a conjugated diene polymer having a vinyl group in the side chain.
  • the component (c1) one type may be used alone, or two or more types may be used in combination.
  • the component (c1) is preferably a conjugated diene polymer having a plurality of vinyl groups in the side chain.
  • the number of vinyl groups contained in one molecule of the component (c1) is not particularly limited, but is preferably 3 or more, more preferably 5 or more, still more preferably 10 or more from the viewpoint of dielectric properties and heat resistance. be.
  • the conjugated diene polymer means a polymer of a conjugated diene compound.
  • the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene and the like.
  • the conjugated diene polymer may be a polymer of one kind of conjugated diene compound or a copolymer of two or more kinds of conjugated diene compounds.
  • the conjugated diene polymer may be a copolymer of one or more kinds of conjugated diene compounds and one or more kinds of monomers other than the conjugated diene compounds.
  • the polymerization mode in that case is not particularly limited, and may be any of random polymerization, block polymerization and graft polymerization.
  • component (c1) examples include polybutadiene having a 1,2-vinyl group, a butadiene-styrene copolymer having a 1,2-vinyl group, polyisoprene having a 1,2-vinyl group, and the like. Be done. Among these, polybutadiene having a 1,2-vinyl group and a butadiene-styrene copolymer having a 1,2-vinyl group are preferable, and polybutadiene having a 1,2-vinyl group is preferable from the viewpoint of dielectric properties and heat resistance. More preferred.
  • the butadiene-derived 1,2-vinyl group contained in the component (c1) is a vinyl group contained in the butadiene-derived structural unit represented by the following formula (c1-1).
  • the component (c1) is polybutadiene having a 1,2-vinyl group
  • the content of the structural unit having a 1,2-vinyl group with respect to all the structural units derived from butadiene constituting the polybutadiene [hereinafter, "vinyl”. It may be referred to as "group content”. ] Is not particularly limited, but is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol, from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance. % Or more, particularly preferably 80 mol% or more, and most preferably 85 mol% or more.
  • the upper limit of the vinyl group content is not particularly limited, and may be 100 mol% or less, 95 mol% or less, or 90 mol% or less.
  • the structural unit having a 1,2-vinyl group a structural unit derived from butadiene represented by the above formula (c1-1) is preferable. From the same viewpoint, the polybutadiene having a 1,2-vinyl group is preferably a 1,2-polybutadiene homopolymer.
  • the number average molecular weight of the component (c1) is not particularly limited, but is preferably 400 to 2,500, more preferably 500 to 500, from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance. It is 2,000, more preferably 600 to 1,800, and particularly preferably 700 to 1,500.
  • the component (C1) is a modified conjugated diene polymer obtained by modifying (c1) a conjugated diene polymer having a vinyl group in the side chain with (c2) a maleimide compound having two or more N-substituted maleimide groups.
  • the component (c2) may be any maleimide compound having two or more N-substituted maleimide groups, and the above-mentioned maleimide compound or the derivative (B) thereof can be used.
  • the component (c2) one type may be used alone, or two or more types may be used in combination.
  • the components (c2) include solubility in an organic solvent, suppression of gelation during the reaction, compatibility of the component (C1) with other resins, dielectric properties, low thermal expansion, and heat resistance. Therefore, an aromatic bismaleimide compound substituted with an aliphatic hydrocarbon group is preferable, and a compound represented by the following general formula (c2-1) is more preferable.
  • R c1 and R c2 are independently aliphatic hydrocarbon groups having 1 to 5 carbon atoms.
  • X c1 is an alkylene group having 1 to 5 carbon atoms and an alkylidene group having 2 to 5 carbon atoms.
  • Q1 and q2 are independently, respectively. It is an integer of 0 to 4, and q1 + q2 is an integer of 1 or more.
  • Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R c1 and R c2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and a t-butyl group. Examples thereof include an n-pentyl group.
  • an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is preferable from the viewpoint of compatibility with other resins and suppression of gelation during the reaction. Is more preferable, and a methyl group and an ethyl group are further preferable.
  • Examples of the alkylene group having 1 to 5 carbon atoms represented by X c1 include a methylene group, a 1,2-dimethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group and the like. Can be mentioned.
  • an alkylene group having 1 to 3 carbon atoms is preferable, an alkylene group having 1 or 2 carbon atoms is more preferable, and a methylene group is further preferable.
  • Examples of the alkylidene group having 2 to 5 carbon atoms represented by X c1 include an ethylidene group, a propyridene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group and an isopentylidene group.
  • q1 and q2 are independently integers of 0 to 4, and are preferably integers of 1 to 3 from the viewpoints of availability, compatibility with other resins, and suppression of gelation during the reaction. , More preferably 1 or 2, still more preferably 2. From the same viewpoint, q1 + q2 is preferably an integer of 1 to 8, more preferably an integer of 2 to 6, and even more preferably 4. When q1 or q2 is an integer of 2 or more, the plurality of R c1s or R c2s may be the same or different from each other.
  • the divalent group represented by the general formula (c2-1-1) represented by X c1 is as follows.
  • R c3 and R c4 are independently aliphatic hydrocarbon groups or halogen atoms having 1 to 5 carbon atoms.
  • X c2 is an alkylene group having 1 to 5 carbon atoms and 2 to 5 carbon atoms. It is an alkylidene group, an ether group, a sulfide group, a sulfonyl group, a carbonyloxy group, a keto group or a single bond.
  • Q3 and q4 are independently integers of 0 to 4).
  • the aliphatic hydrocarbon group having 1 to 5 carbon atoms and the halogen atom represented by R c3 and R c4 will be described in the same manner as in the case of R c1 .
  • Examples of the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X c2 are the same as the alkylene group having 1 to 5 carbon atoms and the alkylidene group having 2 to 5 carbon atoms represented by X c1 .
  • q3 and q4 are each independently an integer of 0 to 4, and from the viewpoint of availability, both are preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
  • the plurality of R c3s or R c4s may be the same or different from each other.
  • Examples of the compound represented by the general formula (c2-1) include solubility in an organic solvent and suppression of gelation during the reaction, compatibility with the obtained component (C1) with other resins, and dielectric. From the viewpoint of properties, low thermal expansion and heat resistance, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide is preferable.
  • the modified conjugated diene polymer (C1) is a substituent formed by reacting a vinyl group of the conjugated diene polymer (c1) with an N-substituted maleimide group of the maleimide compound (c2) in the side chain [hereinafter, "" It may be referred to as "substituent (x)". ] It is preferable to have.
  • the substituent (x) has the following general formula (C-11) or (C) as a structure derived from the maleimide compound (c2) from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance. It is preferable that the group contains the structure represented by -12).
  • X C1 is a divalent organic group
  • * C1 is a site where the conjugated diene polymer (c1) is bonded to a carbon atom derived from a vinyl group in the side chain.
  • * C2 is another It is a part that binds to an atom.
  • the substituent (x) is represented by the following general formula (C-21) as a structure derived from the maleimide compound (c2) from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance. It is more preferable to include at least one selected from the group consisting of the above-mentioned structure and the structure represented by the following general formula (C-22).
  • the modified conjugated diene polymer (C1) preferably has a substituent (x) and a vinyl group (y) in the side chain.
  • the extent to which the substituent (x) is present in the modified conjugated diene polymer (C1) is the degree to which the vinyl group of the component (c1) is modified by the component (c2) [hereinafter, "vinyl group modification rate”. May be called. ] Can be used as an index.
  • the vinyl group modification rate is not particularly limited, but is preferably 20 to 70%, more preferably 30 to 60%, still more preferably, from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance. Is 35 to 50%.
  • the vinyl group modification rate is a value obtained by the method described in Examples.
  • the vinyl group (y) is preferably a 1,2-vinyl group having a structural unit derived from butadiene.
  • the component (C1) can be produced by reacting a conjugated diene polymer (c1) with a maleimide compound (c2).
  • the method for reacting the conjugated diene polymer (c1) with the maleimide compound (c2) is not particularly limited.
  • the component (C1) is obtained by charging a conjugated diene polymer (c1), a maleimide compound (c2), a reaction catalyst and an organic solvent into a reaction vessel and reacting them with heating, heat retention, stirring, etc., if necessary. Can be done.
  • the reaction temperature of the above reaction is preferably 70 to 120 ° C., more preferably 80 to 110 ° C., still more preferably 85 to 105 ° C. from the viewpoint of workability and suppression of gelation during the reaction.
  • the reaction time of the above reaction is preferably 0.5 to 15 hours, more preferably 1 to 10 hours, still more preferably 3 to 7 hours.
  • these reaction conditions can be appropriately adjusted according to the type of raw material used and the like, and are not particularly limited.
  • organic solvent used in the above reaction examples include alcohol solvents such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether and propylene glycol monomethyl ether; and ketone solvents such as acetone, methyl ethyl acetate, methyl isobutyl ketone and cyclohexanone.
  • alcohol solvents such as methanol, ethanol, butanol, butyl cellosolve, ethylene glycol monomethyl ether and propylene glycol monomethyl ether
  • ketone solvents such as acetone, methyl ethyl acetate, methyl isobutyl ketone and cyclohexanone.
  • Aromatic hydrocarbon solvents such as toluene, xylene, mesitylen; ester solvents such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate; N, N-dimethylformamide, N, N-dimethylacetamide, N Examples thereof include a nitrogen atom-containing solvent such as methyl-2-pyrrolidone.
  • the organic solvent one kind may be used alone, or two or more kinds may be used in combination. Among these, toluene is preferable from the viewpoint of resin solubility.
  • the total content of the conjugated diene polymer (c1) and the maleimide compound (c2) in the reaction solution is not particularly limited, but is preferably 10 to 70% by mass, more preferably 15 to. It is 60% by mass, more preferably 20 to 50% by mass.
  • the total content of the conjugated diene polymer (c1) and the maleimide compound (c2) is at least the above lower limit, a good reaction rate is obtained and the productivity tends to be better.
  • the total content of the conjugated diene polymer (c1) and the maleimide compound (c2) is not more than the above upper limit value, better solubility is obtained, stirring efficiency is improved, and gelation tends to be further suppressed. be.
  • reaction catalyst organic peroxide is preferable from the viewpoint of obtaining sufficient reactivity while suppressing gelation during the reaction, and ⁇ , ⁇ '-bis (t-butylperoxy) diisopropylbenzene is more preferable. preferable.
  • One type of reaction catalyst may be used alone, or two or more types may be used in combination.
  • the amount of the reaction catalyst used is not particularly limited, but is preferably 0.01 to 1.2 parts by mass, more preferably 0, with respect to 100 parts by mass of the total amount of the conjugated diene polymer (c1) and the maleimide compound (c2). It is 03 to 1.0 part by mass, more preferably 0.05 to 0.8 part by mass.
  • the ratio of the number of moles (M m ) of the N-substituted maleimide group of the maleimide compound (c2) to the number of moles (M v ) of the side chain vinyl group of the conjugated diene polymer (c1) in carrying out the above reaction is not particularly limited, but is preferably 0.001 to 0.5, from the viewpoint of compatibility with other resins of the obtained (C1) component and suppression of gelation during the reaction. It is preferably 0.005 to 0.1, more preferably 0.008 to 0.05.
  • the number average molecular weight of the component (C) is not particularly limited, but is preferably 700 to 6,000, more preferably 800 to 6,000, from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance. It is 5,000, more preferably 900 to 4,500, and particularly preferably 1,000 to 4,000.
  • the content thereof is not particularly limited, but from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance, the resin.
  • the content thereof is not particularly limited, but from the viewpoint of compatibility with other resins, dielectric properties, low thermal expansion and heat resistance, the resin.
  • 100 parts by mass of the total resin components in the composition preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, still more preferably 10 to 30 parts by mass, and particularly preferably 15 to 25 parts by mass. be.
  • the component (D) is not particularly limited as long as it is a thermoplastic elastomer having a structural unit derived from a styrene compound.
  • the component (D) one type may be used alone, or two or more types may be used in combination.
  • the component (D) preferably has a structural unit represented by the following general formula (d-1).
  • R d1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R d2 is an alkyl group having 1 to 5 carbon atoms
  • K is an integer of 0 to 5).
  • Examples of the alkyl group having 1 to 5 carbon atoms represented by R d1 and R d2 include a methyl group, an ethyl group, an n-propyl group and the like. Among these, an alkyl group having 1 to 3 carbon atoms is preferable, an alkyl group having 1 or 2 carbon atoms is more preferable, and a methyl group is further preferable.
  • k is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0.
  • Examples of the structural unit other than the structural unit derived from the styrene compound contained in the component (D) include a structural unit derived from butadiene, a structural unit derived from isoprene, a structural unit derived from maleic acid, a structural unit derived from maleic anhydride, and the like. Can be mentioned.
  • the structural unit derived from butadiene and the structural unit derived from isoprene may be hydrogenated.
  • the structural unit derived from butadiene is a structural unit in which ethylene units and butylene units are mixed
  • the structural unit derived from isoprene is a structural unit in which ethylene units and propylene units are mixed.
  • the components (D) include hydrogenated additives (SEBS, SBBS) of a styrene-butadiene-styrene block copolymer and styrene from the viewpoints of dielectric properties, adhesion to conductors, heat resistance, glass transition temperature and low thermal expansion.
  • SEBS hydrogenated additives
  • SBBS hydrogenated additives
  • SEPS hydrogenated additive
  • SMA styrene-maleic anhydride copolymer
  • SEBS hydrogen additive
  • SEPS hydrogen additive
  • styrene content the content of structural units derived from styrene
  • styrene content Is not particularly limited, but is preferably 5 to 80% by mass, more preferably 10 to 75% by mass, still more preferably, from the viewpoints of dielectric properties, adhesiveness to conductors, heat resistance, glass transition temperature and low thermal expansion. Is 15 to 70% by mass, particularly preferably 20 to 50% by mass.
  • the melt flow rate (MFR) of SEBS is not particularly limited, but is preferably 0.1 to 20 g / 10 min, more preferably 0.3 to 17 g under the measurement conditions of 230 ° C. and a load of 2.16 kgf (21.2 N). / 10 min, more preferably 0.5 to 15 g / 10 min.
  • the weight average molecular weight (Mw) of the component (D) is not particularly limited, but is preferably 12,000 to 1,000,000, more preferably 30,000 to 500,000, still more preferably 50,000 to 120, 000, particularly preferably 70,000 to 100,000.
  • the weight average molecular weight (Mw) means a value measured by gel permeation chromatography (GPC) in terms of polystyrene.
  • the content thereof is not particularly limited, but from the viewpoint of dielectric properties, heat resistance, moldability and compatibility, the resin component in the resin composition It is preferably 10 to 60 parts by mass, more preferably 15 to 50 parts by mass, still more preferably 20 to 40 parts by mass, and particularly preferably 25 to 30 parts by mass with respect to 100 parts by mass of the total.
  • the resin composition of the present embodiment tends to exhibit excellent dielectric properties while having even better heat resistance.
  • the component (E) one type may be used alone, or two or more types may be used in combination.
  • component (E) examples include 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, and 2-ethyl-1-methyl.
  • Imidazole 1,2-diethylimidazole, 1-ethyl-2-methylimidazole, 2-ethyl-4-methylimidazole, 4-ethyl-2-methylimidazole, 1-isobutyl-2-methylimidazole, 2-phenyl-4 -Methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4- Methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 2, 4-Diamino-6- [2'-methylimidazolyl- (1')] eth
  • Examples thereof include a salt of the above-mentioned imidazole compound and a salt of isocyanuric acid, and a modified imidazole compound such as a salt of the above-mentioned imidazole compound and hydrobromic acid.
  • the modified imidazole compound represented by the following general formula (e-1) or the following general formula (e-2) is preferable.
  • R e1 , R e2 , R e3 and R e4 are each independently a hydrogen atom, an aliphatic hydrocarbon group or a phenyl group having 1 to 20 carbon atoms, and X e1 is an alkylene group or a divalent group. It is an aromatic hydrocarbon group of.
  • R e5 , R e6 , R e7 and R e8 are independently hydrogen atoms, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or a phenyl group, and X e2 is an alkylene group and an alkylidene group. , Ether group or sulfonyl group.
  • the resin composition of the present embodiment is further excellent in compatibility of the resin component by containing the modified imidazole compound represented by the general formula (e-1) or the general formula (e-2). It will be.
  • the cause is not clear, but it is presumed as follows.
  • the modified imidazole compound has an imidazolyl group as a highly polar group, and "-CH 2 -X e1 -CH 2- " in the general formula (e-1) and the general formula (e-2) as a group having a low polarity. It has a hydrocarbon group represented by "-Ph-X e2 -Ph-" in it. Therefore, it is presumed that the modified imidazole compound functions as a compatibilizer between the highly polar component (B) and the less polar elastomer.
  • the resin composition containing the modified imidazole compound represented by the above general formula (e-1) tends to have particularly excellent dielectric properties while having good heat resistance. Further, the resin composition containing the modified imidazole compound represented by the general formula (e-2) tends to have particularly excellent heat resistance as well as improved dielectric properties.
  • the aliphatic hydrocarbon group represented by R e1 , R e2 , R e3 and R e4 in the above general formula (e-1) has 1 to 20 carbon atoms, preferably 1 to 10 and more preferably 1 to 5 carbon atoms. , More preferably 1 or 2.
  • Examples of the aliphatic hydrocarbon group represented by R e1 , R e2 , R e3 and R e4 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a decyl group.
  • Alkyl groups such as dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group and stearyl group; alkenyl group; alkynyl group and the like can be mentioned.
  • These aliphatic hydrocarbon groups may be linear or branched chain. Among these, a methyl group and an ethyl group are preferable.
  • the carbon number of the alkylene group represented by Xe1 in the general formula (e-1) is preferably 1 to 10, more preferably 2 to 8, and even more preferably 3 to 5.
  • Examples of the alkylene group represented by X e1 include a methylene group, an ethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, a 1,6-hexamethylene group and the like. Be done. Among these, a 1,4-tetramethylene group is preferable.
  • the number of carbon atoms of the divalent aromatic hydrocarbon group represented by X e1 is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 12.
  • Examples of the divalent aromatic hydrocarbon group represented by X e1 include a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, an anthrylene group and the like.
  • the aliphatic hydrocarbon group represented by R e5 , R e6 , R e7 and R e8 in the above general formula (e-2) has 1 to 20 carbon atoms, preferably 1 to 10 and more preferably 1 to 5 carbon atoms. , More preferably 1 or 2.
  • Examples of the aliphatic hydrocarbon group represented by R e5 , R e6 , R e7 and R e8 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group and a decyl group.
  • Alkyl groups such as dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group and stearyl group; alkenyl group; alkynyl group and the like can be mentioned.
  • These aliphatic hydrocarbon groups may be linear or branched chain.
  • R e5 , R e6 , R e7 and R e8 , R e5 and R e6 are preferably hydrogen atoms, and R e7 and R e8 are preferably phenyl groups.
  • the carbon number of the alkylene group represented by Xe2 in the general formula ( e -2) is preferably 1 to 10, more preferably 2 to 8, and even more preferably 3 to 5.
  • Examples of the alkylene group represented by X e2 include a methylene group, an ethylene group, a 1,3-trimethylene group, a 1,4-tetramethylene group, a 1,5-pentamethylene group, a 1,6-hexamethylene group and the like. Be done.
  • the carbon number of the alkylidene group represented by X- e2 is preferably 3 to 10, more preferably 3 to 8, and even more preferably 3 to 5.
  • Examples of the alkylidene group represented by X- e2 include an ethylidene group, a propyridene group, an isopropylidene group, a butylidene group, an isobutylidene group, a pentylidene group, and an isopentylidene group.
  • the propylidene group is preferable.
  • the content thereof is not particularly limited, but the total of the resin components in the resin composition is 100 from the viewpoint of compatibility, dielectric properties and heat resistance. It is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 6 parts by mass, still more preferably 0.5 to 4 parts by mass, and particularly preferably 0.8 to 2 parts by mass with respect to parts by mass. ..
  • the resin composition of the present embodiment may be referred to as an inorganic filler (F) [hereinafter, "(F) component”. ],
  • the coefficient of thermal expansion, elastic modulus, heat resistance and flame retardancy tend to be further improved.
  • the inorganic filler (F) one type may be used alone, or two or more types may be used in combination.
  • the component (F) is not particularly limited, but is, for example, silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, and hydroxide.
  • examples thereof include aluminum, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay, talc, aluminum borate, silicon carbide and the like.
  • silica, alumina, mica, and talc are preferable, silica and alumina are more preferable, and silica is further preferable, from the viewpoints of thermal expansion coefficient, elastic modulus, heat resistance, and flame retardancy.
  • silica examples include precipitated silica produced by a wet method and having a high water content, and dry silica produced by a dry method and containing almost no bound water or the like. Further, as the dry method silica, for example, crushed silica, fumed silica, molten silica and the like can be mentioned depending on the difference in the manufacturing method.
  • the particle size of the inorganic filler (F) is not particularly limited, but is preferably 0.01 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m, still more preferably 0.2 to 1 ⁇ m, and particularly preferably 0.3 to 0. It is 0.8 ⁇ m.
  • the particle size of the inorganic filler (F) refers to the average particle size, and when the cumulative frequency distribution curve by the particle size is obtained with the total volume of the particles as 100%, the particles having a volume corresponding to 50%. It is the diameter.
  • the particle size of the inorganic filler (F) can be measured by a particle size distribution measuring device or the like using a laser diffraction / scattering method.
  • Examples of the shape of the inorganic filler (F) include a spherical shape and a crushed shape, and the shape is preferably spherical.
  • the content of the inorganic filler (F) in the resin composition is not particularly limited, but has low thermal expansion property, elastic modulus, heat resistance and heat resistance. From the viewpoint of flame retardancy, it is preferably 10 to 70% by mass, more preferably 20 to 65% by mass, still more preferably 30 to 60% by mass, particularly, with respect to the total solid content (100% by mass) of the resin composition. It is preferably 40 to 55% by mass.
  • the resin composition of the present embodiment contains the inorganic filler (F)
  • a coupling agent is used in combination as necessary for the purpose of improving the dispersibility of the inorganic filler (F) and the adhesion with the organic component. You may.
  • the resin composition of the present embodiment tends to further improve the flame retardancy of the resin composition by containing the flame retardant (G).
  • the flame retardant (G) may be used alone or in combination of two or more. Further, a flame retardant aid may be contained if necessary.
  • Examples of the flame retardant (G) include phosphorus-based flame retardants, metal hydrates, halogen-based flame retardants, and the like. Among these, phosphorus-based flame retardants and metal hydrates are preferable from the viewpoint of environmental problems.
  • -Phosphorus flame retardant- Phosphorus-based flame retardants which are generally used as flame retardants, can be used without particular limitation as long as they contain phosphorus atoms, but from the viewpoint of environmental problems, they do not contain halogen atoms. Is preferable.
  • the phosphorus-based flame retardant may be an inorganic phosphorus-based flame retardant, but is organic from the viewpoints of dielectric properties, adhesion to conductors, heat resistance, glass transition temperature, low thermal expansion and flame retardancy. Phosphorus flame retardants are preferred.
  • inorganic phosphorus-based flame retardant examples include red phosphorus; ammonium phosphate such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. Phosphoric acid; phosphine oxide and the like.
  • organic phosphorus-based flame retardant examples include aromatic phosphoric acid esters, mono-substituted phosphonic acid diesters, 2-substituted phosphinic acid esters, metal salts of 2-substituted phosphinic acid, organic nitrogen-containing phosphorus compounds, and cyclic organic phosphorus compounds.
  • examples thereof include phosphine oxide compounds.
  • aromatic phosphate esters, metal salts of disubstituted phosphinic acid, and phosphine oxide compounds are preferable.
  • the metal salt of the disubstituted phosphinic acid include lithium salt, sodium salt, potassium salt, calcium salt, magnesium salt, aluminum salt, titanium salt, zinc salt and the like. Among these, aluminum salts are preferable.
  • aromatic phosphate ester examples include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresyldi-2,6-xylenyl phosphate, resorcinolbis (diphenyl phosphate), 1,3. -Phenylene bis (di-2,6-xylenyl phosphate), bisphenol A-bis (diphenyl phosphate), 1,3-phenylene bis (diphenyl phosphate) and the like can be mentioned.
  • Examples of the mono-substituted phosphonic acid diester include divinyl phenylphosphonate, diallyl phenylphosphonate, and bis (1-butenyl) phenylphosphonate.
  • Examples of the disubstituted phosphinic acid ester include phenyl diphenylphosphine acid and methyl diphenylphosphine acid.
  • Examples of the metal salt of disubstituted phosphinic acid include a metal salt of dialkylphosphinic acid, a metal salt of diallylphosphinic acid, a metal salt of divinylphosphinic acid, a metal salt of diarylphosphinic acid and the like. As these metal salts, aluminum salts are preferable.
  • organic nitrogen-containing phosphorus compound examples include phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicredylphosphazene; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; and melam polyphosphate.
  • phosphazene compounds such as bis (2-allylphenoxy) phosphazene and dicredylphosphazene; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; and melam polyphosphate.
  • cyclic organic phosphorus compound examples include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-. Examples thereof include 10-phosphaphenanthrene-10-oxide.
  • Examples of the phosphine oxide compound include paraxylylene bisdiphenylphosphine oxide, paraphenylene bisdiphenylphosphine oxide, ethylene bisdiphenylphosphine oxide, biphenylene bisdiphenylphosphine oxide, and naphthylene bisdiphenylphosphine oxide.
  • aromatic phosphoric acid esters aromatic phosphoric acid esters, metal salts of disubstituted phosphinic acid, and phosphinoxide compounds are preferable, and 1,3-phenylenebis (di-2,6-xylenyl phosphate).
  • 1,3-phenylenebis di-2,6-xylenyl phosphate
  • Aluminum salt of dialkylphosphinic acid, paraxylylene bisdiphenylphosphine oxide are more preferred.
  • Metal hydrate examples include aluminum hydroxide hydrate and magnesium hydroxide hydrate.
  • halogen-based flame retardant examples include chlorine-based flame retardants and brominated flame retardants.
  • chlorine-based flame retardant examples include chlorinated paraffin and the like.
  • the content of the phosphorus-based flame retardant in the resin composition is not particularly limited, but is flame-retardant, moldable and heat-resistant.
  • the total amount of the resin components in the resin composition is 100 parts by mass, preferably 0.2 to 10 parts by mass, more preferably 0.3 to 7 parts by mass, still more preferably, in terms of phosphorus atoms. It is 0.5 to 5 parts by mass, particularly preferably 1 to 3 parts by mass.
  • the resin composition of the present embodiment may be further referred to as a component (H) [hereinafter, "(H) component” other than the above. ] May be contained.
  • the other component (H) include thermosetting resins, thermoplastic polymers, curing accelerators, flame retardants, additives, organic solvents, and the like, in addition to the above components.
  • the component (H) one type may be used alone or two or more types may be used in combination for each.
  • Examples of the curing accelerator as the component (H) include an acidic catalyst such as p-toluenesulfonic acid; an amine compound such as triethylamine, pyridine and tributylamine; a tertiary amine compound; a quaternary ammonium compound; triphenylphosphine.
  • an acidic catalyst such as p-toluenesulfonic acid
  • an amine compound such as triethylamine, pyridine and tributylamine
  • a tertiary amine compound such as triethylamine, pyridine and tributylamine
  • a tertiary amine compound such as triethylamine, pyridine and tributylamine
  • a tertiary amine compound such as triethylamine, pyridine and tributylamine
  • a tertiary amine compound such as triethylamine, pyridine and tribu
  • Phosphorus compounds such as: Dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexin-3, 2,5-dimethyl-2,5-bis (t-butylperoxy) )
  • Organic peroxides such as hexane, t-butylperoxyisopropyl monocarbonate, ⁇ , ⁇ '-bis (t-butylperoxy) diisopropylbenzene; carboxylates such as manganese, cobalt and zinc.
  • the additive as the component (H) include antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants and the like.
  • the amount of the component (H) used is not particularly limited and may be used within a range that does not impair the effects of the present invention.
  • the resin composition of the present embodiment may contain an organic solvent. Diluting with an organic solvent tends to improve the handleability of the resin composition of the present embodiment and the ease of producing a prepreg described later.
  • the resin composition containing an organic solvent may be generally referred to as a resin varnish or a varnish.
  • organic solvent examples include alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as tetrahydrofuran; Aromatic hydrocarbon solvents such as toluene, xylene and mesitylen; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethylsulfoxide; ester solvents such as ⁇ -butyrolactone Can be mentioned.
  • alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether
  • ketone solvents such as acetone, methyl
  • alcohol-based solvents ketone-based solvents, nitrogen atom-containing solvents, and aromatic hydrocarbon-based solvents are preferable, aromatic hydrocarbon-based solvents are more preferable, and toluene is even more preferable.
  • the solid content concentration of the resin composition is not particularly limited, but is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, and further preferably 40. It is about 60% by mass.
  • the solid content concentration of the resin composition is within the above range, the handleability of the resin composition tends to be easy, the impregnation property into the base material and the appearance of the produced prepreg tend to be better. Further, the solid content concentration of the resin in the prepreg, which will be described later, tends to be easily adjusted, and the production of the prepreg having a desired thickness tends to be easier.
  • the resin composition of the present embodiment can be produced by mixing each of the above components by a known method. At this time, each component may be dissolved or dispersed while stirring. Conditions such as mixing order, temperature, and time are not particularly limited, and may be arbitrarily set according to the type of raw material and the like.
  • the dielectric constant (Dk) of the cured product of the present embodiment at 10 GHz is not particularly limited, but is preferably 3.0 or less, more preferably 2.9 or less, still more preferably 2.8 or less.
  • the dielectric constant (Dk) is a value based on the cavity resonator perturbation method, and more specifically, a value measured by the method described in the examples. Further, in the present specification, the term "dielectric constant" simply means the relative permittivity.
  • the dielectric loss tangent (Df) of the cured product of the resin composition of the present embodiment at 10 GHz is not particularly limited, but is preferably 0.0050 or less, more preferably 0.0040 or less, still more preferably 0.0030 or less, and particularly preferably 0.0030 or less. Is 0.0025 or less, most preferably 0.0022 or less.
  • the dielectric loss tangent (Df) is a value based on the cavity resonator perturbation method, and more specifically, a value measured by the method described in Examples.
  • the resin composition of the present embodiment is not particularly limited, but the glass transition temperature measured by the method described in Examples is preferably 190 ° C. or higher, more preferably 200 ° C. or higher, still more preferably 210 ° C. or higher. ..
  • the prepreg of the present embodiment is a prepreg containing the resin composition of the present embodiment.
  • a known sheet-shaped fiber reinforced base material used for various laminated plates for electrical insulating materials can be used as the sheet-shaped fiber reinforced base material contained in the prepreg of the present embodiment.
  • the material of the sheet-shaped fiber reinforcing base material include inorganic fibers such as E glass, D glass, S glass, and Q glass; organic fibers such as polyimide, polyester, and tetrafluoroethylene; and a mixture thereof.
  • These sheet-shaped fiber reinforced base materials have shapes such as woven fabrics, non-woven fabrics, robinks, chopped strand mats, and surfaced mats.
  • the thickness of the sheet-shaped fiber reinforced base material is not particularly limited, but is, for example, 0.02 to 0.5 mm.
  • the sheet-shaped fiber reinforced base material may be surface-treated with a coupling agent or the like from the viewpoints of impregnation property of the resin composition, heat resistance when formed into a laminated board, hygroscopicity and processability, and may be a machine. It may be the one which has been subjected to the fiber opening treatment.
  • the prepreg of the present embodiment can be produced, for example, by impregnating or applying the resin composition of the present embodiment to a sheet-shaped fiber reinforced base material and then drying it, if necessary.
  • a method of impregnating or applying the resin composition to the sheet-shaped fiber reinforced base material for example, a hot melt method, a solvent method, or the like can be adopted.
  • the hot melt method is a method of impregnating or applying a resin composition containing no organic solvent to a sheet-shaped fiber reinforced base material.
  • One aspect of the hot melt method is a method in which the resin composition is once coated on coated paper having good peelability, and then the coated resin composition is laminated on a sheet-shaped fiber reinforced base material.
  • the solvent method is a method of impregnating or applying a resin composition containing an organic solvent to a sheet-shaped fiber reinforced base material. Specifically, for example, a method of immersing a sheet-shaped fiber reinforced base material in a resin composition containing an organic solvent and then drying it can be mentioned.
  • the drying conditions of the solvent method can be, for example, a condition of heating at 80 to 200 ° C. for 1 to 30 minutes. By drying, the organic solvent is removed and the resin composition is semi-cured (B-staged) to obtain the prepreg of the present embodiment.
  • the solid content concentration derived from the resin composition in the prepreg of the present embodiment is not particularly limited, but is preferably 30 to 90% by mass. When the solid content concentration derived from the resin composition in the prepreg is within the above range, better formability tends to be obtained when the laminated board is formed.
  • the resin film of the present embodiment is a resin film containing the resin composition of the present embodiment.
  • the resin film of the present embodiment can be produced, for example, by applying a resin composition containing an organic solvent, that is, a resin varnish, to a support and then heat-drying the support.
  • a resin composition containing an organic solvent that is, a resin varnish
  • the support for example, a film of a polyolefin such as polyethylene, polypropylene, or polyvinyl chloride; polyethylene terephthalate [hereinafter, may be referred to as "PET". ].
  • Polyester film such as polyethylene naphthalate
  • various plastic films such as polycarbonate film and polyimide film
  • metal foil such as copper foil and aluminum foil
  • release paper and the like for example, by applying a resin composition containing an organic solvent, that is, a resin varnish.
  • the support may be surface-treated such as matte treatment and corona treatment. Further, the support may be one that has been subjected to a mold release treatment with a silicone resin-based mold release agent, an alkyd resin-based mold release agent, a fluororesin-based mold release agent, or the like.
  • the thickness of the support is not particularly limited, but is preferably 10 to 150 ⁇ m, more preferably 20 to 100 ⁇ m, and even more preferably 25 to 50 ⁇ m.
  • a coating device for coating the resin varnish for example, a coating device known to those skilled in the art such as a comma coater, a bar coater, a kiss coater, a roll coater, a gravure coater, and a die coater can be used. These coating devices may be appropriately selected according to the film thickness to be formed.
  • the drying conditions after the resin composition is applied may be appropriately determined according to the content of the organic solvent, the boiling point, and the like, and are not particularly limited. For example, in the case of a resin varnish containing 40 to 60% by mass of an aromatic hydrocarbon solvent, a resin film can be suitably formed by drying at 50 to 200 ° C. for about 3 to 10 minutes.
  • the laminated board of this embodiment is a laminated board containing the prepreg of this embodiment and a metal foil.
  • the laminated board having a metal foil may be referred to as a metal-clad laminated board.
  • the metal of the metal foil is not particularly limited as long as it is used for electrical insulating materials, but from the viewpoint of conductivity, copper, gold, silver, nickel, platinum, molybdenum, ruthenium, aluminum, tungsten, iron and titanium. , Chromium, alloys containing at least one of these metal elements are preferred, copper and aluminum are more preferred, and copper is even more preferred.
  • the laminated board of the present embodiment can be manufactured, for example, by arranging a metal foil on one side or both sides of the prepreg of the present embodiment and then heat-pressing molding. At that time, only one prepreg may be used, or two or more prepregs may be laminated and used.
  • the conditions for heat-press molding are not particularly limited, but for example, the temperature can be 100 to 300 ° C., the pressure can be 0.2 to 10 MPa, and the time can be 0.1 to 5 hours. Further, for the heat and pressure molding, a method of holding the vacuum state for 0.5 to 5 hours by using a vacuum press or the like may be adopted.
  • the multilayer printed wiring board of the present embodiment contains one or more selected from the group consisting of the prepreg, the resin film, and the laminated board of the present embodiment. That is, the multilayer printed wiring board of the present embodiment includes at least a multilayer structure and a conductor circuit layer containing a cured product of the prepreg of the present embodiment, a cured product of the resin film of the present embodiment, or the laminated plate of the present embodiment. include.
  • the multilayer printed wiring board of the present embodiment is subjected to conductor circuit formation and multi-layer adhesive processing by a known method for one or more selected from the group consisting of the prepreg, the resin film and the laminated board of the present embodiment. Can be manufactured by.
  • the conductor circuit can be formed, for example, by appropriately performing drilling, metal plating, etching of a metal foil, or the like.
  • the semiconductor package of this embodiment is a semiconductor package formed by using the multilayer printed wiring board of this embodiment.
  • the semiconductor package of this embodiment is, for example, a semiconductor package mounted on a multilayer printed wiring board of this embodiment.
  • the semiconductor package of the present embodiment can be manufactured, for example, by mounting a semiconductor chip, a memory, or the like on the multilayer printed wiring board of the present embodiment by a known method.
  • the number average molecular weight was measured by the following procedure. (Measurement method of number average molecular weight) The number average molecular weight was converted from the calibration curve using standard polystyrene by gel permeation chromatography (GPC).
  • the calibration curve is standard polystyrene: TSKstandard POLYSTYRENE (Type; A-2500, A-5000, F-1, F-2, F-4, F-10, F-20, F-40) [manufactured by Tosoh Corporation, Product name] was used for approximation by a cubic equation.
  • the measurement conditions of GPC are shown below.
  • HLC-8320GPC Detector Ultraviolet absorption detector UV-8320 [manufactured by Tosoh Corporation]
  • Eluent Tetrahydrofuran ⁇ Sample concentration: 10 mg / 5 mL ⁇ Injection amount: 25 ⁇ L ⁇ Flow rate: 1.00 mL / min ⁇ Measurement temperature: 40 ° C
  • X a2 is a divalent organic group and is described in the same manner as X a2 in the above general formula (a-5).
  • the vinyl group modification rate of the component (c2) was 40%, and the number average molecular weight of the obtained modified conjugated diene polymer was 3,500.
  • a low profile copper foil manufactured by Mitsui Mining & Smelting Co., Ltd., trade name: 3EC-VLP-18
  • the low profile copper foil was arranged with the M side facing the resin powder side.
  • the laminate was heat-press molded under the conditions of a temperature of 230 ° C., a pressure of 2.0 MPa, and a time of 120 minutes to form and cure the resin powder on the resin plate to obtain a resin plate with double-sided copper foil.
  • the thickness of the resin plate portion of the obtained resin plate with double-sided copper foil was 1 mm.
  • the image for calculating the average domain size DL of the separated portion was taken at an observation magnification of 65 times for any 6 visual fields.
  • backscattered electron images were acquired even at the observation magnifications of 200 times and 1,000 times.
  • phase-separated resin region that looks relatively dark was identified as the "separated portion”, and the other regions were identified as the "non-separated portion".
  • the separated portion could be clearly identified, for example, as shown in FIG.
  • Binarization processing of reflected electron image The reflected electron image obtained above is used as a condition for binarization processing by image analysis processing software (manufactured by Nippon Roper Co., Ltd., product name: Image-Pro Analyzer 7.0J).
  • a binarized image is obtained by adjusting the RGB threshold in the range of 40 to 100 and binarizing under the condition that the separated portion specified in (3) above has one value and the non-separated portion has the other value. Obtained.
  • the copper foil was removed by immersing the resin plate with double-sided copper foil obtained in each example in a 10% by mass solution of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Company, Inc.), which is a copper etching solution, to prepare a 2 mm ⁇ 50 mm test piece. did.
  • the relative permittivity (Dk) and the dielectric loss tangent (Df) of the test piece were measured in the 10 GHz band at an atmospheric temperature of 25 ° C. according to the cavity resonator perturbation method.
  • thermomechanical measuring device (manufactured by TA Instruments Japan Co., Ltd., Q400 (model number)]
  • IPC The Institute for Interconnecting and Packaging Electronic Circuits
  • Compounds that are tetramethylene groups-Modified imidazole compounds represented by the general formula (e-2): R e5 and R e6 in the above general formula (e-2) are hydrogen atoms, R e7 and R e8 are phenyl groups, and X.
  • -Metal phosphate salt aluminum dialkylphosphinic acid salt, metal salt of disubstituted phosphinic acid, phosphorus content 23.5% by mass (manufactured by Clariant, trade name "OP-935”)
  • -Paraxylylene bisdiphenylphosphine oxide Phosphorus content 12.0% by mass
  • the cured products obtained in Examples 1 to 5 of the present embodiment have an area ratio R w of the non- separable portion of 50% or more and an average domain size DL of the separated portion of 120 ⁇ m or less. It can be seen that it is excellent in dielectric properties and heat resistance. On the other hand, the cured product of Comparative Example 1 in which the average domain size DL of the separated portion exceeded 120 ⁇ m was inferior in dielectric properties.
  • thermosetting resin composition of the present embodiment can evaluate the compatibility that affects the physical properties such as the dielectric properties and heat resistance of the thermosetting resin composition, it is possible to evaluate the compatibility. It is useful as a substrate material used for printed wiring boards.

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PCT/JP2021/045494 2020-12-14 2021-12-10 熱硬化性樹脂組成物の相容性評価方法、熱硬化性樹脂組成物、プリプレグ、樹脂フィルム、積層板、多層プリント配線板及び半導体パッケージ Ceased WO2022131151A1 (ja)

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KR1020237019829A KR20230118575A (ko) 2020-12-14 2021-12-10 열경화성 수지 조성물의 상용성 평가 방법, 열경화성 수지 조성물, 프리프레그, 수지 필름, 적층판, 다층 프린트 배선판 및 반도체 패키지
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