Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
• • 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
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
  • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
• • 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

Definitions

• a resin composition containing a specific polyphenylene ether derivative, a specific thermosetting resin, and a styrene-based thermoplastic elastomer has been proposed with the objective of providing a resin composition that has particularly good compatibility, high frequency characteristics, high adhesion to conductors, excellent heat resistance, a high glass transition temperature, a low coefficient of thermal expansion, and high flame retardancy (see Patent Document 1).
• the present invention aims to provide a resin composition capable of forming a cured product that has excellent high-frequency characteristics and in which the size of depressions on the surface after desmearing is suppressed to be small, and to provide a resin film, a prepreg, a laminate, a printed wiring board, and a semiconductor package that use the resin composition.
• a resin composition comprising: a maleic anhydride-modified styrene-based elastomer (A) having a modification rate of 1.0 mass% or more; and a thermosetting resin (B).
• thermosetting resin (B) is at least one selected from the group consisting of an epoxy resin, a maleimide compound, a phenolic resin, a polyimide resin, a cyanate resin, an isocyanate resin, a benzoxazine resin, an oxetane resin, an amino resin, an unsaturated polyester resin, an allyl resin, a dicyclopentadiene resin, and a silicone resin.
• the content of the (A) component is 1 to 50 parts by mass per 100 parts by mass of the solid content in the resin composition.
• a semiconductor package comprising the printed wiring board according to [10] above and a semiconductor element.
• the present invention provides a resin composition capable of forming a cured product that has excellent high-frequency characteristics and reduces the size of depressions on the resin layer surface after desmearing, and also provides a resin film, a prepreg, a laminate, a printed wiring board, and a semiconductor package that use the resin composition.
• the conjugated diene compounds include 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 1,3-pentadiene (piperylene), 1-phenyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene, etc.
• 1,3-butadiene and isoprene are preferred, and 1,3-butadiene is more preferred.
• the thermosetting resin more preferably contains at least one selected from the group consisting of epoxy resins, maleimide compounds, phenolic resins, polyimide resins, cyanate resins, and isocyanate resins, and further preferably contains at least one selected from epoxy resins, maleimide compounds, and cyanate resins, and particularly preferably contains a maleimide compound.
• the maleimide compound is preferably at least one selected from the group consisting of maleimide compounds having two or more N-substituted maleimide groups [hereinafter, sometimes simply referred to as "maleimide compound (b1)” or “component (b1)”] and derivatives thereof.
• the “derivative thereof” may be an addition reaction product between a maleimide compound having two or more N-substituted maleimide groups and an amine compound such as a diamine compound described later.
• aromatic maleimide compounds are preferred, aromatic bismaleimide compounds are more preferred, and 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane and 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide are even more preferred.
• the maleimide compound from the viewpoints of solubility in organic solvents, compatibility, adhesion to conductors, and high-frequency characteristics, a derivative of the maleimide compound (b1) is preferred.
• the derivative of the maleimide compound (b1) is preferably a modified maleimide compound [hereinafter, sometimes abbreviated as "modified maleimide compound (X)" or “component (X)] having a structural unit derived from the maleimide compound (b1) and a structural unit derived from an amine compound having a primary amino group [hereinafter, sometimes abbreviated as simply "component (b2)].
• the structural unit derived from the component (b1) and the structural unit derived from the component (b2) contained in the modified maleimide compound (X) may each be one type or a combination of two or more types.
• the modified maleimide compound (X) is preferably a compound having a structure represented by the following formula (B-1), which is formed by an addition reaction between a maleimide group in the component (b1) and a primary amino group in the component (b2). (* indicates the bond position to other structures.)
• the amine compound (b2) is preferably a compound having two or more amino groups, and more preferably a diamine compound having two amino groups.
• examples of the amine compound (b2) include 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ketone, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-di Aminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(
• 3,3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane is preferred.
• 2,2-bis[4-(4-aminophenoxy)phenyl]propane is preferred.
• the functional group equivalent weight of the amine-modified siloxane compound is not particularly limited, but is preferably 300 to 3,000 g/mol, more preferably 400 to 2,000 g/mol, and even more preferably 600 to 1,000 g/mol.
• an aromatic diamine compound and an amine-modified siloxane compound in combination.
• the ratio of the aromatic diamine compound and the amine-modified siloxane compound used [aromatic diamine compound/amine-modified siloxane compound] is not particularly limited, but is preferably 20/80 to 80/20, more preferably 40/60 to 70/30, and even more preferably 50/50 to 65/35, in mass ratio.
• the content of the structural unit derived from component (b2) in the modified maleimide compound (X) is not particularly limited, but is preferably 5 to 50 mass%, more preferably 8 to 30 mass%, and even more preferably 10 to 15 mass%.
• the content of the structural unit derived from component (b2) is within the above range, there is a tendency for excellent high-frequency characteristics, as well as better heat resistance, flame retardancy, and glass transition temperature to be obtained.
• the content ratio of the structural unit derived from component (b1) and the structural unit derived from component (b2) in the modified maleimide compound (X) is not particularly limited, but is preferably such that the equivalent ratio (Ta1/Ta2) of the total equivalent (Ta1) of the groups derived from the maleimide groups (including maleimide groups ) derived from component (b1) to the total equivalent (Ta2) of the groups derived from the -NH2 groups (including -NH2) of component (b2) is 0.05 to 10, more preferably 1 to 5.
• the equivalent ratio (Ta1/Ta2) is within the above range, excellent high frequency characteristics, and better heat resistance, flame retardancy, and glass transition temperature tend to be obtained.
• the component (X) can be obtained as a reaction product between the components (b1) and (b2), and can be produced, for example, by reacting the components (b1) and (b2) in an organic solvent. Specifically, a reactor is charged with predetermined amounts of the components (b1), (b2), and, if necessary, other components, and the components (b1) and (b2) are subjected to a Michael addition reaction (hereinafter, sometimes abbreviated as "pre-reaction") to obtain the modified maleimide compound (X).
• pre-reaction Michael addition reaction
• the reaction conditions in the pre-reaction are not particularly limited, but from the viewpoint of obtaining good reactivity and workability while suppressing gelation, the reaction temperature is preferably 50 to 160° C. and the reaction time is preferably 1 to 10 hours.
• the (C) component is not particularly limited, but includes silica, alumina, titanium oxide, mica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide, aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay (calcined clay, etc.), molybdic acid compounds (zinc molybdate, etc.), talc, aluminum borate, silicon carbide, etc.
• the (C) component may be used alone or in combination of two or more.
• silica from the viewpoint of thermal expansion coefficient, heat resistance and flame retardancy, silica, alumina, mica, and talc are preferred, silica and alumina are more preferred, and silica is even more preferred.
• examples of silica include crushed silica, fumed silica, and fused silica (fused spherical silica).
• the content of the component (C) is not particularly limited, but from the viewpoints of thermal expansion coefficient, heat resistance, and flame retardancy, it is preferably 5 to 70 parts by mass, more preferably 15 to 65 parts by mass, even more preferably 20 to 60 parts by mass, and particularly preferably 30 to 55 parts by mass, relative to 100 parts by mass of the solid content in the resin composition.
• the so-called integral blending method may be used in which the coupling agent is added after the (C) component is blended into the resin composition, but it is preferable to use an inorganic filler that has been surface-treated in advance with a coupling agent by a dry or wet method. By adopting this method, the characteristics of the (C) component can be more effectively expressed.
• component (C) when component (C) is used in this embodiment, in order to improve the dispersibility of component (C) in the resin composition, component (C) may be used as a slurry in which it is dispersed in an organic solvent beforehand, if necessary.
• organic solvent include the same organic solvents as those described below.
• the resin composition of the present embodiment may contain a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group as component (D) (hereinafter, may be simply referred to as "polyphenylene ether derivative (D)").
• component (D) polyphenylene ether derivative having an ethylenically unsaturated bond-containing group
• the resin composition of the present embodiment contains component (D)
• the high frequency characteristics are further improved, and the compatibility between components (A) and (B) tends to be improved.
• the component (D) is preferably a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at a terminal thereof, and more preferably a polyphenylene ether derivative having an ethylenically unsaturated bond-containing group at both terminals.
• ethylenically unsaturated bond-containing group refers to a substituent containing a carbon-carbon double bond capable of undergoing an addition reaction, and does not include a double bond in an aromatic ring.
• the polyphenylene ether derivative (D) may be used alone or in combination of two or more kinds.
• the ethylenically unsaturated bond-containing group examples include unsaturated aliphatic hydrocarbon groups such as vinyl, allyl, 1-methylallyl, isopropenyl, 2-butenyl, 3-butenyl, and styryl groups; maleimide groups, and groups containing a heteroatom and an ethylenically unsaturated bond, such as the group represented by the following general formula (D-1).
• unsaturated aliphatic hydrocarbon groups such as vinyl, allyl, 1-methylallyl, isopropenyl, 2-butenyl, 3-butenyl, and styryl groups
• maleimide groups groups containing a heteroatom and an ethylenically unsaturated bond, such as the group represented by the following general formula (D-1).
• R d1 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
• the alkyl group having 1 to 20 carbon atoms represented by R d1 may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group, and is preferably a linear alkyl group.
• the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 1 carbon atom.
• alkyl group examples 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, a decyl group, a pentadecyl group, a hexadecyl group, and a heptadecyl group.
• a methyl group is preferred.
• ⁇ Curing Accelerator (E)> By further containing a curing accelerator as component (E) in the resin composition of the present embodiment, the curability is improved, and more excellent high frequency characteristics, heat resistance, adhesion to a conductor, elastic modulus, and glass transition temperature tend to be obtained.
• a suitable curing accelerator (E) may be appropriately selected depending on the type of the thermosetting resin (B) component used.
• the curing accelerator (E) may be used alone or in combination of two or more kinds.
• organic peroxides may also be used in combination, but from the viewpoint of the physical properties of the cured product, it is preferable not to contain an organic peroxide.
• the printed wiring board of the present embodiment has a cured product of the resin composition of the present embodiment. It can also be said that the printed wiring board of the present embodiment has one or more selected from the group consisting of a cured product of the thermosetting resin composition of the present embodiment, a cured product of the resin film of the present embodiment, a cured product of the prepreg of the present embodiment, and a laminate of the present embodiment.
• the printed wiring board of this embodiment can be manufactured by performing a circuit formation process such as drilling, metal plating, and etching of metal foil by a known method using one or more selected from the group consisting of the prepreg of this embodiment, the resin film of this embodiment, and the laminate of this embodiment.
• a multilayer printed wiring board can be manufactured by further performing a multilayer adhesive process as necessary.
• the prepreg of this embodiment and the resin film of this embodiment are C-staged.
• the resin composition, resin film, prepreg, laminate, printed wiring board, and semiconductor package of this embodiment can be suitably used in electronic devices that handle high-frequency signals of 10 GHz or more.
• the printed wiring board is useful as a printed wiring board for millimeter-wave radar.
• Modification rate [acid value (mg KOH/g)/molecular weight of KOH (mg/mol)] ⁇ 0.5 ⁇ molecular weight of maleic anhydride (g/mol) ⁇ 100(%)
• the mixture was concentrated at the reflux temperature for 3 hours to produce a modified maleimide compound (X-1) solution having a solid content of 65% by mass.
• the weight average molecular weight (Mw) of the obtained modified maleimide compound (X-1) was about 2,700.
• the PET films on both sides of this resin-attached PET film with a resin thickness of 325 ⁇ m were peeled off, and low-profile copper foil (BF-ANP18, Rz of M side: 1.5 ⁇ m, manufactured by CIRCUIT FOIL Co., Ltd.) with a thickness of 18 ⁇ m was laminated on the top and bottom of the resin so that the M side was in contact with the resin, and this laminate was placed in a mold with a thickness of 300 ⁇ m.
• the laminate was heated and pressurized at a temperature of 230°C, a pressure of 3.0 MPa, and a time of 90 minutes to produce a double-sided copper-clad laminate.
• the double-sided copper-clad laminate obtained in each example was immersed in a copper etching solution to remove the copper foil, and a desmear treatment was performed by carrying out the following (1) to (4) in this order to prepare a resin plate.
• a swelling liquid manufactured by Atotech Japan, product name "Swelling Dip Securigant P", an aqueous solution of glycol ethers and sodium hydroxide
• the surface of the resin plate (resin layer) after the desmear treatment obtained above was observed using a scanning electron microscope (SEM) (manufactured by Hitachi High-Technologies Corporation, product name: SV-4700) under conditions of secondary electron mode, accelerating voltage of 10 kV, and observation magnification of 5,000 times.
• SEM scanning electron microscope
• the sizes of any five of the depressions present within an area of 30 x 20 ⁇ m on the surface of the resin plate (resin layer) were measured, and the average value was calculated.
• the size of the depression here means the length of the longest straight line that can be drawn within the area of the depression in a plan view of the resin plate.
• a resin plate was prepared under the same conditions as in the "Measurement of the size of the dents" above, and cut into a test piece with a length of 60 mm and a width of 2 mm to measure the dielectric constant and dielectric loss tangent by the cavity resonator perturbation method.
• the measuring device used was a vector network analyzer "N5227A” manufactured by Agilent Technologies, the cavity resonator was "CP129” (10 GHz band resonator) manufactured by Kanto Electronics Application Development Co., Ltd., and the measurement program was "CPMA-V2". The measurement was performed under conditions of a frequency of 10 GHz and a measurement temperature of 25°C.
• Maleic anhydride-modified styrene-based elastomer 3 Maleic anhydride-modified styrene-based elastomer 3 having a modification rate of 1.6% by mass obtained in Production Example 2
• Maleic anhydride-modified styrene-based elastomer 4 Maleic anhydride-modified styrene-based elastomer 4 having a modification rate of 3.3% by mass obtained in Production Example 3
• Maleic anhydride-modified styrene-based elastomer 5 Maleic anhydride-modified styrene-based elastomer 5 having a modification rate of 4.6% by mass obtained in Production Example 4
• Maleic anhydride-modified styrene-based elastomer 6 Maleic anhydride-modified sttyren
• Modified maleimide compound Modified maleimide compound (X-1) prepared in Production Example 6
• Component (C): Inorganic filler Silica: spherical fused silica, average particle size: 0.5 ⁇ m, methyl isobutyl ketone 70% by mass slurry
• the copper-clad laminates of Examples 1 to 4 which were made using the resin composition of this embodiment, had excellent high-frequency characteristics, while minimizing the depressions on the resin layer that occurred in the copper-clad laminates of Comparative Examples 1 and 2, that is, minimizing the depressions to a diameter of 1 ⁇ m or less.

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• Chemical Kinetics & Catalysis (AREA)
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• Engineering & Computer Science (AREA)
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Citations (3)

• 2024
  • 2024-12-23 CN CN202480028582.6A patent/CN121195027A/zh active Pending
  • 2024-12-23 JP JP2025567057A patent/JPWO2025142841A1/ja active Pending
  • 2024-12-23 WO PCT/JP2024/045472 patent/WO2025142841A1/ja active Pending
  • 2024-12-24 TW TW113150387A patent/TW202535963A/zh unknown

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