CN111372960B - Thermosetting resin composition, insulating film, interlayer insulating film, multilayer wiring board, and semiconductor device - Google Patents
Thermosetting resin composition, insulating film, interlayer insulating film, multilayer wiring board, and semiconductor device Download PDFInfo
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- CN111372960B CN111372960B CN201880074803.8A CN201880074803A CN111372960B CN 111372960 B CN111372960 B CN 111372960B CN 201880074803 A CN201880074803 A CN 201880074803A CN 111372960 B CN111372960 B CN 111372960B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- 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
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- 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
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- 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
Abstract
The purpose of the present invention is to provide a thermosetting resin composition having excellent heat resistance, moisture resistance reliability, and moisture absorption reflow resistance. A thermosetting resin composition, characterized in that it comprises: (A) a thermosetting resin having an unsaturated double bond at the terminal; (B) A silica filler surface-treated with a specific long-chain spacer type silane coupling agent containing an alkyl group having an unsaturated double bond at least at the terminal; and (C) a resin for imparting flexibility (wherein the component (A) is excluded). The unsaturated double bond of the component (B) is preferably a vinyl group.
Description
Technical Field
The invention relates to a thermosetting resin composition, an insulating film, an interlayer insulating film, a multilayer wiring board and a semiconductor device. In particular, it relates to a thermosetting resin composition, an insulating film, an interlayer insulating film, a multilayer wiring board and a semiconductor device which can cope with high frequency.
Background
Currently, electronic devices such as various communication devices are often required to have a higher frequency. For example, low transmission loss is often required for printed wiring boards for high-frequency applications such as millimeter wave communication. As a material used for an adhesive layer, a cover layer or a substrate itself of a printed wiring board for high frequency use, it is known to use a thermosetting polyphenylene ether (PPE).
In the application of printed wiring boards for these high-frequency applications, a low thermal expansion coefficient (low CTE) is sometimes desired, and for example, a silica filler is added to PPE to obtain a desired CTE. For this reason, it has been reported that a printed wiring board having a low dielectric constant is manufactured by adding a predetermined hollow filler (silica balloon) to PPE (patent document 1).
Here, the adhesive layer, the cover layer, the substrate itself, and the like are required to have moisture resistance reliability (long-term reliability in an environment of 85 ℃ and 85% humidity), heat resistance (in this specification, heat resistance at the time of soldering is particularly indicated, and means instantaneous heat resistance), and moisture absorption reflow resistance.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2007-56170
Disclosure of Invention
Problems to be solved by the invention
However, when a silica filler (including a silica balloon) is added to PPE, the change rate of the dielectric loss tangent (tan δ) increases in the moisture resistance reliability test. Further, there is also a drawback that peeling or swelling occurs at the interface between the adhesive layer, the cover layer, or the substrate in the moisture absorption reflow resistance test.
The invention aims to: from the above-mentioned viewpoints, a thermosetting resin composition excellent in moisture resistance reliability, heat resistance and moisture absorption reflow resistance is provided.
Means for solving the problems
The present invention relates to a thermosetting resin composition, an insulating film, an interlayer insulating film, a multilayer wiring board, and a semiconductor device, which have the following configurations and solve the above problems.
[ 1] A thermosetting resin composition characterized by comprising:
(A) A thermosetting resin having an unsaturated double bond at the terminal;
(B) A silica filler surface-treated with a silane coupling agent represented by the general formula (1),
[ solution 1]
(in the formula, R 1 ～R 3 Each independently an alkyl group having 1 to 3 carbon atoms, R 4 A functional group having an unsaturated double bond at least at the terminal, and n is 5 to 9); and
(C) A resin which imparts flexibility (except for the component (A)).
[ 2] the thermosetting resin composition according to [ 1] above, wherein R of the general formula (1) 4 Is vinyl or (meth) acryloyl.
[ 3] the thermosetting resin composition according to the above [ 1] or [ 2], wherein the component (C) is a styrene-based thermoplastic elastomer.
[ 4] an insulating film comprising the thermosetting resin composition according to any one of [ 1] to [ 3] above.
[ 5] an interlayer insulating film comprising the thermosetting resin composition according to any one of [ 1] to [ 3] above.
[ 6] A cured product of the thermosetting resin composition according to any one of [ 1] to [ 3], the insulating film according to [ 4], or the interlayer insulating film according to [ 5 ].
[ 7] A multilayer wiring board having a cured product of the thermosetting resin composition according to any one of [ 1] to [ 3] above, a cured product of the insulating film according to [ 4] above, or a cured product of the interlayer insulating film according to [ 5] above.
[ 8] A semiconductor device having a cured product of the thermosetting resin composition according to any one of [ 1] to [ 3] above, a cured product of the insulating film according to [ 4] above, or a cured product of the interlayer insulating film according to [ 5] above.
Effects of the invention
According to the present invention [ 1], a thermosetting resin composition excellent in heat resistance, moisture resistance reliability and moisture absorption reflow resistance can be provided.
According to the present invention [ 4], an insulating film comprising a thermosetting resin composition excellent in heat resistance, moisture resistance reliability and moisture absorption reflow resistance can be provided.
According to the present invention [ 5], an interlayer insulating film comprising a thermosetting resin composition excellent in heat resistance, moisture resistance reliability and moisture absorption reflow resistance can be provided.
According to the invention [ 6], a multilayer wiring board having excellent moisture resistance reliability and moisture absorption reflow resistance can be provided by the cured product of the thermosetting resin composition, the cured product of the insulating film, or the cured product of the interlayer insulating film.
According to the present invention [ 7], a multilayer wiring board having excellent moisture resistance reliability and moisture absorption reflow resistance can be provided by the cured product of the thermosetting resin composition, the cured product of the insulating film, or the cured product of the interlayer insulating film.
According to the present invention [ 8], a semiconductor device having excellent moisture resistance reliability and moisture absorption reflow resistance can be provided by the cured product of the thermosetting resin composition, the cured product of the insulating film, or the cured product of the interlayer insulating film.
Detailed Description
[ thermosetting resin composition ]
The thermosetting resin composition of the present invention comprises:
(A) A thermosetting resin having an unsaturated double bond at the terminal;
(B) A silica filler surface-treated with a silane coupling agent represented by the general formula (1),
[ solution 2]
(in the formula, R 1 ～R 3 Each independently an alkyl group having 1 to 3 carbon atoms, R 4 A functional group having an unsaturated double bond at least at the terminal, and n is 5 to 9); and
(C) A resin which imparts flexibility (except for the component (A)).
(A) The component (B) imparts adhesiveness, high-frequency characteristics and heat resistance to the thermosetting resin composition of the present invention (hereinafter referred to as thermosetting resin composition). Here, the high frequency characteristics refer to a property of reducing transmission loss in a high frequency region. From the viewpoint of high-frequency characteristics, the component (a) is preferably: the dielectric constant (. Epsilon.) at 10GHz is 3.5 or less, and the dielectric loss tangent (tan. Delta.) is 0.003 or less. The component (A) is preferably a resin having a styrene group at the terminal. Further, as the resin having a styrene group at a terminal, a thermosetting resin (PPE) having a styrene group at a terminal and a phenylene ether skeleton in a main chain is preferable.
As the thermosetting resin (PPE) having a styrene group at the terminal and a phenylene ether skeleton in the main chain, a compound represented by the general formula (2) is preferable in order to obtain excellent high-frequency characteristics and a small temperature dependence of dielectric characteristics (particularly tan. Delta.) (change of a measured value at a high temperature (120 ℃ C.) with respect to a measured value at a normal temperature (25 ℃ C.)).
[ solution 3]
(wherein- (O-X-O) -in the formula (2) is represented by the general formula (3) or (4))
[ solution 4]
[ solution 5]
(in the formula (3), R 5 、R 6 、R 7 、R 11 、R 12 May be the same or different and is an alkyl group having 6 or less carbon atoms or a phenyl group. R 8 、R 9 、R 10 May be the same or different and is a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. )
(in the formula (4), R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 May be the same or different and is a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. -A-is a linear, branched or cyclic 2-valent hydrocarbon group having not more than 20 carbon atoms. )
(in the formula (2), - (Y-O) -represented by the general formula (5) and having 1 structure or 2 or more structures arranged randomly.)
[ solution 6]
(in the formula (5), R 21 、R 22 May be the same or different and is an alkyl group having 6 or less carbon atoms or a phenyl group. R 23 、R 24 May be the same or different and is a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. )
(in the formula (2), a and b represent an integer of 0 to 100, and at least one is not 0.)
(examples of-A-in the formula (4) include, but are not limited to, 2-valent organic groups such as methylene, ethylene, 1-methylethylene, 1-propylene, 1, 4-phenylenebis (1-methylethylene), 1, 3-phenylenebis (1-methylethylene), cyclohexylene, phenylmethylene, naphthylmethylene, and 1-phenylethylene.)
(As the compound represented by the formula (2), preferred isIs R 5 、R 6 、R 7 、R 11 、R 12 、R 21 、R 22 Is an alkyl group having 3 or less carbon atoms and R 8 、R 9 、R 10 、R 13 、R 14 、R 15 、R 16 、R 17 、R 18 、R 19 、R 20 、R 23 、R 24 A compound which is a hydrogen atom or an alkyl group having 3 or less carbon atoms, particularly more preferably- (O-X-O) -represented by the formula (3) or the formula (4) is one of the formulae (6), (7) or a compound represented by the general formula (8) wherein- (Y-O) -represented by the general formula (5) is a compound having a structure represented by the formula (9) or the formula (10), or a structure represented by the formula (9) and the formula (10) which are randomly arranged. )
[ solution 7]
[ solution 8]
[ solution 9]
[ solution 10]
[ solution 11]
The method for producing the compound represented by the formula (2) is not particularly limited, and for example, it can be produced by vinylbenzyletherification of the terminal phenolic hydroxyl group of a 2-functional phenylene ether oligomer obtained by oxidative coupling of a 2-functional phenol compound and a 1-functional phenol compound.
(A) The number average molecular weight of the thermosetting resin of component (a) is preferably in the range of 500 to 4500, more preferably 800 to 3500, and still more preferably 1000 to 2500 in terms of polystyrene by GPC method. When the number average molecular weight is 500 or more, the resin composition of the present invention is not easily sticky when formed into a coating film, and when the number average molecular weight is 4500 or less, the resin composition can be prevented from being lowered in solubility in a solvent.
(A) The component (A) may be 1 kind alone or 2 or more kinds in combination.
(B) The component (B) imparts low thermal expansion, heat resistance, moisture resistance reliability, and moisture absorption reflow resistance to the thermosetting resin composition. (B) The component (A) is a silica filler surface-treated with a silane coupling agent represented by the general formula (1).
[ solution 12]
(wherein R is 1 ～R 3 Each independently is an alkyl group having 1 to 3 carbon atoms, R 4 A functional group having an unsaturated double bond at least at the terminal, n is 5 to 9)
As R 4 Specific examples thereof include a vinyl group and a (meth) acryloyl group. R in the general formula (1) 4 From the viewpoint of adhesiveness to the component (a) due to reactivity, a vinyl group or a (meth) acryloyl group is preferable, and from the viewpoint of peel strength, a vinyl group is more preferable.
Examples of the silane coupling agent used as component (B) include octenyltrialkoxysilanes and (meth) acryloyloxyalkyltrialkoxysilanes. Examples of the octenyltrialkoxysilane include octenyltrimethoxysilane, octenyltriethoxysilane and the like. Examples of the (meth) acryloyloxyalkyltrialkoxysilane include (meth) acryloyloxyoctyltrimethoxysilane, (meth) acryloyloxyoctyltriethoxysilane, and the like. Octenyltrimethoxysilane is more preferable from the viewpoint of improving the peel strength. Commercially available silane coupling agents as component (B) include octenyltrimethoxysilane (product name: KBM-1083) manufactured by shin-Etsu chemical Co., ltd., and methacryloxyoctyltrimethoxysilane (product name: KBM-5803) manufactured by shin-Etsu chemical Co., ltd.). (B) The silane coupling agent used in the component (a) may be 1 kind alone or 2 or more kinds.
Examples of the silica filler used in component (B) include fused silica, general silica, spherical silica, crushed silica, crystalline silica, amorphous silica, and the like, and are not particularly limited. Spherical fused silica is preferable from the viewpoints of dispersibility of the silica filler, fluidity of the thermosetting resin composition, surface smoothness of the cured product, dielectric characteristics, low thermal expansion coefficient, adhesiveness, and the like. The average particle diameter (average maximum diameter in the case where the silica filler is not spherical) of the silica filler is not particularly limited, but is preferably 0.05 to 20 μm, more preferably 0.1 to 10 μm, and still more preferably 1 to 10 μm, from the viewpoint of improving moisture resistance after curing by reducing the specific surface area. Here, the average particle diameter of the silica filler refers to a volume-based median particle diameter measured by a laser scattering diffraction particle size distribution measuring apparatus. (B) The silica filler used in the component (a) may be 1 type alone or 2 or more types.
The method for surface-treating the silica filler with the coupling agent is not particularly limited, and examples thereof include a dry method and a wet method.
The dry method is as follows: a method of adding a silica filler and a silane coupling agent in an appropriate amount relative to the surface area of the silica filler to a stirring device and stirring them under appropriate conditions, or a method of adding a silane coupling agent in an appropriate amount relative to the surface area of the silica filler to a stirring device in advance and stirring them under appropriate conditions, adding the silane coupling agent in the form of a stock solution or a solution by dropping or spraying, etc., and uniformly adhering the silane coupling agent to the surface of the silica filler by stirring and performing surface treatment by hydrolyzing the silane coupling agent. Examples of the stirring device include a mixer capable of stirring and mixing at high speed rotation, such as a henschel mixer, but are not particularly limited.
The wet method is as follows: the surface treatment is carried out by adding a silica filler to a surface treatment solution in which a silane coupling agent having a sufficient amount of surface area to the silica filler subjected to surface treatment is dissolved in water or an organic solvent, stirring the mixture to form a slurry, allowing the silane coupling agent and the silica filler to react sufficiently, separating the silica filler from the surface treatment solution by filtration, centrifugation or the like, and heating and drying the separated silica filler.
(B) The component may be used alone in 1 kind or in combination of 2 or more kinds.
(C) The component (A) is a resin which imparts flexibility to the thermosetting resin composition and imparts flexibility thereto (except for the component (A)). (C) The component (a) is not particularly limited as long as it is a component different from the component (a), and may be a resin or an elastomer.
The component (C) is preferably a styrene-based thermoplastic elastomer from the viewpoint of dielectric properties, and more preferably a hydrogenated styrene-based thermoplastic elastomer from the viewpoint of reducing the temperature dependence of dielectric properties (particularly tan δ) (change in measured value at high temperature (120 ℃) relative to measured value at normal temperature (25 ℃)). Although a hydride obtained by hydrogenating polybutadiene has good heat resistance, temperature dependency may increase.
The hydrogenated styrene-based thermoplastic elastomer which is preferable as the component (C) is a styrene-based block copolymer in which unsaturated double bonds of a main chain in a molecule are hydrogenated, and examples of the hydrogenated styrene-based block copolymer include a styrene-ethylene/butylene-styrene block copolymer (SEBS), a styrene- (ethylene-ethylene/propylene) -styrene block copolymer (SEEPS), a styrene-ethylene/propylene-styrene block copolymer (SEPS), and the like, and SEBS and SEEPS are preferable. This is due to: SEBS and SEEPS have excellent dielectric properties, have good compatibility with polyphenylene ether (PPE), modified PPE, and the like, which are optional components of the component (a), and can form a heat-resistant thermosetting resin composition. Further, the styrene-based block copolymer contributes to the low elasticity of the thermosetting resin composition, and therefore, it imparts flexibility to the insulating film and is suitable for applications in which low elasticity of 3GPa or less is required for a cured product of the thermosetting resin composition.
(C) The weight average molecular weight of component (A) is preferably 30000 to 200000, more preferably 80000 to 120000. The weight average molecular weight is a value obtained using Gel Permeation Chromatography (GPC) using a calibration curve based on standard polystyrene. (C) The components may be used alone in 1 kind, or in combination of 2 or more kinds.
The total resin component in the thermosetting resin composition (excluding the solvent) is preferably 1 to 65% by mass, more preferably 10 to 40% by mass, and particularly preferably 20 to 30% by mass. As the resin other than the component (a) and the component (C), for example, an epoxy resin, a maleimide resin, a cyanate resin, or the like can be used in combination.
The amount of component (a) is preferably 10 to 50 parts by mass, more preferably 20 to 40 parts by mass, based on 100 parts by mass of the total of components (a) and (C). If the amount of component (a) is small, the cured product is insufficiently cured, and defects such as a decrease in peel strength, an increase in Coefficient of Thermal Expansion (CTE), and a decrease in heat resistance are likely to occur. When the component (a) is contained in a large amount, the film becomes hard and brittle, and is likely to be broken to impair the film properties, and the cured product also becomes hard and brittle, and is likely to suffer from disadvantages such as a decrease in peel strength and a tendency to crack due to thermal shock.
(B) The component (B) is preferably 45 to 75% by volume (64 to 88% by mass if it is a solid silica filler) and more preferably 50 to 70% by volume (69 to 85% by mass if it is a solid silica filler) in the thermosetting resin composition (excluding the solvent). If the amount of the component (B) is small, the desired CTE cannot be achieved, and if the amount of the component (B) is large, the peel strength tends to be reduced.
(C) Component (C) is preferably 90 to 50 parts by mass, more preferably 80 to 60 parts by mass, based on 100 parts by mass of the total of component (a) and component (C).
The thermosetting resin composition may contain additives such as an organic peroxide as the curing accelerator of the component (a), a coupling agent (integral blend) such as a silane coupling agent, a flame retardant, a tackifier, an antifoaming agent, a flow control agent, a thixotropic agent, a dispersing agent, an antioxidant, and a flame retardant, within a range not to impair the effects of the present invention. Examples of the silane coupling agent include p-styryltrimethoxysilane (KBM-1403, manufactured by shin-Etsu chemical Co., ltd.), bis (triethoxysilylpropyl) tetrasulfide (KBE-846, manufactured by shin-Etsu chemical Co., ltd.), octenyltrimethoxysilane (KBM-1083, manufactured by shin-Etsu chemical Co., ltd.), methacryloxyoctyltrimethoxysilane (KBM-5803, manufactured by shin-Etsu chemical Co., ltd.), 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by shin-Etsu chemical Co., ltd.), 3-methacryloxypropyltriethoxysilane (KBE-503, manufactured by shin-Etsu chemical Co., ltd.), 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by shin chemical Co., ltd.), 3-glycidoxypropyltriethoxysilane (KBE-403, manufactured by shin chemical Co., ltd.), and KBE-403). Examples of the flame retardant include metal phosphonates (OP-935, manufactured by Clariant JAPAN).
The thermosetting resin composition can be produced by dissolving or dispersing raw materials such as the components (a), (B), and (C) constituting the resin composition in an organic solvent. The apparatus for dissolving, dispersing, or the like of these raw materials is not particularly limited, but a stirrer, a dissolver, a kneader, a three-roll mill, a ball mill, a planetary stirrer, a bead mill, or the like provided with a heating device may be used. These devices may be used in combination as appropriate.
Examples of the organic solvent include aromatic solvents such as toluene and xylene, and examples of the ketone solvents include methyl ethyl ketone and methyl isobutyl ketone. The organic solvent may be used alone in 1 kind, or may be used in combination of 2 or more kinds. The viscosity of the thermosetting resin composition is preferably in the range of 200 to 3000 mPas from the viewpoint of workability. The viscosity was measured at 25 ℃ at 50rpm using an E-type viscometer.
The obtained thermosetting resin composition is excellent in heat resistance, moisture resistance reliability and moisture absorption reflow resistance.
[ insulating film ]
The insulating film of the present invention comprises the above thermosetting resin composition. The insulating film is formed into a desired shape from the thermosetting resin composition. Specifically, the insulating film can be obtained by applying the thermosetting resin composition described above to a support and then drying the composition. The support is not particularly limited, and includes: metal foils such as copper and aluminum; and organic films such as polyester resins, polyethylene resins, and polyethylene terephthalate resins (PET). The support may be subjected to a mold release treatment with a silicon-based compound or the like. The thermosetting resin composition can be used in various shapes, and the shape is not particularly limited.
The method for applying the thermosetting resin composition to the support is not particularly limited, but from the viewpoint of making the thermosetting resin composition thin and controlling the film thickness, the gravure method, the slit die method, and the doctor blade method are preferable. An uncured film of the thermosetting resin composition having a thickness of 5 to 300 μm, that is, an insulating film can be obtained by the slit die method.
The drying conditions may be appropriately set depending on the kind and amount of the organic solvent used in the thermosetting resin composition, the thickness of the coating, and the like, and may be set to about 1 to 60 minutes at 50 to 120 ℃. The insulating film thus obtained has good storage stability. The insulating film can be peeled off from the support at a desired timing.
The insulating film can be cured at, for example, 150 to 230 ℃ for 30 to 180 minutes. The interlayer insulating film of the present invention can be produced and cured by the same method as described above. In the case of using an insulating film as the interlayer insulating film, the interlayer insulating film may be cured after the interlayer insulating film is sandwiched between substrates having wiring formed of copper foil or the like, or may be cured after the interlayer insulating films having wiring formed of copper foil or the like are appropriately laminated. The insulating film may be used as a cover film for protecting the wiring on the substrate, and the same curing conditions are applied in this case. The thermosetting resin composition may be similarly cured. In addition, at the time of curing, it may be cured by pressing under a pressure of, for example, 1 to 5 MPa.
[ multilayer Wiring Board ]
The multilayer wiring board of the present invention has a cured product of the thermosetting resin composition, a cured product of the insulating film, or a cured product of the interlayer insulating film. The printed wiring board of the present invention is produced by curing the thermosetting resin composition, the insulating film, or the interlayer insulating film. The printed wiring board is excellent in heat resistance, moisture resistance reliability, and moisture absorption reflow resistance by a cured product of the thermosetting resin composition, a cured product of the insulating film, or a cured product of the interlayer insulating film. Examples of the multilayer wiring board include a substrate for microwave and millimeter wave communication, and particularly a printed wiring board for high frequency applications such as a millimeter wave radar substrate for vehicle mounting. The method for producing the multilayer wiring board is not particularly limited, and the same method as that in the case of producing a printed wiring board using a general prepreg can be used.
[ semiconductor device ]
The semiconductor device of the present invention is produced by curing the thermosetting resin composition, the insulating film, or the interlayer insulating film. The semiconductor device is excellent in heat resistance, moisture resistance reliability, and moisture absorption reflow resistance by a cured product of the thermosetting resin composition, a cured product of the insulating film, or a cured product of the interlayer insulating film. Here, the semiconductor device refers to all devices that can function by utilizing semiconductor characteristics, and includes electronic components, semiconductor circuits, modules assembled from these, electronic devices, and the like.
Examples
The present invention will be described with reference to examples, but the present invention is not limited to these examples. In the following examples, parts and% are parts by mass and% by mass unless otherwise specified.
[ examples 1 to 8 and comparative examples 1 to 6]
Production of thermosetting resin composition
According to the formulation shown in tables 1 to 2, each component was weighed into a container, stirred and mixed for 3 minutes by a rotation/revolution type stirrer (MAZERUSTAR (registered trademark), manufactured by kurabbo), dispersed by a bead mill, and subjected to viscosity adjustment with toluene to prepare a thermosetting resin composition. Then, the thermosetting resin composition is applied to a polyethylene terephthalate (PET) substrate by a coater so as to have a thickness of 50 to 100 μm, and dried at 100 to 120 ℃ for 10 to 20 minutes to form a thin film.
Here, OPE-2St 2200 described in tables 1 to 2 is styrene-end-modified PPE (molecular weight (Mn): 2200) manufactured by Mitsubishi gas chemical Co., ltd.
SEBS (elastomer having a styrene ratio of 30%) manufactured by Kraton Polymer was used as G1652.
SEBS (elastomer having a styrene ratio of 20%) manufactured by Asahi Kasei corporation was used as H1052.
FB-3SDX spherical silica (average particle diameter: 3.4 μm) manufactured by Denka was used.
For MP-8FS, toxon spherical silica (average particle size: 0.5 μm) was used.
As SFP-130MC, spherical silica (average particle diameter: 0.7 μm) manufactured by Denka was used.
KBM-1403 was p-styryltrimethoxysilane manufactured by shin-Etsu chemical Co., ltd.
KBE-846 uses bis (triethoxysilylpropyl) tetrasulfide, manufactured by shin-Etsu chemical Co., ltd.
7-Octenyltrimethoxysilane manufactured by shin-Etsu chemical Co., ltd. Was used for KBM-1083.
8-methacryloyloxyoctyltrimethoxysilane (manufactured by shin-Etsu chemical Co., ltd.) was used as KBM-5803.
3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by shin-Etsu chemical Co., ltd.) was used.
Octyl triethoxysilane was used as KBE-3083 (manufactured by shin-Etsu chemical Co., ltd.).
[ evaluation method ]
Peeling Strength
The film peeled from the PET substrate was sandwiched between 2 pieces of Cu foil (CF-T9 FZSV, manufactured by Futian Metal foil powder industries, ltd.), press-cured at 200 ℃ for 1 hour and 3MPa, and then cut into 1cm X10 cm to obtain test pieces, and 180 ℃ peel strength of one piece of Cu foil was measured using a universal tester. Here, the S-side is the peel strength between the bright surfaces (glossy surfaces) of the copper foil, and the M-side is the peel strength between the matte surfaces (roughened surfaces) of the copper foil. The S-plane is preferably 2.5N/cm or more, and the M-plane is preferably 5N/cm or more.
Coefficient of thermal expansion (z-direction CTE)
The film peeled from the PET substrate was laminated to have a thickness of about 2mm, subjected to press curing at 200 ℃ for 1 hour under 1MPa, and then cut into about 5mm square pieces, and the coefficient of thermal expansion in the thickness direction (z-direction CTE) was measured as a test piece using TMA4000S manufactured by Netzsch JAPAN (ltd). The thermal expansion coefficient is preferably 70 ppm/DEG C or less.
Dielectric characteristics
The film peeled from the PET substrate was cured by pressing under conditions of 200 ℃ for 1 hour and 1MPa, cut into 70X 50mm, and the relative permittivity (. Epsilon.) and dielectric loss tangent (tan. Delta.) at normal temperature and normal humidity were measured at a dielectric resonance frequency of 10GHz by using a split dielectric resonator (SPDR). It is preferable that: a relative permittivity of 3.5 or less and a dielectric loss tangent of 0.0030 or less. The results are shown in tables 1 to 2.
Moisture resistance reliability (tan delta variation)
The cured film having the above-described dielectric properties was left in a constant temperature and humidity chamber (85 ℃/85% RH) for 1000 hours, and then tan. Delta. Was measured by the SPDR method (10 GHz) at normal temperature and humidity to determine the amount and rate of change of tan. Delta. The rate of change is preferably 80% or less. The results are shown in tables 1 to 2.
Solder heat resistance
The film peeled from the PET substrate was sandwiched between 2 sheets of Cu foil (CF-T9 FZSV), pressed and cured under conditions of 200 ℃,1 hour, and 3MPa to bond, and then cut into 3cm × 3cm, and as a test piece, the film was floated in a solder bath at each temperature shown in table 3 for 60 seconds to visually confirm the presence or absence of swelling. The case where no change in appearance such as swelling occurred was regarded as "OK" (acceptable), and the case where swelling was observed was regarded as "NG" (unacceptable). The solder heat resistance is preferably 270 ℃ or higher. The results are shown in table 3.
Moisture-absorption-resistant reflux property
The film peeled from the PET substrate was held between 2 pieces of Cu foil (CF-T9 FZSV), press-cured and bonded under conditions of 200 ℃ for 1 hour and 3MPa, and then cut into 1cm X10 cm pieces, which were used as test pieces, subjected to a pressure cooker test (PCT: 121 ℃ C., 2 atm saturated steam) for 16 hours, passed through a solder reflow furnace, and then peeled off, and the presence or absence of film expansion was confirmed by an optical microscope photograph. The "very good" was the area of swelling of less than 5%, the "good" was the area of 5% or more and less than 30%, and the "poor" was the area of 30% or more. The results are shown in table 4. The solder reflow furnace was provided with 5 heaters, and the furnace length was about 2.5m, and 1 of them was set to a peak temperature of 260 ℃, and after the furnace was brought to a constant temperature state, the test piece was passed at a conveyor speed of 0.35 m/min.
[ Table 1]
The filler ratio (volume percentage (Vol%)) was determined as follows.
(filler volume) = (silica filler mass)/(silica filler density), (volume of raw material other than silica filler) = (mass total of raw material other than silica filler)/(density of raw material other than silica filler), filler ratio (volume percentage (Vol%)) = [ (silica filler volume)/{ (silica filler volume) + (volume of raw material other than silica filler) }]X 100. Here, the density of the silica filler was calculated to be 2.2g/cm 3 The density of the raw materials (organic matter) other than the silica filler was approximately 1.0g/cm 3 。
[ Table 2]
[ Table 3]
[ Table 4]
As can be seen from tables 1 to 4: examples 1 to 8 were all good in peel strength, thermal expansion coefficient, relative dielectric constant (. Epsilon.), dielectric loss tangent (tan. Delta.), moisture resistance reliability (change amount and change rate of tan. Delta.), solder heat resistance, and moisture absorption reflow resistance. In contrast, comparative examples 1 to 3 in which component (B) was not used had a large variation rate in the moisture resistance reliability. Comparative examples 4 to 6 in which component (B) was not used were inferior in solder heat resistance. The results of the moisture absorption and reflow resistance of comparative examples 3 to 6 in which the component (B) was not used were also poor.
Industrial applicability of the invention
The thermosetting resin composition of the present invention is useful for forming an insulating film or an interlayer insulating film having excellent heat resistance, moisture resistance reliability, and moisture absorption reflow resistance. The multilayer wiring board of the present invention is excellent in heat resistance, moisture resistance reliability, and moisture reflow resistance due to the cured product of the thermosetting resin composition, the cured product of the insulating film, or the cured product of the interlayer insulating film. The semiconductor device of the present invention is suitable for high-frequency applications because it has excellent moisture resistance reliability and moisture absorption reflow resistance due to the cured product of the thermosetting resin composition, the cured product of the insulating film, or the cured product of the interlayer insulating film.
Claims (8)
1. A thermosetting resin composition, comprising:
(A) A thermosetting resin having an unsaturated double bond at a terminal and a phenylene ether skeleton in a main chain;
(B) A silica filler surface-treated with a silane coupling agent represented by the general formula (1),
in the formula, R 1 ～R 3 Each independently is an alkyl group having 1 to 3 carbon atoms, R 4 A functional group having an unsaturated double bond at least at the terminal, and n is 5 to 9; and
(C) A resin which imparts flexibility, excluding the component (A).
2. The thermosetting resin composition as claimed in claim 1, wherein R of the general formula (1) 4 Is vinyl or (meth) acryloyl.
3. The thermosetting resin composition according to claim 1 or 2, wherein the component (C) is a styrene-based thermoplastic elastomer.
4. An insulating film comprising the thermosetting resin composition according to any one of claims 1 to 3.
5. An interlayer insulating film comprising the thermosetting resin composition according to any one of claims 1 to 3.
6. A cured product of the thermosetting resin composition according to any one of claims 1 to 3, a cured product of the insulating film according to claim 4, or a cured product of the interlayer insulating film according to claim 5.
7. A multilayer wiring board comprising a cured product of the thermosetting resin composition according to any one of claims 1 to 3, a cured product of the insulating film according to claim 4, or a cured product of the interlayer insulating film according to claim 5.
8. A semiconductor device comprising a cured product of the thermosetting resin composition according to any one of claims 1 to 3, a cured product of the insulating film according to claim 4, or a cured product of the interlayer insulating film according to claim 5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017-225470 | 2017-11-24 | ||
| JP2017225470 | 2017-11-24 | ||
| PCT/JP2018/043120 WO2019103082A1 (en) | 2017-11-24 | 2018-11-22 | Thermosetting resin composition, dielectric film, interlayer dielectric film, multilayer wiring board, and semiconductor device |
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| CN111372960A CN111372960A (en) | 2020-07-03 |
| CN111372960B true CN111372960B (en) | 2023-01-24 |
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| JP (1) | JP7204214B2 (en) |
| KR (1) | KR102657819B1 (en) |
| CN (1) | CN111372960B (en) |
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| WO (1) | WO2019103082A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010111758A (en) * | 2008-11-06 | 2010-05-20 | Hitachi Chem Co Ltd | Resin composition, prepreg, laminate and printed board |
| CN104321376A (en) * | 2012-05-21 | 2015-01-28 | 昭和电工株式会社 | Curable composition and cured material of the same |
| JP2017009715A (en) * | 2015-06-18 | 2017-01-12 | 太陽インキ製造株式会社 | Photocurable resin composition, dry film, cured product and printed wiring board |
| CN106433025A (en) * | 2015-08-07 | 2017-02-22 | 味之素株式会社 | Resin composition |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6352782B2 (en) * | 1999-12-01 | 2002-03-05 | General Electric Company | Poly(phenylene ether)-polyvinyl thermosetting resin |
| JP4561534B2 (en) | 2005-08-25 | 2010-10-13 | パナソニック電工株式会社 | Polyphenylene ether resin composition, prepreg and laminate |
| JP2013111758A (en) * | 2011-11-25 | 2013-06-10 | Canon Inc | Printing apparatus and colorimetry apparatus |
| JP6638380B2 (en) * | 2015-12-22 | 2020-01-29 | 日立化成株式会社 | Pre-supply type underfill material and cured product thereof, electronic component device and method of manufacturing the same |
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2018
- 2018-11-22 WO PCT/JP2018/043120 patent/WO2019103082A1/en active Application Filing
- 2018-11-22 CN CN201880074803.8A patent/CN111372960B/en active Active
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- 2018-11-22 JP JP2019555355A patent/JP7204214B2/en active Active
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010111758A (en) * | 2008-11-06 | 2010-05-20 | Hitachi Chem Co Ltd | Resin composition, prepreg, laminate and printed board |
| CN104321376A (en) * | 2012-05-21 | 2015-01-28 | 昭和电工株式会社 | Curable composition and cured material of the same |
| JP2017009715A (en) * | 2015-06-18 | 2017-01-12 | 太陽インキ製造株式会社 | Photocurable resin composition, dry film, cured product and printed wiring board |
| CN106433025A (en) * | 2015-08-07 | 2017-02-22 | 味之素株式会社 | Resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP7204214B2 (en) | 2023-01-16 |
| TW201930463A (en) | 2019-08-01 |
| WO2019103082A1 (en) | 2019-05-31 |
| KR20200079508A (en) | 2020-07-03 |
| KR102657819B1 (en) | 2024-04-15 |
| TWI772562B (en) | 2022-08-01 |
| JPWO2019103082A1 (en) | 2020-12-03 |
| CN111372960A (en) | 2020-07-03 |
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