Classifications

• • 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
  • C08F290/062—Polyethers
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • 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
  • C08F226/00—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
  • C08F226/06—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 single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
• • 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
• • 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
  • C08J5/24—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
  • 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
• • 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
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
  • H05K1/0313—Organic insulating material
  • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
  • H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers

Definitions

• the present invention relates to a resin composition, and a cured product using the same, a prepreg, a printed wiring board, and an electronic component for high frequency.
• thermosetting polyphenylene ether is used as a material for adhesive layers, coverlays, substrates, etc. of multilayer printed wiring boards for high frequency applications (see, for example, Patent Document 1). It is said that thermosetting polyphenylene ether preferably has a low molecular weight from the viewpoint of reactivity and solubility in solvents, and is preferably a vinyl compound (a functional group having a vinyl group).
• polyphenylene ether cured products obtained by reacting thermosetting polyphenylene ethers with vinyl groups as functional groups undergo oxidative deterioration very quickly at high temperatures, and have a large dielectric loss tangent (tan ⁇ ) value in terms of heat resistance reliability.
• the inventors of the present invention have discovered that there is a problem of fluctuations.
• the present invention has been made in view of the problems of the prior art.
• the present invention provides a resin composition that has excellent heat resistance reliability (in other words, the rate of change in dielectric loss tangent (tan ⁇ ) is small). Furthermore, the present invention provides cured products, prepregs, printed wiring boards, and high-frequency electronic components using such resin compositions.
• the following resin compositions, cured products, prepregs, printed wiring boards, and high frequency electronic components are provided.
• R 1 represents a hydrogen atom or an alkyl group.
• R 2 is an alkyl group having 4 to 14 carbon atoms.
• a printed wiring board comprising a cured layer made of the resin composition according to any one of [1] to [11] above.
• a high-frequency electronic component comprising the cured product according to [12] above.
• the resin composition of the present invention has excellent heat resistance reliability (in other words, the rate of change in dielectric loss tangent (tan ⁇ ) is small). Furthermore, the resin composition of the present invention has good fluidity, so it has good embedding properties in a substrate, and also has excellent film forming properties. Therefore, the resin composition of the present invention can be suitably used for cured products, prepregs, printed wiring boards, electronic components for high frequencies, and the like.
• the cured products, prepregs, printed wiring boards, and high-frequency electronic components of the present invention use the resin composition of the present invention described above, and have excellent dielectric properties, as well as excellent heat resistance and embeddability. .
• FIG. 3 is a plan view showing patterning in evaluation of substrate pattern embeddability. This is an example of a photograph when the embeddability is good in evaluating the embeddability of a substrate pattern. This is an example of a photograph when the embeddability is poor in evaluating the embeddability of a substrate pattern.
• One embodiment of the resin composition of the present invention comprises (A) a polyphenylene ether resin having a group represented by the following formula (1) at its terminal, and (B) an isocyanuric ring structure and two allyl groups in one molecule. and a compound that is liquid at 25°C.
• component (A) a polyphenylene ether resin having a group represented by the following formula (1) at its terminal may be referred to as component (A).
• component (B) that has an isocyanuric ring structure and two allyl groups in one molecule and is liquid at 25°C may be referred to as component (B).
• R 1 represents a hydrogen atom or an alkyl group.
• the resin composition of this embodiment has excellent high frequency characteristics, heat resistance, and heat resistance reliability.
• excellent heat resistance reliability means that the change in dielectric loss tangent (tan ⁇ ) in the heat resistance reliability test is small.
• an example of excellent heat resistance reliability is that after being left in an environment of 125° C. for 1000 hours, the rate of change in dielectric loss tangent (tan ⁇ ) is smaller than before being left in an environment.
• the resin composition of this embodiment has good fluidity, it also has good embeddability into a substrate.
• the polyphenylene ether resin as component (A) has a group represented by the above formula (1) at its terminal, and can improve the heat resistance and heat resistance reliability described above.
• the present inventors have succeeded in developing a resin composition with excellent dielectric properties and heat resistance for use in adhesive layers, coverlays, substrates, etc. of multilayer printed wiring boards for high frequency applications.
• This resin composition comprises (A) a polyphenylene ether resin having a functional group containing a carbon-carbon double bond at the end, and (B) an isocyanuric ring structure and two allyl groups in one molecule, and and a liquid compound.
• the present inventors found that by terminally connecting the polyphenylene ether resin used as component (A) with the group shown in formula (1) above, the resin composition can be improved.
• the inventors have discovered that the heat resistance and heat resistance reliability of products are significantly improved, and have completed the present invention.
• the compound as component (B) is a compound having an isocyanuric ring structure and two allyl groups in one molecule, which lowers the melt viscosity of the resin composition and improves embeddability in wiring. can be done.
• the compound as component (B) has two allyl groups, so that extremely good low dielectric properties can be obtained.
• the resin composition of this embodiment can obtain high heat resistance and heat resistance reliability by crosslinking and curing such components (A) and (B).
• the resin composition of this embodiment contains other components such as (C) a thermoplastic resin, (D) an inorganic filler, and (E) a curing catalyst. May contain.
• C a thermoplastic resin
• D an inorganic filler
• E a curing catalyst
• Component (A) is a polyphenylene ether resin having a group represented by the above formula (1) at its terminal end.
• Component (A) has a group represented by the above formula (1) at its terminal and is not particularly limited as long as it has a polyphenylene ether skeleton.
• heat resistance and heat resistance reliability can be extremely effectively improved.
• the polyphenylene ether resin having the group represented by the above formula (1) as component (A) may be referred to as modified polyphenylene ether.
• the modified polyphenylene ether of component (A) is preferably a thermosetting resin.
• R 1 represents a hydrogen atom or an alkyl group.
• the alkyl group for R 1 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 carbon number. Specific examples include methyl group, ethyl group, propyl group, and the like.
• examples of the group represented by formula (1) include an acrylate group and a methacrylate group.
• a modified polyphenylene ether having a group represented by formula (1) has a polyphenylene ether chain in the molecule, for example, a repeating unit represented by the following structural formula (3) in the molecule.
• a repeating unit represented by the following structural formula (3) in the molecule.
• m represents 1 to 50.
• R 22 to R 25 are each independent and may be the same or different from each other.
• R 22 to R 25 represent a hydrogen atom or an alkyl group.
• the alkyl group in R 22 to R 25 is not particularly limited, but is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. Specific examples include methyl group, ethyl group, propyl group, hexyl group, and octyl group.
• modified polyphenylene ether having a group represented by the above formula (1) for example, a group represented by the above formula (1) is added to the terminal of a polyphenylene ether represented by the following formula (4) or formula (5). Examples include those that have. Specific examples of the modified polyphenylene ether include modified polyphenylene ethers represented by the following formula (6) or formula (7).
• s and t are preferably such that the total value of s and t is 1 to 30, for example. Further, s is preferably from 0 to 20, and t is preferably from 0 to 20. That is, s preferably represents 0 to 20, t represents 0 to 20, and the sum of s and t preferably represents 1 to 30. Further, in formulas (4) to (7), Y represents an alkylene group having 1 to 3 carbon atoms or a direct bond, and examples of the alkylene group include a dimethylmethylene group. Moreover, in formula (6) and formula (7), R 1 is the same as R 1 in the above formula (1), and represents a hydrogen atom or an alkyl group.
• alkyl group is not particularly limited, and for example, an alkyl group having 1 to 3 carbon atoms is preferable, and an alkyl group having 1 carbon number is more preferable. Specific examples include methyl group, ethyl group, propyl group, and the like.
• the number average molecular weight (Mn) of the modified polyphenylene ether having the group represented by formula (1) is not particularly limited. Specifically, it is preferably 500 to 5,000, more preferably 800 to 4,000, and even more preferably 1,000 to 3,000.
• the number average molecular weight may be one measured by a general molecular weight measurement method, and specifically, a value measured using gel permeation chromatography (GPC), etc. can be mentioned.
• GPC gel permeation chromatography
• m is the weight average molecular weight of the modified polyphenylene ether such that It is preferable that the value falls within a certain range. Specifically, m is preferably 1 to 50.
• the modified polyphenylene ether having the group represented by formula (1) When the number average molecular weight of the modified polyphenylene ether having the group represented by formula (1) is within the above numerical range, it has excellent dielectric properties derived from polyphenylene ether and has excellent embeddability into the substrate. .
• the molecular weight of conventional polyphenylene ether when the number average molecular weight of conventional polyphenylene ether is within the above-mentioned numerical range, the molecular weight is relatively low, and the embeddability into the substrate tends to be excellent.
• the modified polyphenylene ether having the group represented by the formula (1) above has the group represented by the formula (1) at the end, and therefore can improve the heat resistance and heat resistance reliability of the cured product.
• the average number of groups represented by the above formula (1) at the molecular ends (number of terminal functional groups) per molecule of modified polyphenylene ether is not particularly limited. . Specifically, the number is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.5 to 3. If the number of terminal functional groups is too small, curability tends to be poor, and it is difficult to obtain a cured product with sufficient strength, adhesiveness, or heat resistance. In addition, if the number of terminal functional groups is too large, the reactivity becomes too high, and for example, the storage stability of the resin composition decreases, the fluidity of the resin composition decreases, the cured product becomes brittle, and the adhesiveness decreases.
• the number of terminal functional groups of the above-mentioned modified polyphenylene ether is a numerical value representing the average value of the groups represented by the above formula (1) per molecule of all the modified polyphenylene ethers present in 1 mole of the modified polyphenylene ether. Can be mentioned.
• the number of terminal functional groups can be measured, for example, by measuring the number of hydroxyl groups remaining in the obtained modified polyphenylene ether and calculating the decrease from the number of hydroxyl groups in the polyphenylene ether before modification.
• the number of terminal functional groups is the decrease from the number of hydroxyl groups in the polyphenylene ether before modification.
• the method for measuring the number of hydroxyl groups remaining in modified polyphenylene ether is to add a quaternary ammonium salt (tetraethylammonium hydroxide) that associates with hydroxyl groups to a solution of modified polyphenylene ether, and measure the UV absorbance of the mixed solution. It can be found by
• the method for synthesizing the modified polyphenylene ether used as component (A) is not particularly limited as long as it can synthesize a modified polyphenylene ether having a group represented by the above formula (1) at its terminal.
• Component (A) may be a modified polyphenylene ether having a group represented by the above formula (1) at its end, or a modified polyphenylene ether having a group represented by the above formula (1) at its end. You may use two or more types in combination.
• component (A) in the resin composition there is no particular restriction on the content of component (A) in the resin composition, but it is preferable to contain 10 to 50 parts by mass of component (A), and 20 to 45 parts by mass, based on a total of 100 parts by mass of the resin components. It is more preferable to contain 25 to 40 parts by weight, and particularly preferably 25 to 40 parts by weight.
• the content of component (A) in the total 100 parts by mass of the resin components is within this range, the curability is good, and the flexibility of the resin composition, the heat resistance of the cured product, and the processability such as film formation are improved. It has the advantage that the hardness of the cured product is improved, the toughness of the cured product is not lost, and the adhesiveness etc. are not deteriorated.
• the content of component (A) in the resin component can be measured by, for example, an infrared spectrophotometer (FTIR) or a gas chromatograph mass spectrometry method.
• the resin components in the resin composition include, in particular, component (A), component (B), and optional component (C).
• the content of component (A) with respect to 100 parts by mass of the total resin components in the resin composition means, for example, the content of component (A) with respect to 100 parts by mass of the total mass of components (A), (B), and (C).
• the content of component (B) based on a total of 100 parts by mass of resin components, which will be described later, can also be calculated as described above.
• Component (B) has an isocyanuric ring structure and two allyl groups in one molecule, and is a liquid compound at 25°C.
• component (B) the melt viscosity of the resin composition can be lowered and the embeddability into wiring can be improved.
• the compound as component (B) has two allyl groups, so that extremely good low dielectric properties can be obtained.
• component (B) when a compound having an isocyanuric ring structure and three allyl groups in one molecule is used instead of component (B), sufficient low dielectric properties cannot be obtained.
• component (B) it is assumed that the dielectric properties will be insufficient due to a three-dimensional crosslinked structure.
• the compound has an allyl group, it will have a linear crosslinked structure and the dipole moment, which is a measure of molecular polarization, will be small, so it is presumed that low dielectric properties can be obtained. It is presumed that component (B) having an isocyanuric ring structure improves the heat resistance and heat resistance reliability of the resin composition.
• component (B) of the resin composition of this embodiment is a compound that is liquid at 25° C., the embeddability is improved. On the other hand, if component (B) is a compound that is solid at 25° C., the embeddability becomes poor, which is not preferable.
• the molecular weight of component (B) is preferably 300 to 400, more preferably 320 to 400. When the molecular weight of component (B) is within the above range, it has excellent dielectric properties and fluidity.
• component (B) is a compound represented by the following formula (2).
• R 2 is an alkyl group having 4 to 14 carbon atoms, preferably an alkyl group having 8 to 14 carbon atoms, and R 2 is an alkyl group having 10 to 12 carbon atoms. It is particularly preferable that
• the content of component (B) is preferably 20 to 80 parts by mass based on 100 parts by mass of component (A). By configuring in this way, the melt viscosity of the resin composition can be lowered, the embeddability into wiring can be improved, and the heat resistance and heat resistance reliability can also be improved.
• the content of component (B) is more preferably 25 to 75 parts by mass, and 30 to 70 parts by mass, based on 100 parts by mass of component (A). It is even more preferable.
• the component (B) is contained in 3 to 40 parts by mass, more preferably 5 to 30 parts by mass, and particularly preferably 10 to 25 parts by mass. .
• the content ratio of component (B) in the total 100 parts by mass of the resin components is within this range, the melt viscosity of the resin composition can be lowered, the embeddability into wiring can be improved, and the heat resistance of the cured product can be improved. Also, the heat resistance reliability is not deteriorated, and the dielectric properties are not deteriorated.
• the content ratio of component (B) and the content in the resin component can be measured by, for example, an infrared spectrophotometer (FTIR) or a gas chromatograph mass spectrometry method.
• FTIR infrared spectrophotometer
• Component (C) is a thermoplastic resin.
• the thermoplastic resin as component (C) is not particularly limited, but is preferably a thermoplastic elastomer having a dielectric loss tangent (tan ⁇ ) of less than 0.005 in the frequency range of 1 to 100 GHz. This can contribute to the excellent dielectric properties in the high frequency region of the thermosetting film formed from the resin composition of this embodiment.
• the "thermoplastic elastomer having a dielectric loss tangent (tan ⁇ ) of less than 0.005 in the frequency range of 1 to 100 GHz” is preferably a styrene-based thermoplastic elastomer.
• styrenic thermoplastic elastomer examples include block copolymers containing a block of styrene or its analog as at least one end block and an elastomer block of a conjugated diene as at least one intermediate block.
• SBS styrene/butadiene/styrene block copolymer
• SBBS styrene/butadiene/butylene/styrene block copolymer
• SEBS styrene/ethylene/butylene/styrene block copolymer
• SEEPS styrene/ethylene/ethylene/propylene/styrene block copolymer
• the thermoplastic resin of component (C) is more preferably styrene/ethylene/butylene/styrene block copolymer (SEBS), styrene/ethylene/ethylene/propylene/styrene block copolymer (SEEPS), or the like.
• SEBS styrene/ethylene/butylene/styrene block copolymer
• SEEPS styrene/ethylene/ethylene/propylene/styrene block copolymer
• the hydrogenated styrene-based thermoplastic elastomer improves dielectric properties and improves heat resistance reliability (dielectric loss tangent ( tan ⁇ ) can be reduced).
• component (C) there is no particular restriction on the content of component (C), but when component (C) is included, 20 to 80 parts of component (C) is added to 100 parts by mass of the resin components of the resin composition. It preferably contains 30 to 70 parts by mass, and even more preferably 40 to 60 parts by mass. When the content of component (C) is within this range, the heat resistance reliability of the resin composition can be improved (the rate of change in dielectric loss tangent (tan ⁇ ) is reduced), and the soldering heat resistance is further improved.
• the number average molecular weight of the thermoplastic resin as component (C) is preferably 30,000 or more, more preferably 40,000 or more, and even more preferably 50,000 or more.
• the number average molecular weight of the thermoplastic resin (C) is preferably 30,000 to 150,000, more preferably 40,000 to 120,000, particularly preferably 50,000 to 100,000. When the number average molecular weight is within this range, soldering heat resistance is improved.
• the melt viscosity of the resin composition increases, and the embeddability into the substrate tends to deteriorate.
• component (B) which has an isocyanuric ring structure and two allyl groups in one molecule and is a liquid compound at 25°C, even when using a thermoplastic resin with a large molecular weight, , it is possible to lower the melt viscosity of the resin composition and improve its embeddability into wiring.
• Component (D) is an inorganic filler.
• Inorganic fillers are required to have insulation properties and a low coefficient of thermal expansion.
• common inorganic fillers can be used.
• inorganic fillers include silica, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, oxidized Examples include titanium, zinc oxide, silicon carbide, silicon nitride, and boron nitride.
• the inorganic fillers may be used alone or in combination of two or more. In particular, from the viewpoint of low coefficient of thermal expansion and low dielectric properties, silica filler is preferred.
• the inorganic filler is a silane coupling agent having one or more functional groups selected from acrylic, methacrylic, styryl, amino, epoxy, vinyl, ureido, mercapto, isocyanate, and sulfide, or a silane cup having a long-chain hydrocarbon group.
• the surface may be treated with a ring agent.
• inorganic fillers include aminosilane coupling agents, ureidosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, vinylsilane coupling agents, styrylsilane coupling agents, (meth)acrylate
• Surface treatment agents such as silane coupling agents, isocyanate silane coupling agents, sulfide silane coupling agents, octylsilane coupling agents, octenylsilane coupling agents, organosilazane compounds, titanate coupling agents, etc. It is preferable to use surface treatment to improve moisture resistance, dispersibility, etc. These may be used alone or in combination of two or more.
• a silica filler surface-treated with a vinyl silane coupling agent it is preferable to use.
• a silica filler surface-treated with a vinyl silane coupling agent By using a silica filler surface-treated with a vinyl silane coupling agent, the toughness and adhesiveness of the cured product can be improved by reacting with the components (A) and (B).
• a silica filler whose surface has been treated with a silane coupling agent having a long-chain hydrocarbon group By using a silica filler surface-treated with a silane coupling agent having a long-chain hydrocarbon group, the moisture resistance of the cured product can be improved.
• the shape of the inorganic filler is not particularly limited, and examples include spherical, scaly, acicular, and amorphous shapes.
• a spherical shape is preferable from the viewpoint of high filling property and dispersibility of the inorganic filler in the resin composition, fluidity of the resin composition, and low coefficient of thermal expansion of the cured product.
• the average particle diameter is preferably 0.05 to 20 ⁇ m, more preferably 0.1 to 15 ⁇ m, and even more preferably 0.5 to 10 ⁇ m. When the average particle size of the inorganic filler is within this range, it has excellent embedding properties between the fine structures of substrates and electronic components. Further, it becomes possible to form a thin film of the resin composition.
• the average particle diameter is the particle diameter at an integrated value of 50% in a volume-based particle size distribution measured by a laser diffraction/scattering method.
• the average particle diameter can be measured, for example, using a laser scattering diffraction particle size distribution analyzer: LS13320 (manufactured by Beckman Coulter, wet type).
• component (D) When containing component (D), it is not particularly limited, but it is preferable that component (D) is contained in 50% by mass or more, and 60% by mass in 100% by mass of nonvolatile components in the resin composition. It is more preferable to contain 65% by mass or more, and even more preferably 65% by mass or more. With this configuration, the coefficient of thermal expansion can be reduced. More specifically, by having the content ratio of component (D) within the above range, the linear expansion coefficient ⁇ 1 of the cured product of the resin composition below the glass transition temperature, and the coefficient of linear expansion ⁇ 1 of the cured product above the glass transition temperature The linear expansion coefficient ⁇ 2 can be reduced.
• the component (D) is contained in 50 to 95% by mass, more preferably 60 to 90% by mass, and even more preferably 65 to 85% by mass in 100% by mass of the nonvolatile components in the resin composition. preferable.
• the content ratio of component (D) is within the above range, it is possible to reduce the coefficient of linear expansion ⁇ 2 above the glass transition temperature, and also to reduce the generation of stress during the heat resistance reliability test of the multilayer substrate.
• component (D) in order to lower the coefficient of thermal expansion of the resin composition, when the component (D) is contained in an amount of 50% by mass or more as described above, if the inorganic filler is highly loaded, the melt viscosity of the resin composition will increase, and the melt viscosity of the resin composition will increase. There is a tendency for the embeddability to deteriorate.
• component (B) which is a compound that has an isocyanuric ring structure and two allyl groups in one molecule and is liquid at 25°C, the resin composition It is possible to lower the melt viscosity of a substance and improve its embedding ability in wiring.
• the silica filler used in component (D) includes fused silica, ordinary silica, spherical silica, crushed silica, crystalline silica, amorphous silica, etc., and is not particularly limited. Spherical fused silica is desirable from the viewpoints of dispersibility of the silica filler, fluidity of the thermosetting resin composition, surface smoothness of the cured product, dielectric properties, low coefficient of thermal expansion, adhesiveness, etc.
• the method of surface-treating the silica filler using the above-mentioned coupling agent is not particularly limited, and examples thereof include a dry method, a wet method, and the like.
• silica filler and an appropriate amount of silane coupling agent for the surface area of the silica filler are placed in a stirring device and stirred under appropriate conditions, or the silica filler is placed in a stirring device in advance and the silane coupling agent is placed in an appropriate amount for the surface area of the silica filler and stirred under appropriate conditions.
• stirring add an appropriate amount of silane coupling agent to the surface area of the silica filler by dropping or spraying as a stock solution or solution, and uniformly adhere the silane coupling agent to the surface of the silica filler by stirring, This is a method of surface treatment (by hydrolysis).
• the stirring device include, but are not particularly limited to, mixers capable of stirring and mixing at high speed, such as a Henschel mixer.
• silica filler is added to a surface treatment solution in which a sufficient amount of silane coupling agent is dissolved in water or an organic solvent for the surface area of the silica filler to be surface treated, and the mixture is stirred to form a slurry.
• the silane coupling agent and the silica filler are sufficiently reacted, and then the silica filler is separated from the surface treatment solution using filtration, centrifugation, etc., and then heated and dried to perform surface treatment.
• Component (E) is a curing catalyst.
• the curing catalyst as component (E) is an additive for favorably starting the reaction of component (A) and component (B).
• component (E) By including such component (E), the degree of curing of the resin composition can be improved at a certain curing temperature and time. For this reason, it is preferable that the resin composition of this embodiment further contains a curing catalyst as component (E).
• the curing catalyst for component (E) may be any catalyst that causes the curing reaction of components (A) and (B), and conventionally known reaction initiators (for example, polymerization initiators) can be used.
• examples of the curing catalyst include organic peroxides and azo compounds.
• examples of the curing catalyst for component (E) include organic peroxides manufactured by NOF Corporation under the trade name "Percmil D" and "Perbutyl C” (trade name).
• Component (E) may be used alone or in combination of two or more.
• the content of component (E) is preferably 0.1 to 5 parts by mass based on the total 100 parts by mass of the resin components of the resin composition. With this configuration, heat resistance and adhesiveness can be improved satisfactorily.
• the content of component (E) is more preferably 0.1 to 4 parts by mass based on the total 100 parts by mass of the resin components of the resin composition, and 0. More preferably, the amount is .1 to 3 parts by mass.
• Component (F) is an antioxidant.
• the antioxidant component (F) is an additive for improving heat resistance reliability. By including such component (F), heat resistance reliability can be improved.
• Component (G) is a silane coupling agent. Adhesion can be improved by adding component (G), a silane coupling agent.
• the resin composition of this embodiment may further contain components other than the components (A) to (E) described above.
• other components include various additives such as a solvent, a dispersant, an antifoaming agent, a leveling agent, a thixotropic agent, a flame retardant, and a fluxing agent.
• the resin composition of this embodiment can be manufactured by a conventional method.
• the resin composition of this embodiment can be prepared by combining each of the components described above with a solvent using, for example, a bead mill, a laika machine, a pot mill, a three-roll mill, a rotary mixer, a twin-shaft mixer, a dissolver, an agitator, etc. It can be manufactured by dissolving, mixing and dispersing them together.
• the resin composition of this embodiment can be suitably used as a resin composition for protective agents, adhesives, and adhesive films used in electronic components. Further, the resin composition of the present embodiment can be suitably used as an interlayer bonding sheet or an interlayer adhesive for multilayer wiring boards.
• the resin composition of this embodiment is used for various applications for electronic components, there are no particular restrictions on the electronic components to be bonded, including various printed wiring boards such as ceramic substrates and organic substrates, various electronic components, semiconductor chips, etc. Examples include semiconductor devices.
• Adhesive films, interlayer bonding sheets, interlayer adhesives, etc. using the resin composition of the present embodiment are included as cured products of the resin composition in laminates and semiconductor devices constituting electronic components and the like. Therefore, it is preferable that a cured product of the resin composition of this embodiment be included in a laminate or a semiconductor device constituting an electronic component or the like.
• the resin composition of this embodiment can also be used as a prepreg using the resin composition or a high-frequency electronic component having a cured product of the resin composition.
• the resin composition of this embodiment preferably has an elastic modulus of 1.0 to 15.0 GPa, more preferably 1.5 to 12.0 GPa, and 2.0 to 10 GPa at room temperature (25°C). It is more preferably .0 GPa, and particularly preferably 4.1 to 9.0 GPa.
• the elastic modulus at 25° C. is within the above range, it is possible to obtain a cured product that is hard to be scratched on the surface of the cured product and has high hardness.
• the elastic modulus is lower than the above range, the cured product will be soft and defects such as scratches and bends may occur in the cured product during the process of manufacturing wiring boards.
• the resin composition of the present embodiment preferably has an elastic modulus of 0.1 to 5.0 GPa at 200°C, and preferably 0.1 to 3.0 GPa, from the viewpoint of reducing stress and distortion during heating. It is more preferably 0 GPa, and even more preferably 0.1 to 2.0 GPa.
• the resin composition of this embodiment preferably has a glass transition temperature of 120 to 170°C, more preferably 130 to 165°C, even more preferably 135 to 160°C, and even more preferably 140 to 158°C. It is particularly preferable that there be.
• the glass transition temperature is within the above range, it is possible to obtain a cured product that has sufficient flexibility to follow deformation and has good impact resistance. If the glass transition temperature is higher than the above range, the cured product tends to become brittle, and defects such as scratches, chips, and cracks may occur in the cured product during the process of manufacturing wiring boards.
• stress generation during a reliability test for example, a thermal cycle test
• a reliability test for example, a thermal cycle test
• Example preparation After weighing each component other than component (D) and component (E) so that the proportions (parts by mass) are shown in Tables 1 to 5 below, they are poured into a container in which they are dissolved together with a specified solvent, and the lid is closed. While stirring using a stirrer at a rotation speed of 100 to 400 rpm, the mixture was heated to 70° C. and mixed at normal pressure for 3 to 6 hours. Thereafter, the mixture was cooled to room temperature, component (D) was added thereto, and the mixture was stirred and mixed at a rotational speed of 100 to 400 rpm for 1 hour, followed by dispersion using a bead mill.
• component (E) was added and stirred and mixed using a stirrer at a rotation speed of 100 to 400 rpm for 1 hour.
• dissolved dispersions containing the resin compositions of Examples 1 to 16 and Comparative Examples 1 to 5 were prepared.
• the raw materials used to prepare the dissolved dispersions containing the resin compositions in Examples 1 to 16 and Comparative Examples 1 to 5 are as follows.
• [(A) component] (A1) Polyphenylene ether resin having a group represented by formula (1) at the end, manufactured by SABIC Innovative Plastics, trade name "Noryl SA9000", Mn: 1850-1950.
• Component (B) compound having an isocyanuric ring structure and two allyl groups in one molecule
• B1 Manufactured by Shikoku Kasei Co., Ltd., trade name "L-DAIC”, compound represented by the above formula (2).
• R 2 is an alkyl group having 4 to 14 carbon atoms.
• B'2 Manufactured by Mitsubishi Chemical Corporation, trade name "TAIC", a compound having an isocyanuric ring structure and three allyl groups in one molecule.
• (C1) Hydrogenated styrenic thermoplastic elastomer (SEBS) manufactured by Kraton Polymer Co., Ltd., trade name "Kraton G1652", Mn: 54,000.
• (C2) Hydrogenated styrene thermoplastic elastomer (SEEPS) manufactured by Kuraray Co., Ltd., trade name "Septon 4033", Mn: 74,000.
• (C3) Hydrogenated styrene thermoplastic elastomer (SEBS) manufactured by Kuraray Co., Ltd., trade name "Septon 8004", Mn: 76,000.
• D1 Spherical silica surface-treated with 7-octenyltrimethoxysilane (silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. (product name "KBM-1083”)) (spherical silica is manufactured by Denka Co., Ltd., product name "KBM-1083").
• FB-3SDX average particle size 3 ⁇ m was used).
• D2 Spherical silica surface-treated with octyltriethoxysilane (silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd.
• Component (F): Antioxidant (F1): Hindered phenol antioxidant manufactured by ADEKA (melting point 220-222°C), trade name "AO-20”. (F2): Hindered phenol antioxidant manufactured by ADEKA (melting point 51-54°C), trade name "AO-50”.
• Component (G) Silane coupling agent
• (G1) Silane coupling agent (bis(triethoxysilylpropyl)tetrasulfide) manufactured by Osaka Soda Co., Ltd., trade name "Cabras 4".
• total resin component column in Tables 1 to 4 shows the total amount (parts by mass) of the components corresponding to the resin component among the raw materials used for preparing the resin composition.
• total solid content column in Tables 1 to 4 shows the total amount (parts by mass) of the components corresponding to the solid content among the raw materials used for preparing the resin composition.
• the "Filler ratio (Wt%)” column in Tables 1 to 4 shows the ratio (mass%) of component (D) in the solid raw material used for preparing the resin composition.
• soldering heat resistance (280°C, 290°C, 300°C)
• the resin film produced by the method described above was sandwiched between 18 ⁇ m thick copper foils and cured at a temperature of 200°C for 1 hour under a pressure of 3 MPa to prepare a sample (double-sided copper-clad board) for evaluating solder heat resistance. Created.
• the fabricated double-sided copper-clad board was cut into 25 mm square pieces and floated in solder baths at 280°C, 290°C, and 300°C for 1 minute each, during which time the appearance of each sample was visually confirmed and evaluated based on the following evaluation criteria. I did it. If the evaluation result is “ ⁇ ”, it is considered a pass.
• ⁇ No change.
• ⁇ Blistering and peeling of copper foil.
• FIG. 1 is a plan view showing patterning in evaluation of substrate pattern embeddability.
• L/S in FIG. 1 indicates line and space.
• the resin film and copper foil (18 ⁇ m) were cut into 100 x 100 mm pieces, and the copper foil, resin film, embeddability evaluation board, resin film, and copper foil were laminated in this order, and this was heated at 200°C for 1 hour. After curing at a pressure of 3 MPa, only the copper foil on one side was removed by etching to expose the surface of the resin film, and the embeddability was evaluated by observing its appearance.
• FIG. 2 An example of a photograph with good embeddability is shown in FIG. 2, and an example of a photograph with poor embeddability is shown in FIG.
• FIG. 3 when the embedding property is poor and there is a part (defective embedding part) in which the resin film is not embedded between the patterns, the color of the defective embedding part is observed to be mottled and whitish. If the evaluation result is “ ⁇ ”, it is considered a pass. ⁇ : No embedding defect is observed. ⁇ : Poor embedding part is observed.
• ⁇ Evaluation of elastic modulus ⁇ Measurement was performed using dynamic viscoelasticity measurement (DMA). Specifically, the film was heated and cured at 200°C, peeled off from the support, and then a test piece (10 ⁇ 0.5 mm x 40 ⁇ 1 mm) was cut out from the adhesive film, and the width and thickness of the test piece were measured. . Thereafter, measurement was performed using DMS6100 (3°C/min 23-250°C 10Hz). The storage elastic modulus at 25°C was defined as "the elastic modulus at room temperature (25°C)", and the storage elastic modulus at 200°C was defined as the "elastic modulus at 200°C”.
• DMA dynamic viscoelasticity measurement
• Tg ⁇ Glass transition temperature (Tg) ⁇ Measurement was performed using the dynamic viscoelasticity measurement (DMA) described above. Specifically, the film was heated and cured at 200°C, peeled off from the support, and then a test piece (10 ⁇ 0.5 mm x 40 ⁇ 1 mm) was cut out from the adhesive film, and the width and thickness of the test piece were measured. . Thereafter, measurement was performed using DMS6100 (3°C/min 23-250°C 10Hz). The peak temperature of tan ⁇ was read and defined as Tg.
• DMA dynamic viscoelasticity measurement
• ⁇ Impact resistance ⁇ Ball impact drop strength was measured. Specifically, the film was heated and cured at 200° C., and a test piece of 20 mm ⁇ 30 mm and 1 mm thick was prepared. This test piece was placed on an iron plate, and an alumina ball weighing 25 g was dropped from a height of 50 cm from above to conduct an impact resistance test. The test was conducted three times, and those in which no cracking occurred in any of the tests were evaluated as good.
• Comparative Example 1 in which the component (A) of Example 7 was replaced with OPE-2ST 2200, had a large rate of change in tan ⁇ of heat resistance reliability of 58.9%, and was inferior in this respect.
• Comparative Example 2 in which the component (B) of Example 1 was replaced with TAIC, had an initial value of tan ⁇ of 0.0022, which was larger than 0.002 and was inferior in this respect.
• Comparative Example 3 in which component (A) of Example 1 was replaced with OPE-2ST 2200, the rate of change in tan ⁇ was 24.1%, which was 20% or more, which was large in terms of heat resistance reliability, and the rate of change in tan ⁇ was large at 280°C in terms of soldering heat resistance.
• Comparative Example 1 which similarly used OPE-2ST 2200, passed the soldering heat resistance even at 300°C, but this is because Comparative Example 3 uses Kabras 4, which is the component (G). This is because the difference in heat resistance between SA-9000 and OPE-2ST 2200 became more pronounced.
• Comparative Example 4 in which L-DAIC as component (B) was further removed from Comparative Example 3 and its reduced amount was replaced with component (C), was inferior in solder heat resistance as in Comparative Example 3, and also had poor board pattern embedding properties. It was a failure.
• Table 4 shows the case where the inorganic filler of component (D) is not used, but regarding the heat resistance reliability, the rate of change in tan ⁇ was 176.8% in Example 11 where SA-9000 was used as the component (A).
• Comparative Example 5 using OPE-2St 2200 it was as large as 222.2%, and Example 11 was superior.
• solder heat resistance Example 11 passed at 300°C
• both Example 11 and Comparative Example 5 passed the test because L-DAIC was used as the component (B).
• the heat resistance reliability of ⁇ there was generally little change, and all Examples and Comparative Examples were good.
• Example 7 and Examples 12 to 16 the elastic modulus at room temperature (25°C) is 4.1 to 9.0 Gpa or less, and the elastic modulus at 200°C is 0. It was good at 1 to 2.0 Gpa or less. In addition, the glass transition temperature of Example 7 and Examples 12 to 16 was in the range of 140 to 158°C, which was good. Regarding impact resistance, no defects such as cracks were observed in any of the examples. Ta.
• the resin composition of the present invention can be used as an adhesive for use in electronic components or as a resin composition for adhesive films. Furthermore, the resin composition of the present invention can be used as an interlayer bonding sheet or an interlayer adhesive for multilayer wiring boards. Further, the resin composition of the present invention can also be used as a prepreg using a cured product of the resin composition, or as an electronic component for high frequencies having a cured product of the resin composition.

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• 2023
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