WO2022255078A1 - 樹脂組成物及びその製造方法、並びに接着フィルム及び層間接着用ボンディングシート - Google Patents

樹脂組成物及びその製造方法、並びに接着フィルム及び層間接着用ボンディングシート Download PDF

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WO2022255078A1
WO2022255078A1 PCT/JP2022/020427 JP2022020427W WO2022255078A1 WO 2022255078 A1 WO2022255078 A1 WO 2022255078A1 JP 2022020427 W JP2022020427 W JP 2022020427W WO 2022255078 A1 WO2022255078 A1 WO 2022255078A1
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component
styrene
resin composition
resin
ratio
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PCT/JP2022/020427
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English (en)
French (fr)
Japanese (ja)
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宗俊 日馬
遼 宇佐美
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ナミックス株式会社
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Priority to JP2023525703A priority Critical patent/JPWO2022255078A1/ja
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    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated

Definitions

  • the present invention relates to a resin composition, a method for producing the same, an adhesive film, and a bonding sheet for interlayer adhesion.
  • LCP liquid crystal polymers
  • Patent Literature 1 As materials used for FPCs and RF cables, for example, a thermosetting resin composition using a specific vinyl compound and rubber or a thermoplastic elastomer and an uncured film made thereof have been proposed (see, for example, Patent Document 1). .
  • the technique described in Patent Literature 1 aims at achieving a low dielectric constant and a low dielectric loss tangent in a low elasticity and high frequency region.
  • Patent Document 1 the technique described in Patent Document 1 is intended to achieve a low dielectric constant and a low dielectric loss tangent in the low elasticity and high frequency regions as described above, but the resin flow (for example, fluidity) of the film was not considered.
  • the resin flow (fluidity) of the film as described above may be referred to as "resin flow”.
  • the present invention has been made in view of such problems of the prior art.
  • the present invention provides a resin composition for an adhesive film that can provide sufficient adhesive strength while having a low dielectric loss and can suppress the resin flow of the adhesive film, a method for producing the same, an adhesive film, and bonding for interlayer adhesion. provide a sheet.
  • the following resin composition, method for producing the same, adhesive film and bonding sheet for interlayer adhesion are provided.
  • the component (A) is (A1) a first styrene/butadiene/butylene/styrene block copolymer having a styrene ratio of 40% or more; (A2) a second styrene/butadiene/butylene/styrene block copolymer having a styrene proportion of less than 40%;
  • a step of mixing (A) a styrene/butadiene/butylene/styrene block copolymer, (B) an epoxy resin, and (C) a thermosetting resin other than an epoxy resin;
  • As the component (A), (A1) a first styrene/butadiene/butylene/styrene block copolymer having a styrene ratio of 40% or more and (A2) a second styrene/butadiene/butylene/styrene block copolymer having a styrene ratio of 40% or less.
  • a method for producing a resin composition wherein the compounding ratio of the component (A1) and the component (A2) is adjusted so that the styrene ratio of the component (A) is 31 to 60%.
  • the resin composition of the present invention can be suitably used as a resin composition for adhesive films.
  • it has the effect of obtaining sufficient adhesive strength while maintaining low dielectric loss and suppressing resin flow in adhesive films. It is something that plays.
  • the resin composition of the present invention when used as a bonding sheet for a multi-layered substrate, it is possible to suppress the resin flow at the perforated portion of the multi-layered substrate.
  • the method for producing a resin composition of the present invention can easily produce the resin composition described above.
  • the adhesive film and the bonding sheet for interlayer adhesion of the present invention use the resin composition described above, and provide sufficient adhesive strength while maintaining low dielectric loss. This is effective in that the flow can be suppressed.
  • Resin composition One embodiment of the resin composition of the present invention comprises (A) a styrene/butadiene/butylene/styrene block copolymer (hereinafter also referred to as “component (A)”) and (B) an epoxy resin (hereinafter referred to as “(B ) component”) and (C) a thermosetting resin other than an epoxy resin (hereinafter also referred to as “(C) component”).
  • the styrene ratio of component (A) is 31 to 60%.
  • the resin composition constructed as described above can be suitably used as a resin composition for an adhesive film. Resin flow can be suppressed.
  • the resin composition of the present embodiment includes other components such as (D) a curing catalyst and (E) an organic peroxide. may contain ingredients.
  • Component (A) is a styrene/butadiene/butylene/styrene block copolymer having a styrene ratio of 31 to 60%.
  • SBBS styrene/butadiene/butylene/styrene block copolymer
  • Styrene/butadiene/butylene/styrene block copolymer (SBBS) as component (A) is a highly selective 1,2-bond in the polybutadiene block of styrene/butadiene/styrene block copolymer (hereinafter also referred to as “SBS”). It is a hydrogenated styrenic thermoplastic elastomer obtained by hydrogenating the By including SBBS as the component (A), solder heat resistance and dielectric properties can be improved.
  • the presence or absence of component (A) in the resin composition can be detected by a method such as a Fourier transform infrared spectrophotometer (FTIR).
  • FTIR Fourier transform infrared spectrophotometer
  • the styrene/butadiene/butylene/styrene block copolymer as component (A) includes a styrene/ethylene/butylene/styrene block copolymer obtained by hydrogenating all double bonds in the polybutadiene block (hereinafter referred to as “SEBS”). ) is not included.
  • SEBS polybutadiene block
  • a styrenic thermoplastic elastomer in which all double bonds are hydrogenated is referred to as a "hydrogenated styrenic thermoplastic elastomer".
  • a styrene-based thermoplastic elastomer is sometimes referred to as a "partially hydrogenated styrene-based thermoplastic elastomer”.
  • a non-hydrogenated styrenic thermoplastic elastomer such as styrene/butadiene/styrene block copolymer (hereinafter also referred to as "SBS") is sometimes referred to as a "non-hydrogenated styrenic thermoplastic elastomer”.
  • the (A) component used in the resin composition of the present embodiment has a particularly major configuration in that the styrene ratio is 31 to 60%.
  • the styrene ratio of component (A) is 31 to 60%, resin flow is small and sufficient adhesive strength to LCP can be achieved.
  • the styrene ratio of the component (A) is less than 31%, the adhesion strength is high, but the control of the resin flow cannot be said to be sufficient.
  • the styrene ratio of the component (A) increases, the resin flow can be suppressed, but the adhesive strength becomes weaker.
  • the styrene ratio of the component (A) is preferably 32 to 52% in order to reduce resin flow and obtain sufficient adhesive strength to LCP. More preferably ⁇ 46%.
  • the "styrene ratio” means the percentage (%) of the ratio of the content of the styrene component to the total mass of the styrene-based thermoplastic elastomer.
  • styrene ratio measurements are made using nuclear magnetic resonance (NMR). Specifically, using tetrachloroethane as a solvent, the integrated value of the peak in the range of 5.5 ppm to 6.5 ppm corresponding to styrene and the integrated value of the peak in other ranges were obtained, and from the obtained values calculate.
  • the styrene ratio of the SBBS is the "styrene ratio of the (A) component".
  • the weighted average value of the styrene ratios of the SBBSs is defined as the "styrene ratio of the component (A)".
  • the styrene ratio of the component (A) is sometimes referred to as "average styrene ratio".
  • the average styrene ratio (%) of component (A) can be calculated based on the following formula (1).
  • one of the two types of SBBS is called “SBBS(1)” and the other is called “SBBS(2)".
  • SBBS(1) represents the mass ratio (% by mass) of SBBS (1) in component (A)
  • X (2) represents SBBS (% by mass) in component (A). 2 shows the mass ratio (% by mass).
  • ST (1) indicates the styrene ratio (%) of SBBS (1)
  • ST (2) indicates the styrene ratio (%) of SBBS (2).
  • the styrene ratio of SBBS (1) is 20% and the styrene ratio of SBBS (2) is 40%. Then, when the mass ratio of SBBS (1) in component (A) is 10% by mass and the mass ratio of SBBS (2) is 90% by mass, it is calculated by the following formula (2). be able to. That is, the average styrene ratio of such component (A) is 38%. When three or more types of SBBS with different components (A) are mixed, the weighted average value of the styrene ratios of the three or more types of SBBS can be calculated according to the formula (1) above. good.
  • component (A) is a mixture of two or more types of SBBS with different styrene ratios
  • the resin flow can be appropriately controlled, and sufficient adhesive strength to LCP can be obtained.
  • the component (A) is preferably configured as follows.
  • (A) consists of (A1) a first styrene/butadiene/butylene/styrene block copolymer having a styrene ratio of 40% or more and (A2) a second styrene/butadiene/butylene/styrene having a styrene ratio of less than 40%. and block copolymers.
  • the blending ratio (mass ratio) of the first styrene/butadiene/butylene/styrene block copolymer and (A2) the second styrene/butadiene/butylene/styrene block copolymer is not particularly limited, and includes both (A).
  • the compounding ratio may be such that the average styrene ratio of the components falls within the numerical range of 31 to 60%.
  • Component (A) has good compatibility with components (B) and (C) and film-forming ability, and gives a cured product with excellent strength balance. ,000, more preferably 40,000 to 100,000, even more preferably 50,000 to 80,000.
  • the weight average molecular weight is determined by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.
  • the component (A) may also be a reactive elastomer to which a functional group such as amine has been added. Adhesive strength (peel strength) can be further improved by using a reactive elastomer to which a functional group is added.
  • component (A) There are no particular restrictions on the content of component (A).
  • the content ratio of the component (C) and the component (A) described above if the component (C) is too small (in other words, the amount of the component (A) is too large), the amount of the curing component will decrease and the amount of flow will increase. I don't like it in terms of points.
  • the curing component increases and the film hardens. It is not preferable in that the product becomes hard and adhesiveness is lowered.
  • the component (A) content is preferably 60 to 83% by mass, more preferably 65 to 72% by mass, based on 100% by mass of the resin component in the resin composition.
  • a specific example of the component (A) is the product name "P5051” manufactured by Asahi Kasei Chemicals.
  • the component (A) for example, two or more kinds of product names such as "P1083", “P1500”, “P5051” and “P2000” manufactured by Asahi Kasei Chemicals Co., Ltd. are used so that the average styrene ratio is 31 to 60%. You may mix and use it.
  • ((B) component) (B) Component is an epoxy resin.
  • Epoxy resins of component (B) include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin, siloxane type epoxy resin, biphenyl type epoxy resin, glycidyl ester type epoxy resin. Resins, glycidylamine-type epoxy resins, hydantoin-type epoxy resins, and naphthalene ring-containing epoxy resins can be mentioned.
  • the compounds exemplified here may be used alone, or two or more of them may be mixed and used.
  • the epoxy resin as the component (B) is preferably a solid epoxy resin.
  • the epoxy resin of the component (B) is an epoxy resin having a naphthalene skeleton because the adhesiveness of the film formed using the resin composition is improved.
  • component (B) is preferably contained in an amount of 0.1 to 3% by mass, more preferably 0.5 to 1.5% by mass, based on 100% by mass of the resin component in the resin composition.
  • component (B) By including an epoxy resin as the component (B), it is possible to improve the adhesive strength. For example, if the component (B) is less than 0.1% by mass, it may be difficult to obtain the desired adhesive strength. On the other hand, if the component (B) is too much, the dielectric properties may deteriorate.
  • component (B) examples include bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation under the trade name of "828EL” and epoxy resin manufactured by Nippon Kayaku under the trade name of "502H”.
  • thermosetting resin other than an epoxy resin is a thermosetting resin other than an epoxy resin.
  • Any thermosetting resin can be selected as the thermosetting resin other than the epoxy resin, but a thermosetting resin having a low dielectric constant and a low dielectric loss tangent is preferred. More specifically, the dielectric constant in the frequency range of 10 GHz is preferably 3.0 or less, more preferably 2.5 or less, or the dielectric loss tangent in the frequency range of 10 GHz is 0.004 or less, more preferably 0.003 or less.
  • Thermosetting resins are preferred. From this point of view, a terminal-modified polyphenylene ether resin can be mentioned as a suitable example of the thermosetting resin other than the epoxy resin as the component (C).
  • a modified polyphenylene ether resin having a carbon-carbon double bond at the terminal is more preferable.
  • Modified polyphenylene ether resins having carbon-carbon double bonds at their ends have relatively low polarity and low dielectric loss tangents.
  • thermosetting resin other than the epoxy resin as component (C) preferably has a number average molecular weight of 1000 or more, and more preferably 2000 or more from the viewpoint of suppressing resin flow.
  • component (D) component) (D) Component is a curing catalyst.
  • the component (D) is a component that aids curing of the adhesive film or the bonding sheet for interlayer adhesion formed using the resin composition of the present embodiment.
  • component (D) is preferably a catalyst that accelerates the curing reaction of the epoxy resin of component (B).
  • Examples of the curing catalyst as component (D) include imidazole-based curing catalysts, amine-based curing catalysts, phosphorus-based curing catalysts, and the like.
  • Examples of imidazole-based curing catalysts include 2-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl. -4-imidazole, 2-phenylimidazole, 1-benzyl-2-phenylimidazole, 2-phenyl-4-methylimidazole and other imidazole compounds.
  • Amine-based curing catalysts include triazine compounds such as 2,4-diamino-6-[2′-methylimidazolyl-(1′)]ethyl-s-triazine, 1,8-diazabicyclo[5,4,0]undecene -7 (DBU), triethylenediamine, benzyldimethylamine, triethanolamine and other tertiary amine compounds.
  • triazine compounds such as 2,4-diamino-6-[2′-methylimidazolyl-(1′)]ethyl-s-triazine, 1,8-diazabicyclo[5,4,0]undecene -7 (DBU), triethylenediamine, benzyldimethylamine, triethanolamine and other tertiary amine compounds.
  • 2,4-diamino-6-[2'-methylimidazolyl-(1')]ethyl-s-triazine is preferred.
  • phosphorus-based curing catalysts include triphenylphosphine, tributylphosphine, tri(p-methylphenyl)phosphine, and tri(nonylphenyl)phosphine.
  • imidazole-based curing catalysts are preferable because they can be adjusted with appropriate curability.
  • an imidazole-based curing catalyst having a benzene ring is more preferable because it can increase the adhesive strength over time of an uncured film formed using the resin composition of the present embodiment.
  • imidazole-based curing catalysts examples include 2-phenylimidazole, 1-benzyl-2-phenylimidazole and 2-phenyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole is particularly preferred. .
  • the content of component (D) can be appropriately selected according to the type of curing catalyst used as component (D).
  • an imidazole-based curing catalyst is used as component (D)
  • it is preferably 0.01 to 20 parts by mass, preferably 0.1 to 15 parts by mass, relative to 100 parts by mass of the epoxy resin as component (B). is more preferable, and 1 to 10 parts by mass is even more preferable. If the content of component (D) is too small, curability may deteriorate. On the other hand, if the content of component (D) is too high, the shelf life of the adhesive film may deteriorate.
  • (E) component) (E) Component is an organic peroxide.
  • organic peroxides include, for example, t-butyl peroxybenzoate, t-butyl peroxy isopropyl carbonate, t-butyl peroxy-2-ethylhexyl carbonate, t-butyl peroxy acetate, dicumylper oxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-t-butylperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne- 3,1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-butylperoxy)cyclohexane, methyl ethyl ketone peroxide, 2,5-dimethylhexyl-2 , 5-diperoxybenzoate, t-buty
  • the curing reaction of the (C) component for example, the terminal-modified polyphenylene ether resin
  • the curing reaction of the (C) component for example, the terminal-modified polyphenylene ether resin
  • the component (E) is not activated in the temperature range of 60 to 120 ° C. in the drying process of film formation, and is not activated in the temperature range above that. Those that activate are preferred. Examples of such component (E) include t-butyl peroxybenzoate.
  • the resin composition of the present embodiment may further contain components other than components (A) to (E) described above, if necessary.
  • Specific examples of such components include silane coupling agents, antifoaming agents, flow control agents, film forming aids, dispersants, inorganic particles, and the like.
  • the type and amount of each compounding agent are as per usual methods.
  • the adhesive film formed using the resin composition of the present embodiment does not contain components that adversely affect the high-frequency characteristics.
  • examples of such components include liquid rubbers and flame retardants.
  • the resin composition of the present embodiment preferably has, for example, the following properties. It is preferable that the cured product (for example, thermoset product) of the resin composition of the present embodiment has excellent electrical properties at high frequencies. Specifically, the cured product of the resin composition preferably has a dielectric constant ( ⁇ ) of 2.5 or less, more preferably 2.4 or less, in the frequency range of 1 to 10 GHz. Further, the dielectric loss tangent (tan ⁇ ) in the frequency range of 1 to 10 GHz is more preferably 0.0025 or less, more preferably 0.0022 or less. Since the dielectric constant ( ⁇ ) and the dielectric loss tangent (tan ⁇ ) in the frequency range of 1 to 10 GHz are within the above ranges, electrical signal loss in the frequency range of 1 to 10 GHz can be reduced.
  • ⁇ dielectric constant
  • tan ⁇ dielectric loss tangent
  • the cured product of the resin composition of the present embodiment preferably has sufficient adhesive strength.
  • the cured product of the resin composition preferably has a peel strength (180 degree peel) against the roughened copper foil surface measured in accordance with JIS K6854-2 of 4 N/cm or more.
  • the peel strength (90 degree peel) against the liquid crystal polymer film measured according to JIS K6854-1 is 3 N/cm or more.
  • the resin composition of this embodiment can be produced by a conventional method. For example, first, the components (A) to (C) are mixed in the presence of a solvent to obtain a mixture.
  • a styrene/butadiene/butylene/styrene block copolymer having a styrene ratio of 31 to 60% is used as the component (A).
  • the epoxy resins described above are used as the component (B), and thermosetting resins other than the epoxy resins described above are used as the component (C).
  • the resin composition contains other optional components other than components (A) to (C)
  • these optional components may be added to the mixture described above according to a conventional method.
  • the components (A) to (C) can be mixed using, for example, a heat mixing kneader. There are no particular restrictions on the mixing conditions, and examples include rotation speed of 100 to 1000 rpm, 80° C., and 3 hours.
  • component (A) a first styrene/butadiene/butylene/styrene block copolymer having a styrene ratio of 40% or more, and (A2) a styrene ratio of At least less than 40% of the second styrene/butadiene/butylene/styrene block copolymer is used, and the compounding ratio of components (A1) and (A2) as described above is adjusted so that the average styrene ratio of component (A) is 31 to It is preferable to adjust to 60%.
  • component (A) can be adjusted to a desired value.
  • component (A) can be a commercially available styrene/butadiene/butylene/styrene block copolymer. It is difficult to adjust the styrene ratio of styrene/butadiene/butylene/styrene block copolymers to the desired value.
  • the method described above that is, by mixing and using the component (A1) having a styrene ratio of 40% or more and the component (A2) having a styrene ratio of less than 40%, the styrene of the component (A) It is possible to finely adjust the ratio.
  • the components (D) and (E) are further added as necessary, and the mixture is stirred at room temperature for, for example, 30 to 60 minutes.
  • the resin composition of this embodiment can be produced.
  • the adhesive film of this embodiment is an adhesive film using the resin composition of this embodiment described above.
  • the adhesive film of the present embodiment has a low dielectric loss and sufficient adhesive strength, and in particular, it can suppress resin flow in the perforated portion when the substrate is multilayered.
  • the adhesive film of this embodiment can be obtained from the resin composition of this embodiment by a known method.
  • the resin composition of the present embodiment is diluted with a solvent to form a varnish, which is applied to at least one side of a support, dried, and then provided as a film with a support or a film separated from the support. be able to.
  • solvents that can be used as varnishes include ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic solvents such as toluene and xylene; and high boiling point solvents such as dioctyl phthalate and dibutyl phthalate.
  • the amount of the solvent to be used is not particularly limited, and can be the amount conventionally used, preferably 20 to 90% by mass based on the solid content.
  • the support is appropriately selected according to the desired form in the method of manufacturing the adhesive film, and is not particularly limited, but examples thereof include metal foils such as copper and aluminum, carrier films of resins such as polyester and polyethylene, and the like.
  • the adhesive film is provided in the form of an adhesive film separated from a support, the support is preferably release-treated with a silicone compound or the like.
  • the method of applying the varnish is not particularly limited, and examples thereof include a slot die method, a gravure method, a doctor coater method, and the like, and are appropriately selected depending on the desired thickness of the film. It is preferable because the thickness of can be designed to be thin.
  • the application is carried out so that the thickness of the film formed after drying is the desired thickness. Such thickness can be derived from the solvent content by those skilled in the art.
  • the thickness of the adhesive film is appropriately designed based on properties such as mechanical strength required according to the application. preferable.
  • the drying conditions are appropriately designed according to the type and amount of solvent used in the varnish, the amount of varnish used, the thickness of the coating, etc., and are not particularly limited. It can be carried out under atmospheric pressure.
  • the bonding sheet for interlayer adhesion of this embodiment is also a bonding sheet for interlayer adhesion for multilayer substrates using the resin composition of this embodiment, like the above-described adhesive film. Therefore, sufficient adhesive strength can be obtained while the dielectric loss is low, and in particular, resin flow at the perforated portion can be suppressed when the substrate is multi-layered.
  • the procedure for using it is as follows.
  • the adhesive film of the present embodiment after placing the adhesive film on the surface to be adhered of one object, the other object is placed so that the surface to be adhered is the adhesive film of this embodiment. Place it in contact with the exposed surface of the
  • the adhesive film is placed so that the exposed surface of the adhesive film is in contact with the adherend surface of one of the objects, and the adhesive film is placed on the adherend surface.
  • the temperature at the time of temporary pressure bonding can be set to 130° C., for example.
  • the other object is placed on the surface of the adhesive film exposed by peeling off the support after temporary pressure bonding so that the surface to be adhered is in contact with the exposed surface of the adhesive film. After carrying out these procedures, they are thermally compressed at a predetermined temperature for a predetermined period of time, and then heat-cured. Note that the thermocompression bonding process may be omitted.
  • the temperature during thermocompression bonding is preferably 100 to 150°C.
  • the thermocompression bonding time is preferably 0.5 to 10 minutes.
  • the temperature for heat curing is preferably 150 to 200°C.
  • the heat curing time is preferably 30 to 120 minutes.
  • a varnish obtained by diluting the resin composition of the present embodiment with a solvent is applied to the adherend surface of one of the objects to be adhered, and dried. A procedure of placing the object may be implemented.
  • the procedure for using it is as follows.
  • the adhesive film of the present embodiment is placed at a predetermined position of the wiring-equipped resin substrate having the wiring pattern formed on the main surface, that is, at the position where the wiring pattern is formed, the position covered with the adhesive film. After arranging, they may be temporarily press-bonded, heat-press-bonded, and cured by heating at a predetermined temperature and for a predetermined time. Note that the thermocompression bonding process may be omitted. Temporary pressure bonding, thermocompression bonding, and heat curing temperature and time are the same as in the case of using the adhesive film for electrical and electronic applications.
  • the bonding sheet for interlayer adhesion of the present embodiment is suitable as a bonding sheet for interlayer adhesion for multilayer substrates, and can be used for interlayer adhesion between substrates of semiconductor devices, for example.
  • the objects to be adhered as described in connection with the above-described adhesive film are a plurality of substrates that constitute a semiconductor device and are laminated in multiple layers.
  • a varnish obtained by diluting the resin composition of the present embodiment with a solvent may be used instead of using a preformed film.
  • the substrate that constitutes the semiconductor device there are no particular restrictions on the substrate that constitutes the semiconductor device, and for example, any of organic substrates such as epoxy resins, phenol resins, and bismaleimide triazine resins, and inorganic substrates such as CCL substrates, ceramic substrates, and silicon substrates can be used.
  • organic substrates such as epoxy resins, phenol resins, and bismaleimide triazine resins
  • inorganic substrates such as CCL substrates, ceramic substrates, and silicon substrates
  • a laminate obtained by laminating a member containing a liquid crystal polymer using the bonding sheet for interlayer adhesion of the present embodiment can be cited as a suitable example.
  • the resin composition, the adhesive film, and the bonding sheet for interlayer adhesion described so far can also be provided as a cured product obtained by curing them.
  • a cured product of the resin composition of the present embodiment a cured product of the adhesive film of the present embodiment, and a cured product of a bonding sheet for interlayer adhesion.
  • a cured product comprising a laminate in which a member containing a liquid crystal polymer is laminated using a bonding sheet for interlayer adhesion.
  • the present invention can also provide a laminate using the resin composition described above and a semiconductor device using the resin composition.
  • the resin composition of the present embodiment has a low dielectric loss and a sufficient adhesive strength, and can suppress resin flow in a drilled portion in a multi-layered substrate.
  • Example preparation After weighing and blending each component so that the blending ratio (% by mass) shown in Tables 1 to 4 below, they are put into a reaction kettle heated to 80 ° C. and rotated at a rotation speed of 150 rpm. Atmospheric mixing was carried out for 4 hours. However, the curing catalyst (D) and the organic peroxide (E) were added after cooling. As described above, varnishes containing the resin compositions of Examples 1 to 14 and Comparative Examples 1 to 5 were prepared.
  • A-1 Partially hydrogenated styrene thermoplastic elastomer (SBBS (1)), manufactured by Asahi Kasei Chemicals, trade name “P1083”.
  • A-2) Partially hydrogenated styrene thermoplastic elastomer (SBBS (2)), manufactured by Asahi Kasei Chemicals, trade name “P1500”.
  • A-3) Partially hydrogenated styrene thermoplastic elastomer (SBBS (3)), manufactured by Asahi Kasei Chemicals, trade name “P5051”.
  • A-4) Partially hydrogenated styrene thermoplastic elastomer (SBBS (4)), manufactured by Asahi Kasei Chemicals, trade name “P2000”.
  • [(A') Component] (A'-5): Non-hydrogenated styrene thermoplastic elastomer (SBS (1)), manufactured by JSR, trade name "TR2003”.
  • (A′-6) Hydrogenated styrene thermoplastic elastomer (SEBS (1)), manufactured by Asahi Kasei Chemicals, trade name “H1517”.
  • B-1) Epoxy resin, trade name "EPPN-502H” manufactured by Nippon Kayaku Co., Ltd.
  • (B-2) Epoxy resin, manufactured by Mitsubishi Chemical Corporation, trade name "828EL".
  • [(C) Component] (C-1) thermosetting resin other than epoxy resin, manufactured by Mitsubishi Gas Chemical Company, trade name "OPE-1200”.
  • C-2) thermosetting resin other than epoxy resin, manufactured by Mitsubishi Gas Chemical Company, trade name "OPE-2200”.
  • [(D) component] (D-1) Curing catalyst, imidazole manufactured by Adeka Co., Ltd., trade name "EH2021”.
  • (D-2) Curing catalyst, 2-ethyl-4-methylimidazole manufactured by Shikoku Kasei Co., Ltd., trade name “2E4MZ”.
  • E-1 Organic peroxide, manufactured by NOF Corporation, trade name "PERBUTYL Z”.
  • E-2) Organic peroxide, manufactured by NOF Corporation, trade name "Percumyl D”.
  • [Other compounding agents] Inorganic Particle-1): Fused Silica, manufactured by Denka Co., Ltd., trade name "FB-300MDX”.
  • the varnish containing the obtained resin composition was applied to one side of the support (PET film subjected to release treatment) and dried at 100°C to obtain an adhesive film with support.
  • a release-treated PET film was placed on the support-attached adhesive film prepared in each of Examples and Comparative Examples to obtain a film laminate of PET film/adhesive film/PET film.
  • This film laminate was hot-pressed under the conditions of a press temperature of 200° C., a temperature holding time of 75 minutes, and a press pressure of 0.44 MPa (45 kgf/cm 2 ) to thermally cure the adhesive film. Both sides of the cured adhesive film were removed from the release treated PET film, and the following evaluations were performed. Tables 1 to 4 show the results of each evaluation.
  • the adhesive film was heat-cured at 200° C. for 75 minutes at 0.44 MPa (45 kgf/cm 2 ), peeled off from the support, and then cut out from the adhesive film into a test piece (50 ⁇ 0.5 mm ⁇ 100 ⁇ 2 mm). , the thickness was measured.
  • the dielectric constant ( ⁇ ) and dielectric loss tangent (tan ⁇ ) of the film whose thickness was measured were measured by the dielectric resonator method (SPDR method). In the measurement by the dielectric resonator method, the measurement frequency was 10 GHz.
  • the dielectric constant ( ⁇ ) is preferably 3.0 or less, more preferably 2.5 or less.
  • the dielectric loss tangent (tan ⁇ ) is preferably 0.0025 or less, more preferably 0.0020 or less.
  • FIGS. 1 to 3 are schematic diagrams for explaining the method of measuring the flow amount. 1 to 3, (a) is a plan view of a test piece used for measuring the flow amount, (b) is an AA' cross section in FIG. 1, a BB' cross section in FIG. and the CC' section of FIG. 3, respectively.
  • a copper foil 12 having a thickness of 18 ⁇ m was attached to one side of an adhesive film 11 cut into a size of 100 mm ⁇ 100 mm, with the glossy side facing inward.
  • the size of the copper foil 12 is also 100 mm ⁇ 100 mm, like the adhesive film 11 .
  • a hole 20 having a diameter of 6 mm penetrating through the adhesive film 11 and the copper foil 12 is formed in each intermediate portion of each side of the rectangular periphery of the adhesive film 11 bonded to the copper foil 12. It was opened with a punch to prepare a test piece 10 for measuring the amount of flow.
  • the LCP 13 was attached to one side of the obtained test piece 10, and was thermocompression bonded with a pressing machine. The conditions for thermocompression bonding were 200° C., 75 minutes, and 0.44 MPa (45 kgf/cm 2 ).
  • the parts of the test piece 10 where the holes 20 were made were observed with an electron microscope, and the length ( ⁇ m) of the resin flow at each of the parts (4 points) where the holes 20 were made was measured.
  • the length ( ⁇ m) of the resin flow the length of the largest portion of the resin flow was measured for each hole 20 formed. Then, the average value of the length of the resin flow at the four points was used as the measured value for the evaluation of the amount of flow.
  • the above-described measured value (average value) must be 150 ⁇ m or less, more preferably 80 ⁇ m or less.
  • the resin compositions of Examples 1 to 14 in which the average styrene ratio of component (A) was set to a predetermined value, had dielectric constant ( ⁇ ), dielectric loss tangent (tan ⁇ ), adhesive peel strength ( Copper foil), adhesive peel strength (LCP), flow rate, reliability (moisture absorption reflow), and solder heat resistance test showed good results.
  • the resin compositions of Examples 1 to 14 were able to produce an adhesive film capable of suppressing the resin flow to 150 ⁇ m or less in the measurement of the flow amount. It was possible to suppress
  • the styrene ratio of the component (A) was too high, making it impossible to form a film.
  • the styrene ratio of the component (A) was too low, and the resin flow was 200 ⁇ m in the measurement of the flow amount. Since the resin composition of Comparative Example 3 did not contain an epoxy resin as the component (B), the adhesive peel strength (LCP), reliability (moisture absorption reflow), and solder heat resistance test evaluations failed.
  • the resin composition of Comparative Example 4 did not contain a styrene/butadiene/butylene/styrene block copolymer (SBBS) as component (A), but instead contained a styrene/butadiene/styrene block copolymer (SBS (1)). , and the dielectric loss tangent (tan ⁇ ), adhesion peel strength (LCP) and flow amount evaluations were unsatisfactory.
  • SBBS styrene/butadiene/butylene/styrene block copolymer
  • SBS (1) styrene/butadiene/styrene block copolymer
  • the resin composition of Comparative Example 5 also did not contain styrene/butadiene/butylene/styrene block copolymer (SBBS) as component (A), but instead contained styrene/butadiene/styrene block copolymer (SEBS (1)). , and the evaluation of reliability (moisture absorption reflow) and solder heat resistance test failed.
  • SBBS styrene/butadiene/butylene/styrene block copolymer
  • SEBS (1) styrene/butadiene/styrene block copolymer
  • the resin composition of the present invention can be used as a resin composition for adhesive films. Further, the adhesive film and the bonding sheet for interlayer adhesion of the present invention can be used in the manufacture of interlayer smoke-saving films for printed wiring boards, electronic parts, and the like.
  • test piece 11 adhesive film 12 copper foil 13 LCP 20 holes

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PCT/JP2022/020427 2021-06-02 2022-05-16 樹脂組成物及びその製造方法、並びに接着フィルム及び層間接着用ボンディングシート WO2022255078A1 (ja)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016027131A (ja) * 2014-06-26 2016-02-18 住友電気工業株式会社 接着剤組成物、プリント配線板用カバーレイ、プリント配線板用ボンディングフィルム及びプリント配線板
JP2019006879A (ja) * 2017-06-22 2019-01-17 日立化成株式会社 樹脂組成物、プリプレグ、積層板、多層プリント配線板及び半導体パッケージ
WO2019151014A1 (ja) * 2018-02-05 2019-08-08 デクセリアルズ株式会社 接着剤組成物、熱硬化性接着シート及びプリント配線板
JP2020015859A (ja) * 2018-07-26 2020-01-30 味の素株式会社 樹脂組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016027131A (ja) * 2014-06-26 2016-02-18 住友電気工業株式会社 接着剤組成物、プリント配線板用カバーレイ、プリント配線板用ボンディングフィルム及びプリント配線板
JP2019006879A (ja) * 2017-06-22 2019-01-17 日立化成株式会社 樹脂組成物、プリプレグ、積層板、多層プリント配線板及び半導体パッケージ
WO2019151014A1 (ja) * 2018-02-05 2019-08-08 デクセリアルズ株式会社 接着剤組成物、熱硬化性接着シート及びプリント配線板
JP2020015859A (ja) * 2018-07-26 2020-01-30 味の素株式会社 樹脂組成物

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