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WO2025204278A1 - Composition adhésive, et feuille adhésive, stratifié et carte de circuit imprimé les comprenant - Google Patents

Composition adhésive, et feuille adhésive, stratifié et carte de circuit imprimé les comprenant

Info

Publication number
WO2025204278A1
WO2025204278A1 PCT/JP2025/005271 JP2025005271W WO2025204278A1 WO 2025204278 A1 WO2025204278 A1 WO 2025204278A1 JP 2025005271 W JP2025005271 W JP 2025005271W WO 2025204278 A1 WO2025204278 A1 WO 2025204278A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive composition
mass
heavy metal
parts
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/005271
Other languages
English (en)
Japanese (ja)
Inventor
晃一 坂本
忠彦 三上
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyobo MC Corp
Original Assignee
Toyobo MC Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyobo MC Corp filed Critical Toyobo MC Corp
Publication of WO2025204278A1 publication Critical patent/WO2025204278A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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

Definitions

  • the present invention relates to an adhesive composition. More specifically, it relates to an adhesive composition for printed wiring boards used for bonding to substrates.
  • low-dielectric resins such as fluororesins are increasingly being used instead of the conventional Flame Retardant Type 4 (FR-4), and in the case of flexible printed circuit boards (FPCs), films with low dielectric properties such as liquid crystal polymers (LCPs) and fluororesins are increasingly being used instead of the conventional polyimide films.
  • LCPs liquid crystal polymers
  • CCLs copper-clad laminates
  • Patent Document 1 adhesive compositions that combine polypropylene-based resins and epoxy resins
  • Patent Document 2 adhesive compositions containing styrene-based elastomers
  • Millimeter-wave radar one of the core sensors for autonomous driving, is known for its ability to measure the distance, speed, angle, etc. to distant objects. Because high-frequency signals are used around millimeter-wave radar antennas, adhesive compositions for printed wiring boards are strongly required to have low dielectric properties to reduce transmission loss. Furthermore, for applications requiring high reliability, such as automotive millimeter-wave radar antennas, adhesive compositions are required to maintain their adhesion and low dielectric properties without significant change even after being left in harsh environments such as high-temperature environments (125°C) or high-temperature, high-humidity environments (85°C, 85% RH) for 1,000 hours or more.
  • harsh environments such as high-temperature environments (125°C) or high-temperature, high-humidity environments (85°C, 85% RH) for 1,000 hours or more.
  • the present invention was made in response to these technical issues. Specifically, the object of the present invention is to provide an adhesive composition that exhibits good appearance, excellent adhesion, and excellent low dielectric properties, even after a long-term heat resistance test at 125°C for 1,000 hours, as well as an adhesive sheet, laminate, and printed wiring board that contain the same.
  • the present invention comprises the following features:
  • An adhesive composition comprising a polyimide resin, an antioxidant (A), a heavy metal deactivator (B), and an epoxy resin (C), wherein the content of the antioxidant (A) is 1.0 part by mass or less and the content of the heavy metal deactivator (B) is 1.0 part by mass or less relative to 100 parts by mass of the polyimide resin.
  • the heavy metal deactivator (B) includes at least one of a hydrazine-based heavy metal deactivator and a phosphite-based heavy metal deactivator.
  • the adhesive composition according to any one of [1] to [10] which is for use on a printed wiring board.
  • An adhesive sheet in which the adhesive composition according to any one of [1] to [10] is laminated on a release substrate.
  • a printed wiring board comprising the laminate according to [13] as a component.
  • the polyimide resin in the present invention is a polymer having an imide bond in the main chain, and can be produced by a method such as a method of producing it from a carboxylic acid anhydride component and an isocyanate component (isocyanate method), a method of synthesizing an amic acid by reacting a polycarboxylic acid component with an amine component and then ring-closing the amic acid (direct method), or a method of reacting a compound having a carboxylic acid anhydride and an acid chloride with a diamine.
  • the direct method is advantageous in terms of the wide range of monomer component options.
  • the polyimide resin of the present invention can also contain bond species formed by reactions other than imidization, such as amide bonds, ester bonds, and urethane bonds.
  • bond species formed by reactions other than imidization, such as amide bonds, ester bonds, and urethane bonds.
  • the inclusion of these bond species can impart flexibility to the resin, enabling the formation of a flexible cured coating film.
  • imide bonds due to the symmetry of their structure, partially cancel out polarity, making them advantageous for low dielectric properties. Therefore, it is preferable to keep the content of bond species such as amide bonds, ester bonds, and urethane bonds to the minimum necessary.
  • the amount of imide bonds is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more; even 100 mol% is acceptable.
  • trimellitic anhydride and trimellitic anhydride derivatives such as alkylene glycol bisanhydrotrimellitates, such as ethylene glycol bisanhydrotrimellitate, propylene glycol bisanhydrotrimellitate, and 1,4-butanediol bisanhydrotrimellitate, may also be used. These may be used alone or in combination of two or more.
  • aromatic ring-containing tetrabasic acid dianhydrides and alicyclic tetrabasic acid dianhydrides are preferred, with 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride and 2,2-bis[4-(2,3- or 3,4-dicarboxyphenoxy)phenyl]propane dianhydride (BPADA) being more preferred.
  • BPADA 2,2-bis[4-(2,3- or 3,4-dicarboxyphenoxy)phenyl]propane dianhydride
  • the isocyanate component constituting the polyimide resin in the present invention is not particularly limited, and examples of diisocyanates having an aromatic ring include tolylene diisocyanate (TDI), 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate and its structural isomers, 3,3'-diethyldiphenylmethane-4,4'-diisocyanate and its structural isomers, diphenylmethane-4,4'-diisocyanate, diphenylmethane-3,3'-diisocyanate, diphenylmethane-3,4'-diisocyanate, and diphenylmethane-2,4'-diisocyanate.
  • TDI tolylene diisocyanate
  • diisocyanates having an aromatic ring include tolylene diisocyanate (TDI), 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate and
  • diisocyanates examples include diphenylmethane-2,2'-diisocyanate, diphenylether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2,6-diisocyanate, 3,3'- or 2,2'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'- or 2,2'-diethylbiphenyl-4,4'-diisocyanate, and 3,3'-dimethoxybiphenyl-4,4'-diisocyanate.
  • diphenylmethane-4,4'-diisocyanate (MDI) and 3,3'-dimethylbiphenyl-4,4'-diisocyanate (ToDI) are preferred from the standpoint of polymerizability. These can be used alone or in combination of two or more types.
  • the amine components constituting the polyimide resin of the present invention are not particularly limited, and examples include dimer diamine, m-phenylenediamine, 2,5-diethyl-6-methyl-1,3-benzenediamine, p-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, and 2,3,5,6-tetramethyl-1,4-phenylenediamine.
  • dimer diamine is preferred from the standpoint of low dielectric properties.
  • the polyimide resin of the present invention may contain components other than the above-mentioned carboxylic acid anhydride component, isocyanate component, and amine component.
  • examples include aromatic dicarboxylic acid components, aliphatic dicarboxylic acid components, and diol components.
  • aromatic dicarboxylic acid components include, but are not limited to, terephthalic acid, isophthalic acid, orthophthalic acid, 4,4'-dicarboxybiphenyl, 5-sodium sulfoisophthalic acid, naphthalenedicarboxylic acid, and esters thereof.
  • aliphatic dicarboxylic acids include, but are not limited to, dimer acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and hydrogenated naphthalenedicarboxylic acid.
  • Dimer acid is preferred, as it exhibits excellent dielectric properties.
  • the diol component is not particularly limited, but examples include decanediol, dimer diol, polybutadiene with hydroxyl groups at both ends, hydrogenated polybutadiene with hydroxyl groups at both ends, polyisoprene with hydroxyl groups at both ends, and polyolefin with hydroxyl groups at both ends. Of these, polybutadiene with hydroxyl groups at both ends is preferred due to its excellent dielectric properties.
  • the number average molecular weight (Mn) of the polyimide resin in the present invention is preferably in the range of 10,000 to 50,000. It is more preferably in the range of 15,000 to 45,000, and even more preferably in the range of 20,000 to 40,000.
  • Mn number average molecular weight
  • the glass transition temperature of the polyimide resin in the present invention is preferably -20°C or higher. It is more preferably 0°C or higher, and even more preferably 20°C or higher. Having a glass transition temperature above the lower limit mentioned above can improve solder heat resistance. There is no particular upper limit to the glass transition temperature, but in practice it is 300°C or lower, and it can even be 200°C or lower.
  • the polyimide resin in the present invention preferably has a relative dielectric constant ( ⁇ c) of 3.0 or less at a frequency of 40 GHz. It is more preferably 2.8 or less, and even more preferably 2.6 or less. There is no particular lower limit, but for practical purposes it is 2.0. Furthermore, the relative dielectric constant ( ⁇ c) over the entire frequency range from 1 GHz to 60 GHz is preferably 3.0 or less, more preferably 2.8 or less, and even more preferably 2.6 or less.
  • the polyimide resin in the present invention preferably has a dielectric loss tangent (tan ⁇ ) of 0.005 or less at a frequency of 40 GHz. It is more preferably 0.004 or less, and even more preferably 0.003 or less. There is no particular lower limit, but for practical purposes it is 0.0001 or more. Furthermore, the dielectric loss tangent (tan ⁇ ) over the entire frequency range from 1 GHz to 60 GHz is preferably 0.005 or less, more preferably 0.004 or less, and even more preferably 0.003 or less.
  • Polyimide resins can be obtained, for example, by dissolving a carboxylic acid anhydride component and an isocyanate or amine component in a solvent and heating the mixture.
  • the molar ratio of the acid anhydride groups of the carboxylic acid anhydride component to the isocyanate groups of the isocyanate component or the amino groups of the amine component is preferably 100:91 to 100:109. Outside this range, the molecular weight may not increase sufficiently, resulting in insufficient mechanical strength and possible gelation during polymerization.
  • the imide ring moieties of the polyimide resin are 90% or more closed. To achieve this, sufficient reaction is required during polyimide polymerization, and methods such as increasing the reaction temperature or adding a catalyst are available.
  • Solvents that can be used in the polymerization of the polyimide resin of the present invention include, for example, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, dimethylimidazolidinone, dimethyl sulfoxide, dimethylformamide, N-ethyl-2-pyrrolidone, dimethylacetamide, cyclohexanone, cyclopentanone, tetrahydrofuran, and methylcyclohexane. Of these, cyclohexanone is preferred from the standpoint of polymerizability. Furthermore, after polymerization, the nonvolatile content and solution viscosity can be adjusted by diluting with the solvent used in the polymerization or another low-boiling point solvent.
  • catalysts such as alkali metals such as sodium fluoride, potassium fluoride, and sodium methoxide, amines such as triethylenediamine, triethylamine, diethanolamine, 1,8-diazabicyclo[5,4,0]-7-undecene, and 1,5-diazabicyclo[4,3,0]-5-nonene, and dibutyltin dilaurate can be used to promote the reaction.
  • the adhesive composition of the present invention contains an antioxidant (A).
  • an antioxidant A
  • thermal degradation of the polyimide resin can be suppressed even in a high-temperature environment in the presence of oxygen, and changes in adhesion and low dielectric properties can be suppressed after a long-term heat resistance test.
  • the antioxidant (A) is not particularly limited as long as it can suppress thermal degradation of the polyimide resin, and examples include phenol-based antioxidants, sulfur-based antioxidants, amine-based antioxidants, and phosphorus-based antioxidants. These can be used alone or in combination of two or more types.
  • Sulfur-based antioxidants include pentaerythritol tetrakis-(3-laurylthiopropionate), dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, and bis(2-hydroxy-1-naphthyl) sulfide.
  • Phosphorus-based antioxidants include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, triphenyl phosphite, 2-ethylhexyl acid phosphate, dilauryl phosphite, tri-iso-octyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, trilauryl phosphite, trilauryl-di-thiophosphite, trilauryl-tri-thiophosphite, trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, tris(mononylphenyl) phosphite, tris(dinonylphenyl) phosphite, trioctadecyl phosphite, 1,1,3-tris(2-methyl-d
  • the antioxidant (A) preferably contains at least one of a phenol-based antioxidant and a sulfur-based antioxidant, and more preferably contains both a phenol-based antioxidant and a sulfur-based antioxidant.
  • the antioxidant (A) (preferably a phenolic antioxidant) is preferably one having a chemical structure represented by formula (I) in the molecule.
  • formula (I) * represents a bond
  • R 1 to R 3 each independently represent a hydrogen atom or a C 1-10 alkyl group.
  • the adhesive composition of the present invention contains a heavy metal deactivator (B).
  • a heavy metal deactivator (B) In a high-temperature environment in the presence of oxygen, heavy metal ions such as copper ions are generated from metal substrates such as copper foil with which the adhesive composition comes into contact, regardless of humidity conditions. The generated heavy metal ions accelerate the oxidation of the polyimide resin, resulting in thermal degradation. Since the heavy metal deactivator (B) can trap the generated copper ions, the addition of the heavy metal deactivator (B) can suppress thermal degradation of the polyimide resin.
  • the heavy metal deactivator (B) is not particularly limited as long as it can trap heavy metal ions, and may be, for example, one that can form a chelate with heavy metal ions.
  • Examples of heavy metal deactivators (B) include hydrazine-based heavy metal deactivators, phosphite-based heavy metal deactivators, dibasic acid-based heavy metal deactivators, amino acid-based heavy metal deactivators, and triazole-based heavy metal deactivators. These can be used alone or in combination of two or more types.
  • Hydrazine-based heavy metal deactivators are heavy metal deactivators that have a hydrazine structure (*-NH-NH-*) in the molecule.
  • Hydrazine-based heavy metal deactivators include hydrazine derivatives and those obtained by dehydration condensation of hydrazine derivatives with oxoacids, specifically N,N'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine, bis(2-phenoxypropionylhydrazine) isophthalate, bis(salicyloylhydrazine), and decamethylenedicarboxylic acid.
  • dibasic acid heavy metal deactivators examples include ethylenediaminetetraacetic acid.
  • Amino acid-based heavy metal deactivators include 2-hydroxy-N-1H-1,2,4-triazol-3-ylbenzoamide, N,N-diethyl-N',N'-diphenyloxamide, N,N'-diethyl-N,N'-diphenyloxamide, N,N'-bis[2-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl]oxamide, 2,4,6-triamino-1,3,5-triazine, and 3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)ethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.
  • Triazole-based heavy metal deactivators include benzotriazole and 3-salicyloylamino-1,2,4-triazole.
  • the heavy metal deactivator (B) contains at least one of a hydrazine-based heavy metal deactivator and a phosphite-based heavy metal deactivator, with a hydrazine-based heavy metal deactivator being even more preferable.
  • the heavy metal deactivator (B) (preferably a hydrazine-based heavy metal deactivator) is also preferably one having a chemical structure represented by formula (II) in the molecule.
  • formula (II) * represents a bond, and R 4 to R 6 each independently represent a hydrogen atom or a C 1-10 alkyl group.
  • the C1-10 alkyl group ( -CnH2n +1 , where n is an integer from 1 to 10) in R4 to R6 may be linear or branched, and is preferably a C1-6 alkyl group, more preferably a C1-4 alkyl group, and even more preferably a methyl group, an ethyl group, or a tert-butyl group. From the viewpoint of suppressing deterioration of the polyimide resin, it is more desirable that, of R4 to R6 , R4 is a hydrogen atom, and one of R5 to R6 is a C1-10 alkyl group and the other is a hydrogen atom.
  • the content of heavy metal deactivator (B) is 1.0 part by mass or less, more preferably 0.9 part by mass or less, even more preferably 0.8 part by mass or less, and even more preferably 0.7 part by mass or less, per 100 parts by mass of polyimide resin. If the content exceeds the upper limit, there is a risk of deterioration in dielectric properties after long-term heat resistance testing.
  • the content of heavy metal deactivator (B) is preferably 0.01 part by mass or more, more preferably 0.04 part by mass or more, and even more preferably 0.08 part by mass or more, per 100 parts by mass of polyimide resin.
  • the content of heavy metal deactivator (B) is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass, even more preferably 10 to 70 parts by mass, and even more preferably 13 to 50 parts by mass per 100 parts by mass of antioxidant (A).
  • the adhesive composition can exhibit excellent low dielectric properties even after long-term heat resistance testing.
  • the adhesive composition of the present invention contains an epoxy resin.
  • the epoxy resin is not particularly limited as long as it is a multifunctional epoxy resin having two or more glycidyl groups in the molecule.
  • the carboxyl group and the glycidyl group of the polyimide resin react to form a crosslinked structure, thereby improving the solder heat resistance and adhesiveness of the adhesive composition.
  • the epoxy value of the epoxy resin (C) is preferably 5,000 to 12,000 equivalents/ 10 g, more preferably 6,000 to 11,000 equivalents/ 10 g, and even more preferably 7,000 to 10,000 equivalents/ 10 g.
  • the epoxy value is above the lower limit, the adhesive strength can be improved and the crosslinking density can be increased, thereby improving heat resistance.
  • the epoxy value is below the upper limit, the adhesiveness and low dielectric properties can be improved.
  • the epoxy value can be evaluated in accordance with the provisions of JIS K7236 (the same applies hereinafter).
  • the epoxy resin (C) is not particularly limited, but examples include biphenyl-type epoxy resins, naphthalene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, novolac-type epoxy resins, alicyclic epoxy resins, dicyclopentadiene-type epoxy resins, glycidylamine-type epoxy resins, glycidyl ether-type epoxy resins, epoxy-modified polybutadiene, and glycidyl group-containing isocyanuric acid. These can be used alone or in combination of two or more.
  • glycidylamine-type epoxy resins glycidyl group-containing isocyanuric acid, and alicyclic epoxy resins are preferred from the standpoints of solder heat resistance and low dielectric properties, with glycidylamine-type epoxy resins and alicyclic epoxy resins being more preferred.
  • a glycidylamine-type epoxy resin refers to an epoxy resin containing, within the molecule, a glycidylamino group in which one or two glycidyl groups are bonded to an amino group. It is more preferable for the glycidylamine-type epoxy resin to include at least one of an epoxy resin represented by formula (CA) (hereinafter sometimes simply referred to as epoxy resin (CA)) and an epoxy resin represented by formula (CB) (hereinafter sometimes simply referred to as epoxy resin (CB)). Because epoxy resins (CA) to (CB) contain two or more epoxy groups, they are advantageous for forming a high-density crosslinked structure.
  • CA epoxy resin
  • CB epoxy resin
  • epoxy resins (CA) to (CB) have significant steric hindrance and a structure with poor mobility. Such a structure with significant steric hindrance suppresses atomic movement, making it ideal for obtaining an adhesive composition with a low dielectric dissipation factor.
  • R 11 to R 15 each independently represent a hydrogen atom, a C 1-10 alkyl group, or a glycidyloxy group.
  • R 16 to R 23 each independently represent a hydrogen atom, a C 1-10 alkyl group or a glycidyloxy group.
  • R 24 and R 25 each independently represent a hydrogen atom or a C 1-10 alkyl group.
  • R 11 and R 15 is a C 1-10 alkyl group. If at least one of R 11 and R 15 is a C 1-10 alkyl group, this acts as a steric hindrance and inhibits the movement of the polar group, which is effective in obtaining an adhesive composition with a low dielectric tangent. Furthermore, when at least one of R 11 and R 15 among R 11 to R 15 is a C 1-10 alkyl group, it is preferable that the group other than the C 1-10 alkyl group is a hydrogen atom.
  • R 16 to R 23 preferably 3 or more, more preferably 5 or more, even more preferably 7 or more, and most preferably all 8 are hydrogen atoms.
  • R 24 and R 25 at least one is preferably a hydrogen atom, and more preferably all two are hydrogen atoms.
  • Glycidylamine type epoxy resins include N,N-diglycidylaniline, N,N-(diglycidyl)-O-toluidine, N,N-(diglycidyl)-m-toluidine, N,N-(diglycidyl)-p-toluidine, N,N-diglycidyl-4-glycidyloxyaniline, N,N-(diglycidyl)-4-glycidyloxy-O-toluidine, and N,N-(diglycidyl)-4-glycidyl Oxy-m-toluidine, N,N-(diglycidyl)-4-glycidyloxy-p-toluidine, and 4,4'-methylenebis(N,N-diglycidylaniline) are preferred, and N,N-(diglycidyl)-O-toluidine, N,N-(diglycidyl)-m-toluidine, N,N-(diglycid
  • alicyclic epoxy resins are epoxy resins that have reactive epoxy groups on an alicyclic skeleton.
  • examples of alicyclic epoxy resins include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate.
  • the adhesive composition of the present invention may contain a polycarbodiimide.
  • the polycarbodiimide is not particularly limited as long as it has two or more carbodiimide bonds in the molecule.
  • the carboxy group of the polyimide resin or the epoxy group of the epoxy resin reacts with the carbodiimide bond, thereby improving heat resistance and adhesiveness.
  • the polycarbodiimide content is preferably 1 part by mass or more, more preferably 3 parts by mass or more, per 100 parts by mass of polyimide resin.
  • the content is preferably 20 parts by mass or less, more preferably 10 parts by mass or less.
  • excellent solder heat resistance and low dielectric properties can be achieved. In other words, by keeping the content within the above range, an adhesive composition with excellent solder heat resistance and low dielectric properties can be obtained.
  • the adhesive composition of the present invention may contain an unsaturated hydrocarbon having a terminal unsaturated hydrocarbon group and a 5% weight loss temperature of 260°C or higher.
  • the unsaturated hydrocarbon contains a terminal unsaturated hydrocarbon group
  • the crosslink density can be increased by a curing reaction caused by radicals generated by using a radical generator or the like, thereby improving solder heat resistance.
  • hydroxyl groups that deteriorate dielectric properties are not generated after the reaction, an adhesive with better dielectric properties can be obtained. It is preferable to have two or more terminal unsaturated hydrocarbon groups per molecule, as this further increases the crosslink density.
  • the 5% weight loss temperature of the unsaturated hydrocarbon must be 260°C or higher. Preferably, it is 270°C or higher, more preferably 280°C or higher, and even more preferably 290°C or higher. Having a 5% weight loss temperature above this value makes it possible to perform soldering at temperatures above the melting point of the solder without causing poor appearance. There is no particular upper limit, but 500°C is practical.
  • the unsaturated hydrocarbon preferably has an aromatic ring structure or an alicyclic structure as a structural unit. Having an aromatic ring structure or an alicyclic structure as a structural unit can improve solder heat resistance and also provides excellent dielectric properties. Among these, an aromatic ring structure or an alicyclic structure is preferred as the backbone of the unsaturated hydrocarbon, and polyphenylene ether or a cycloolefin polymer is preferred. Specific examples of polyphenylene ethers with terminal unsaturated hydrocarbon groups include SA-9000 from SABIC and OPE-2St from Mitsubishi Gas Chemical Company. Cycloolefin polymers with terminal unsaturated hydrocarbon groups can be obtained by copolymerizing an olefin monomer with an unsaturated bond with an alicyclic olefin monomer.
  • the number average molecular weight of the unsaturated hydrocarbon is preferably 500 or more, more preferably 1,000 or more. It is also preferably 100,000 or less, more preferably 10,000 or less, and even more preferably 5,000 or less. Within this range, the solubility in solvents is good, and a uniform adhesive coating can be formed.
  • the content of unsaturated hydrocarbon in the adhesive composition of the present invention is preferably 1 part by mass or more, more preferably 2 parts by mass or more, per 100 parts by mass of polyimide resin. It is also preferably 1,000 parts by mass or less, more preferably 500 parts by mass or less, even more preferably 200 parts by mass or less, and even more preferably 100 parts by mass or less.
  • polyphenylene ether having a terminal unsaturated hydrocarbon group as the unsaturated hydrocarbon, it is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, per 100 parts by mass of polyimide resin.
  • the adhesive composition of the present invention can contain a radical generator.
  • the radicals generated by the radical generator efficiently react the terminal unsaturated hydrocarbon groups of the unsaturated hydrocarbon, increasing the crosslink density and thereby improving solder heat resistance and dielectric properties.
  • the radical generator is not particularly limited, but an organic peroxide is preferably used.
  • organic peroxides include, but are not limited to, peroxides such as di-tert-butyl peroxyphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butylperoxy-2-ethylhexanoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, di-tert-butyl peroxide, and lauroyl peroxide; and azonitriles such as azobisisobutyronitrile and azobisisopropionitrile.
  • peroxides such as di-tert-butyl peroxyphthalate, tert-butyl hydroperoxide, dicumyl peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, tert-butylperoxy-2-ethylhexanoate
  • the one-minute half-life temperature of the radical generator used in the present invention is preferably 140°C or higher.
  • the temperature is preferably 140°C or higher.
  • organic solvents include aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane, and ethylcyclohexane; halogenated hydrocarbons such as trichloroethylene, dichloroethylene, chlorobenzene, and chloroform; alcohol-based solvents such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol; acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, and acetophenone.
  • aromatic hydrocarbons such as
  • solvents examples include ketone solvents such as hexane, cellosolves such as methyl cellosolve and ethyl cellosolve, ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, and butyl formate, and glycol ether solvents such as ethylene glycol mono-n-butyl ether, ethylene glycol mono-iso-butyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-iso-butyl ether, triethylene glycol mono-n-butyl ether, and tetraethylene glycol mono-n-butyl ether. These can be used alone or in combination of two or more. Methyl ethyl ketone, methylcyclohexane, or toluene is particularly preferred from the standpoint of work environment and drying properties.
  • the organic solvent is preferably in the range of 100 to 1,000 parts by mass per 100 parts by mass of the solids content of the adhesive composition.
  • the adhesive composition of the present invention may further contain other components as needed.
  • specific examples of such components include flame retardants, tackifiers, fillers, antioxidants, silane coupling agents, etc.
  • the adhesive composition of the present invention may optionally contain a flame retardant.
  • flame retardants include bromine-based, phosphorus-based, nitrogen-based, and metal hydroxide compounds. Phosphorus-based flame retardants are preferred, and phosphorus-based flame retardants such as phosphate esters, phosphate salts, and phosphine oxides can be used alone or in combination of two or more.
  • the content is preferably in the range of 1 to 70% by mass, more preferably 5 to 60% by mass, and most preferably 10 to 50% by mass, based on 100% by mass of the solids content of the adhesive composition. By keeping the content within this range, flame retardancy can be achieved while maintaining adhesion, solder heat resistance, and electrical properties.
  • the adhesive composition of the present invention may optionally contain a tackifier.
  • tackifiers include polyterpene resins, rosin-based resins, aliphatic petroleum resins, alicyclic petroleum resins, copolymerized petroleum resins, styrene resins, and hydrogenated petroleum resins, and are used to improve adhesive strength. These can be used alone or in combination of two or more.
  • a tackifier is added, it is preferably contained in an amount of 1 to 70% by mass, more preferably 5 to 60% by mass, and most preferably 10 to 50% by mass, based on 100% by mass of the solids content of the adhesive composition. By maintaining the amount within this range, the effects of the tackifier can be exerted while maintaining adhesion, solder heat resistance, and electrical properties.
  • the adhesive composition of the present invention may contain a filler as needed.
  • organic fillers include powders of heat-resistant resins such as polyimide, polyamideimide, fluororesin, and liquid crystal polyester.
  • inorganic fillers include silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), tantalum oxide (Ta 2 O 5 ), zirconia (ZrO 2 ), silicon nitride (Si 3 N 4 ), boron nitride (BN), calcium carbonate (CaCO 3 ), calcium sulfate (CaSO 4 ), zinc oxide (ZnO), magnesium titanate (MgO.TiO 2 ), barium sulfate (BaSO 4 ), organic bentonite, clay, mica, aluminum hydroxide, and magnesium hydroxide.
  • silica is preferred due to its ease of dispersion and its heat resistance.
  • Hydrophobic silica and hydrophilic silica are commonly known as silica, but in this case, hydrophobic silica treated with dimethyldichlorosilane, hexamethyldisilazane, octylsilane, etc. is preferred in order to impart moisture absorption resistance.
  • the amount added is preferably 1 to 50 mass% of 100 mass% of the solids content of the adhesive composition, and more preferably 30 to 50 mass%.
  • silica at or above the lower limit even greater heat resistance can be achieved.
  • silica at or below the upper limit poor dispersion of the silica and excessively high solution viscosity can be prevented, improving workability.
  • the magnesium hydroxide content is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 3 parts by mass or less, even more preferably 0.5 parts by mass or less, and most preferably 0 parts by mass, per 100 parts by mass of polyimide resin.
  • a silane coupling agent may be blended into the adhesive composition of the present invention as needed.
  • the inclusion of a silane coupling agent is highly preferred because it improves adhesion to metals and heat resistance.
  • Silane coupling agents are not particularly limited, but examples include those containing unsaturated groups, epoxy groups, and amino groups.
  • silane coupling agents containing epoxy groups such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and ⁇ -(3,4-epoxycyclohexyl)ethyltriethoxysilane, are more preferred from the perspective of heat resistance.
  • the adhesive composition of the present invention exhibits excellent low dielectric properties even after a long-term heat resistance test at 125°C for 1000 hours.
  • the adhesive composition of the present invention is heat-cured at 180°C for 3 hours, and then exposed to an air atmosphere at 125°C for 1000 hours.
  • the dielectric loss tangent (tan ⁇ ) measured at a temperature of 23°C and a frequency of 40 GHz is preferably less than 0.005, more preferably 0.004 or less, and even more preferably 0.003 or less.
  • the measurement method please refer to the "(Relative Dielectric Constant ( ⁇ r ) and Dielectric Loss Tangent (tan ⁇ ))" section in the Examples section. Because a polyimide resin is used in the present invention, it is more likely to exhibit low dielectric properties after a long-term heat resistance test than adhesive compositions based on epoxy resins.
  • the adhesive composition of the present invention exhibits excellent adhesion even after a long-term heat resistance test at 125°C for 1000 hours.
  • the peel strength measured after heating and curing the adhesive composition of the present invention at 180°C for 90 minutes and exposing the cured product to an air atmosphere at 125°C for 1000 hours is preferably 0.5 N/mm or more, more preferably 1.0 N/mm or more, and even more preferably 1.2 N/mm or more, with an upper limit of 5 N/mm, although not particularly limited.
  • the measurement method please refer to "(High-Temperature and High-Humidity Resistance)" in the Examples section, as appropriate.
  • the term "laminated body” refers to a body in which the adhesive composition of the present invention is laminated on a substrate, specifically a body in which the adhesive composition is laminated on a substrate (a two-layer laminate of substrate/adhesive layer), or a three-layer laminate of substrate/adhesive layer/substrate).
  • the term "adhesive layer” refers to a layer of the adhesive composition of the present invention after the adhesive composition of the present invention is applied to a substrate and dried.
  • the laminate of the present invention can be obtained by applying the adhesive composition of the present invention to various substrates and drying them according to a conventional method, and then laminating another substrate on top of it.
  • the laminate of the present invention includes a laminate in which the adhesive composition of the present invention is laminated onto a substrate such as a resin substrate, metal substrate, paper, or inorganic non-metallic substrate, as described below, and a laminate (adhesive sheet) in which the adhesive composition of the present invention is laminated onto a release substrate.
  • a substrate such as a resin substrate, metal substrate, paper, or inorganic non-metallic substrate, as described below
  • a laminate adhesive sheet
  • Examples of laminates of the present invention include copper-clad laminates (CCL), resin-coated metal foils, coverlay films, and bonding sheets.
  • the substrate in the present invention is not particularly limited as long as it is possible to apply the adhesive composition of the present invention to the substrate and dry it to form an adhesive layer.
  • the substrate include resin substrates such as film-like resins, metal substrates such as metal plates and metal foils, paper, inorganic non-metallic substrates, and release substrates.
  • resin substrate materials include epoxy resin, polyester resin, polyamide resin, aramid resin, polyimide resin, polyamideimide resin, liquid crystal polymer, polyphenylene sulfide, polyphenylene ether, polyethersulfone, polyetheretherketone, polycarbonate, polyarylate, syndiotactic polystyrene, polyolefin resin, and fluorine-based resin.
  • the form of the resin substrate is not particularly limited, but examples include films made of the above resins and glass cloth (FR-4) impregnated with the above resins.
  • the above resins may contain fillers such as silica.
  • the metal substrate can be any conventionally known conductive material that can be used for circuit boards. Examples of materials include various metals such as stainless steel, copper, aluminum, iron, steel, zinc, and nickel, as well as their alloys, plated products, and metals treated with other metals such as zinc or chromium compounds.
  • Metal foil is preferred, and copper foil is more preferred. There are no particular limitations on the thickness of the metal foil, but it is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and even more preferably 10 ⁇ m or more. It is also preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and even more preferably 20 ⁇ m or less. If the thickness is too thin, it may be difficult to obtain sufficient electrical performance of the circuit.
  • Metal foil is usually provided in roll form.
  • the form of the metal foil used in manufacturing the printed wiring board of the present invention is not particularly limited.
  • its length is not particularly limited.
  • Its width is also not particularly limited, but is preferably approximately 250 to 500 cm.
  • Examples of paper include fine paper, kraft paper, roll paper, glassine paper, etc.
  • inorganic non-metallic substrates examples include glass and ceramic.
  • the release substrate is not particularly limited, but examples include fine paper, kraft paper, roll paper, glassine paper, etc., with a coating layer of a filler such as clay, polyethylene, or polypropylene applied to both sides, and then a silicone-based, fluorine-based, or alkyd-based release agent applied to each of these coating layers.
  • a coating layer of a filler such as clay, polyethylene, or polypropylene applied to both sides, and then a silicone-based, fluorine-based, or alkyd-based release agent applied to each of these coating layers.
  • Other examples include various olefin films such as polyethylene, polypropylene, ethylene- ⁇ -olefin copolymer, and propylene- ⁇ -olefin copolymer, as well as films such as polyethylene terephthalate coated with the release agent.
  • the method for coating the adhesive composition onto a substrate is not particularly limited, but examples include a comma coater, reverse roll coater, and die coater.
  • an adhesive layer can be applied directly or by transfer to the rolled copper foil or resin substrate that constitutes the printed wiring board.
  • the thickness of the adhesive layer after drying can be adjusted as needed, but is preferably in the range of 5 to 200 ⁇ m.
  • An adhesive film thickness of 5 ⁇ m or more provides sufficient adhesive strength.
  • a thickness of 200 ⁇ m or less makes it easier to control the amount of residual solvent during the drying process, reducing the risk of blisters during pressing in the production of printed wiring boards.
  • the drying conditions are not particularly limited, but a residual solvent ratio of 1% by mass or less after drying is preferred. A ratio of 1% by mass or less prevents residual solvent from foaming during printing wiring board pressing, reducing the risk of blisters.
  • a copper-clad laminate is a laminate in which the metal foil is laminated on one or both sides of the resin substrate.
  • the resin substrate and the metal foil may be laminated via the adhesive composition of the present invention, or the resin substrate and the metal foil may be laminated by thermocompression bonding without the adhesive composition of the present invention.
  • Specific configurations of copper-clad laminates (CCLs) include a metal foil layer/adhesive layer/resin substrate layer/adhesive layer/metal foil layer.
  • the metal foil layer can be etched to form a circuit pattern, allowing it to be used as a laminate material for printed wiring boards.
  • a coverlay film is a laminate of the resin substrate and the release substrate via the adhesive composition of the present invention.
  • the resin substrate in the coverlay film can be any insulating film conventionally known as an insulating film for printed wiring boards.
  • Resins constituting the resin substrate are preferably polyester resins, aramid resins, polyimide resins, polyamideimide resins, liquid crystal polymers, polyphenylene sulfide, polyethersulfone, polyetheretherketone, polycarbonate, polyarylate, syndiotactic polystyrene, polyolefin resins, etc., and more preferably films composed of polyimide resins, liquid crystal polymers, fluorine-based resins, etc.
  • the coverlay film can be produced by applying the adhesive composition of the present invention to the resin substrate, drying it, and then laminating the release substrate thereon.
  • the bonding sheet refers to the adhesive composition of the present invention laminated on the release substrate.
  • Specific configurations include release substrate/adhesive layer/release substrate, or release substrate/adhesive layer/substrate (excluding the release substrate)/adhesive layer/release substrate.
  • Laminating the release substrate functions as a protective layer for the substrate.
  • the release substrate can be peeled from the bonding sheet and used to bond other substrates. From the viewpoint of visibility during the production of printed wiring boards, it is preferable that the release substrate on at least one side of the release substrate laminated on the outermost side of the bonding sheet be opaque.
  • the adhesive composition of the present invention is preferably used for printed wiring boards.
  • the printed wiring board of the present invention comprises, as a component, a laminate having the metal substrate (metal foil) and the resin base material that form a conductor circuit.
  • the printed wiring board of the present invention collectively refers to so-called rigid substrates, flexible printed wiring boards (FPCs), flat cables, circuit boards for tape automated bonding (TAB), etc.
  • the printed wiring board of the present invention can have any laminate structure that can be used as a printed wiring board.
  • the printed wiring board of the present invention preferably comprises, as a component, a laminate in which the adhesive composition of the present invention is laminated to a substrate that is a resin substrate, a metal substrate, paper, or an inorganic non-metallic substrate. If necessary, two or more of the above printed wiring boards can be laminated together. If necessary, two or more layers other than the protective layer of the printed wiring board can be laminated with bonding sheets, and a protective layer such as a coverlay film or solder resist can be provided on top of these.
  • a printed wiring board can be made to have a four-layer structure such as a resin substrate layer/adhesive layer/metal foil layer/coverlay film layer, or a resin substrate layer/metal foil layer/adhesive layer/coverlay film layer.
  • a printed wiring board can be made to have a five-layer structure such as a resin substrate layer/adhesive layer/metal foil layer/adhesive layer/coverlay film layer.
  • the printed wiring board of the present invention can be manufactured using any conventionally known process, except for using the materials for each layer described above.
  • a circuit pattern is formed on a three-layer CCL using adhesive or a two-layer CCL without adhesive, and then laminated by bonding to another CCL with a bonding sheet or prepreg and thermally curing.
  • a protective layer such as a coverlay film or solder resist is formed on the outermost layer, and further surface treatment is performed to obtain a multilayer printed wiring board.
  • the adhesive composition of the present invention can be suitably used in the manufacture of printed wiring boards, and specifically, can be suitably used for each adhesive layer of printed wiring boards.
  • the adhesive composition of the present invention when used as an adhesive, it can bond not only conventional substrates constituting printed wiring boards, such as polyimide film, polyester film, and FR-4, but also low-adhesion substrates such as liquid crystal polymers and fluororesin-impregnated glass cloth to low-roughness copper foil.
  • low-polarity resin substrates such as liquid crystal polymers, polyphenylene sulfide, syndiotactic polystyrene, and polyolefin resins, it can achieve solder reflow resistance.
  • the adhesive layer itself also has excellent low dielectric properties, allowing for printed wiring boards with excellent high-frequency characteristics.
  • the adhesive composition was applied to a 100 ⁇ m thick surface-treated PTFE film (Yodogawa Hutech Co., Ltd., Yodoflon®) to a dry thickness of 25 ⁇ m, and then dried at 100°C for 2 minutes.
  • the adhesive film (B-stage product) thus obtained was then bonded to an 18 ⁇ m thick electrolytic copper foil (Fukuda Metal Foil Powder Co., Ltd., T9DA-SV-18).
  • the bonding was performed by heating the foil from 35°C to 180°C at a rate of 4°C per minute under a pressure of 2 MPa, with the matte side of the foil in contact with the adhesive layer.
  • ADEKA STAB Hydrazine-based heavy metal deactivator
  • CDA-10 Hydrazine-based heavy metal deactivator
  • HOSTANOX registered trademark OSP1
  • Clariant a reaction product of 2,2'-di-tert-butyl-5,5'-dimethyl-4,4'-sulfanediyldiphenol and phosphorus trichloride
  • Example 1 100 parts of polyimide resin, 2.4 parts of epoxy resin, 0.09 parts of antioxidant a1, 0.21 parts of antioxidant a2, and 0.10 parts of heavy metal deactivator b1 were blended and dissolved in toluene to a solids concentration of 40%, to obtain adhesive composition (S1). The obtained adhesive composition (S1) was subjected to various adhesive composition evaluations. The results are shown in Table 1.
  • Adhesive compositions (S2) to (S9) were prepared and evaluated in the same manner as in Example 1, except that the types and amounts of each component of the adhesive composition were changed as shown in Tables 1 and 2. The results are shown in Tables 1 and 2.
  • adhesive compositions containing predetermined amounts of antioxidant (A) and heavy metal deactivator (B) exhibited good appearance and excellent adhesion even after a long-term heat resistance test at 125°C for 1,000 hours. They also exhibited excellent low dielectric properties even after the long-term heat resistance test. Furthermore, as shown by Examples 1 to 4, adhesive compositions containing predetermined amounts of antioxidant (A) and heavy metal deactivator (B) also exhibit excellent solder heat resistance, adhesion, and initial low dielectric properties.
  • Examples 1 to 4 by changing the content ratio and type of heavy metal deactivator (B), it is possible to vary the appearance, adhesion, and dielectric properties after long-term heat resistance testing. Furthermore, a comparison of Examples 2 and 4 shows that using a hydrazine-based heavy metal deactivator as the heavy metal deactivator (B) is effective in obtaining an adhesive composition that has excellent appearance, adhesion, and dielectric properties after long-term heat resistance testing.
  • the adhesive composition of Comparative Example 1 did not contain the heavy metal deactivator (B), and therefore the appearance and adhesion after the long-term heat resistance test were deteriorated.
  • the adhesive composition of Comparative Example 2 did not contain the antioxidant (A), and therefore the appearance, adhesion, and dielectric properties after the long-term heat resistance test were deteriorated.
  • the adhesive compositions of Comparative Examples 3 and 4 contained large amounts of antioxidant (A) or heavy metal deactivator (B), and therefore exhibited poor dielectric properties after long-term heat resistance tests. Furthermore, the adhesive compositions of Comparative Examples 3 and 4 did not achieve sufficient effects in terms of solder heat resistance and initial dielectric properties.
  • the adhesive composition of the present invention retains a good appearance and exhibits excellent adhesion and low dielectric properties, even after a long-term heat resistance test at 125°C for 1,000 hours.
  • the adhesive composition of the present invention also exhibits excellent solder heat resistance, adhesion, and initial low dielectric properties. Therefore, the adhesive composition of the present invention is useful as an adhesive composition for printed wiring boards in the high-frequency range, as well as adhesive sheets, laminates, and printed wiring boards containing the same.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Le but de la présente invention est de fournir : une composition adhésive qui a un bon aspect et qui présente une excellente adhésivité et d'excellentes caractéristiques à faible constante diélectrique même après un test de résistance à la chaleur à long terme à 125 °C pendant 1 000 h ; et une feuille adhésive, un stratifié et une carte de circuit imprimé les comprenant.　Cette composition adhésive est caractérisée en ce qu'elle contient une résine de polyimide, un antioxydant (A), un désactivateur de métal lourd (B), et une résine époxy (C), la teneur en antioxydant (A) étant de 1,0 partie en masse ou moins et la teneur en désactivateur de métal lourd (B) étant de 1,0 partie en masse ou moins par rapport à 100 parties en masse de la résine de polyimide.
PCT/JP2025/005271 2024-03-27 2025-02-18 Composition adhésive, et feuille adhésive, stratifié et carte de circuit imprimé les comprenant Pending WO2025204278A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009090922A1 (fr) * 2008-01-16 2009-07-23 Hitachi Chemical Company, Ltd. Composition adhésive photosensible, adhésif en film, feuille adhésive, motif adhésif, plaquette de semi-conducteur à couche adhésive, dispositif à semi-conducteur et procédé de fabrication du dispositif à semi-conducteur
WO2021251437A1 (fr) * 2020-06-12 2021-12-16 日東電工株式会社 Composition d'adhésif, couche d'adhésif, feuille adhésive, élément optique, et panneau tactile
WO2021251435A1 (fr) * 2020-06-12 2021-12-16 日東電工株式会社 Feuille adhésive, élément optique, et panneau tactile
JP2022521427A (ja) * 2019-02-25 2022-04-07 エスエイチピーピー グローバル テクノロジーズ べスローテン フェンノートシャップ 官能化ポリエーテルイミド由来の架橋性ネットワークおよびそれから得られる熱硬化性ポリマー

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009090922A1 (fr) * 2008-01-16 2009-07-23 Hitachi Chemical Company, Ltd. Composition adhésive photosensible, adhésif en film, feuille adhésive, motif adhésif, plaquette de semi-conducteur à couche adhésive, dispositif à semi-conducteur et procédé de fabrication du dispositif à semi-conducteur
JP2022521427A (ja) * 2019-02-25 2022-04-07 エスエイチピーピー グローバル テクノロジーズ べスローテン フェンノートシャップ 官能化ポリエーテルイミド由来の架橋性ネットワークおよびそれから得られる熱硬化性ポリマー
WO2021251437A1 (fr) * 2020-06-12 2021-12-16 日東電工株式会社 Composition d'adhésif, couche d'adhésif, feuille adhésive, élément optique, et panneau tactile
WO2021251435A1 (fr) * 2020-06-12 2021-12-16 日東電工株式会社 Feuille adhésive, élément optique, et panneau tactile

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