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WO2025204276A1 - Composition adhésive, feuille adhésive, stratifié et carte de circuit imprimé les comprenant - Google Patents

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

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Publication number
WO2025204276A1
WO2025204276A1 PCT/JP2025/005269 JP2025005269W WO2025204276A1 WO 2025204276 A1 WO2025204276 A1 WO 2025204276A1 JP 2025005269 W JP2025005269 W JP 2025005269W WO 2025204276 A1 WO2025204276 A1 WO 2025204276A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive composition
acid
mass
resin
heavy metal
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/JP2025/005269
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 WO2025204276A1 publication Critical patent/WO2025204276A1/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
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • 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
    • C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02—Homopolymers or copolymers of hydrocarbons
    • C09J125/04—Homopolymers or copolymers of 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
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09J201/06—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C09J201/08—Carboxyl groups
    • 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
  • the present invention provides 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. Furthermore, the adhesive composition of the present invention also exhibits excellent solder heat resistance, adhesion, and initial low dielectric properties. Therefore, it is suitable as an adhesive composition for printed wiring boards in the high-frequency range, as well as adhesive sheets, laminates, and printed wiring boards that contain the same.
  • the present invention relates to an adhesive composition comprising an acid-modified 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 per 100 parts by mass of the acid-modified resin.
  • the present invention provides 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.
  • the acid-modified resin used in the present invention is a resin modified with an acid component.
  • the use of the acid-modified resin allows for the formation of an adhesive layer that has excellent adhesion to metal substrates such as copper foil and also has excellent solder heat resistance due to a crosslinking reaction between the epoxy groups of the epoxy resin (C) or the like.
  • the weight-average molecular weight (Mw) of the acid-modified resin used in the present invention is preferably in the range of 10,000 to 1,000,000. It is more preferably in the range of 20,000 to 500,000, even more preferably in the range of 40,000 to 200,000, and particularly preferably in the range of 50,000 to 150,000.
  • Mw weight-average molecular weight
  • the acid-modified resin used in the present invention is preferably an acid-modified resin obtained by acid-modifying a hydrocarbon-based resin, as this has good low dielectric properties.
  • one or more resins selected from the group consisting of acid-modified polystyrene resin, acid-modified cycloolefin polymer, and acid-modified polyolefin are preferred, with acid-modified polyolefin being more preferred.
  • acid-modified polystyrene resin and acid-modified cycloolefin polymer are preferred.
  • Acid-modified resins can be used alone or in combination of two or more types.
  • the acid-modified resin of the present invention preferably has a relative dielectric constant ( ⁇ c) of 2.7 or less at a frequency of 80 GHz. It is more preferably 2.6 or less, and even more preferably 2.3 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 80 GHz is preferably 2.7 or less, more preferably 2.6 or less, and even more preferably 2.3 or less.
  • the acid-modified resin of the present invention preferably has a dielectric loss tangent (tan ⁇ ) of 0.003 or less at a frequency of 80 GHz. It is more preferably 0.0025 or less, and even more preferably 0.002 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 80 GHz is preferably 0.003 or less, more preferably 0.0025 or less, and even more preferably 0.002 or less.
  • Polyolefin resin refers to a polymer primarily composed of a hydrocarbon skeleton, such as a homopolymer of an olefin monomer, exemplified by ethylene, propylene, butene, butadiene, isoprene, etc., or a copolymer with other monomers, or a hydrogenated or halide product of the resulting polymer.
  • the acid-modified polyolefin is preferably one obtained by grafting at least one of an ⁇ , ⁇ -unsaturated carboxylic acid and its acid anhydride onto at least one of polyethylene, polypropylene, and propylene- ⁇ -olefin copolymer.
  • Propylene- ⁇ -olefin copolymers are produced by copolymerizing propylene as the main component with an ⁇ -olefin.
  • ⁇ -olefins include ethylene, 1-butene, 1-heptene, 1-octene, 4-methyl-1-pentene, and vinyl acetate, and these can be used alone or in combination of two or more. Among these ⁇ -olefins, ethylene and 1-butene are preferred.
  • the propylene component is preferably 50 mol% or more, and more preferably 70 mol% or more.
  • these raw materials are not limited to petroleum-derived raw materials; raw materials obtained using chemical recycling technology that utilizes biomass naphtha and waste plastics can also be used.
  • the unsaturated carboxylic acid component is preferably at least one of an ⁇ , ⁇ -unsaturated carboxylic acid and its acid anhydride.
  • Specific examples are as described above, including maleic acid, itaconic acid, citraconic acid, and their acid anhydrides. Of these, acid anhydrides are preferred, with maleic anhydride being more preferred.
  • examples of acid-modified polyolefins include maleic anhydride-modified polypropylene, maleic anhydride-modified propylene-ethylene copolymer, maleic anhydride-modified propylene-butene copolymer, and maleic anhydride-modified propylene-ethylene-butene copolymer. These acid-modified polyolefins can be used alone or in combination of two or more.
  • the acid value of the acid-modified polyolefin preferably has a lower limit of 89 equivalents/10 6 g or more, more preferably 107 equivalents/10 6 g or more, and even more preferably 125 equivalents/10 6 g or more.
  • the upper limit is preferably 713 equivalents/10 6 g or less, more preferably 534 equivalents/10 6 g or less, and even more preferably 400 equivalents/10 6 g or less. Setting the acid value below the upper limit results in good adhesiveness. Furthermore, the viscosity and stability of the solution are improved, resulting in excellent pot life. Furthermore, production efficiency is also improved.
  • the heat of fusion ( ⁇ H) of the acid-modified polyolefin is preferably in the range of 5 J/g to 60 J/g. It is more preferably in the range of 10 J/g to 50 J/g, and most preferably in the range of 20 J/g to 40 J/g.
  • Phenol-based antioxidants include 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)bis(2-methylpropane-2,1-diyl)bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate], 2,6-di-tert-butyl-p-cresol, 2,4,6-tri-tert-butylphenol, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate, diphenyl)propionate, ethylene glycol bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate], 2,6-di-tert-butyl-4-hydroxymethylphenol, 2,5-di-tert-butylhydroquinone, 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol), 2,2'-m
  • Sulfur-based antioxidants include pentaerythritol tetrakis-(3-laurylthiopropionate), dilaurylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, and bis(2-hydroxy-1-naphthyl) sulfide.
  • Amine antioxidants include 4,4'-bis( ⁇ , ⁇ -dimethylbenzyl)diphenylamine, phenyl- ⁇ -naphthylamine, phenyl- ⁇ -naphthylamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di- ⁇ -naphthyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, aldol- ⁇ -naphthylamine, 2,2,4-trimethyl-1,2-dihydroquinone polymer, and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline.
  • 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 content of antioxidant (A) 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 acid-modified resin. If the content exceeds the upper limit, the dielectric properties may deteriorate after a long-term heat resistance test.
  • the content of antioxidant (A) is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, and even more preferably 0.1 part by mass or more, per 100 parts by mass of acid-modified resin.
  • the content is above the lower limit, deterioration due to oxidation of the acid-modified resin is suppressed, and the adhesive composition exhibits a good appearance, excellent adhesion, and excellent low dielectric properties, even after a long-term heat resistance test.
  • 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.
  • Examples include disalicyloyl hydrazide, isophthalic acid bis(2-phenoxypropionyl hydrazide), N'1,N'12-bis(2-hydroxybenzoyl)dodecane dihydrazide, decamethylenedicarboxylic acid bis(N'-salicyloyl hydrazide), oxalic acid bis(benzylidene hydrazide), thiodipropionic acid bis(benzylidene hydrazide), and isophthalic acid bis(2-phenoxypropionyl hydrazide).
  • phosphite-based heavy metal deactivators include reaction products of 2,2'-di-tert-butyl-5,5'-dimethyl-4,4'-sulfanediyldiphenol with phosphorus trichloride, bis[2-tert-butyl-4-thio(2'-methyl-4'-hydroxy-5'-tert-butylphenyl)-5-methylphenyl]pentaerythritol diphosphite, tetrakis[2-tert-butyl-4-thio(2'-methyl-4'-hydroxy-5'-tert-butylphenyl)-5-methylphenyl]-1,6-hexamethylene-bis(N-hydroxyethyl-N-methylsemicarbazide)-diphosphite, and tetrakis[2-tert-butyl-4-thio(2'-methyl-4'-hydroxy-5'-tert-butylphenyl)-5-methylphenyl]-
  • 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 inhibiting deterioration of the acid-modified 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 acid-modified 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 acid-modified resin.
  • the content is above the lower limit, deterioration due to oxidation of the adhesive composition, particularly the acid-modified resin, is suppressed, and the adhesive composition exhibits a good appearance, excellent adhesion, and excellent low dielectric properties even after long-term heat resistance testing.
  • 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 acid-modified 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, 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 and glycidyl group-containing isocyanuric acid are preferred from the standpoints of solder heat resistance and low dielectric properties, with glycidylamine-type 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.
  • the C 1-10 alkyl group (—C n H 2n+1 , where n is an integer from 1 to 10) in R 11 to R 25 may be linear or branched.
  • the C 1-10 alkyl group is preferably a C 1-6 alkyl group, more preferably a C 1-3 alkyl group, and even more preferably a methyl group or an ethyl 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
  • the content of epoxy resin (C) is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 1 part by mass or more, per 100 parts by mass of acid-modified resin. By ensuring that the content is above the lower limit, a sufficient curing effect can be achieved, and excellent adhesion and solder heat resistance can be achieved. Furthermore, the content is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 6 parts by mass or less. By ensuring that the content is below the upper limit, good pot life and low dielectric properties can be achieved.
  • 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 acid-modified resin or the epoxy group of the epoxy resin reacts with the carbodiimide bond, thereby improving heat resistance and adhesiveness.
  • the content of polycarbodiimide is preferably 1 part by mass or more, more preferably 3 parts by mass or more, per 100 parts by mass of acid-modified resin.
  • the crosslink density can be increased, resulting in good solder heat resistance.
  • it 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 it 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 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.
  • the amount of radical generator used in the present invention is preferably 0.1 parts by mass or more, and more preferably 1 part by mass or more, per 100 parts by mass of unsaturated hydrocarbon. It is also preferably 50 parts by mass or less, and more preferably 10 parts by mass or less. By keeping it within this range, an optimal crosslink density can be achieved, and both adhesion and solder heat resistance can be achieved.
  • the adhesive composition of the present invention may further contain an organic solvent.
  • the organic solvent used in the present invention is not particularly limited as long as it can dissolve the acid-modified resin, antioxidant (A), and heavy metal deactivator (B).
  • the adhesive composition of the present invention contains an organic solvent, it is desirable that the acid-modified resin, antioxidant (A), and heavy metal deactivator (B) are uniformly dissolved in the organic solvent.
  • 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 acid-modified 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.
  • a silane coupling agent When a silane coupling agent is blended, its blend amount is preferably 0.5 to 20% by mass based on 100% by mass of the solids content of the adhesive composition. By using a silane coupling agent within this range, solder heat resistance and adhesion can be improved.
  • 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.
  • a resin (adhesive)-coated metal foil is a metal foil having an adhesive layer, which is a cured product of the adhesive composition of the present invention, laminated on one side thereof.
  • Specific configurations include a metal foil layer/adhesive layer or a metal foil layer/adhesive layer/release substrate.
  • the metal foil is preferably a copper foil. Since the adhesive layer in the resin-coated metal foil can be laminated with the resin substrate, the resin-coated metal foil can be used as a material for producing the CCL.
  • 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.
  • Formation of circuits on a metal substrate can be achieved using conventional methods. Additive or subtractive methods may be used. Subtractive methods are preferred.
  • the acid value (equivalent/10 6 g) in the present invention was determined by dissolving the acid-modified resin in toluene and titrating it with a methanol solution of sodium methoxide using phenolphthalein as an indicator.
  • the weight-average molecular weight in the present invention is a value measured by gel permeation chromatography (hereinafter referred to as GPC, standard substance: polystyrene resin, mobile phase: tetrahydrofuran, column: Shodex KF-802 + KF-804L + KF-806L, column temperature: 30°C, flow rate: 1.0 ml/min, detector: RI detector) manufactured by Shimadzu Corporation.
  • GPC gel permeation chromatography
  • the melting point in the present invention is a value measured using a differential scanning calorimeter (hereinafter referred to as DSC, manufactured by TA Instruments Japan, Q-2000) from the top temperature of the melting peak when the material is heated to melt at a rate of 20°C/min, cooled to form a resin, and then heated to melt again.
  • DSC differential scanning calorimeter
  • 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.
  • the resin-containing solution was then centrifuged to separate and purify the acid-modified propylene-butene copolymer graft-polymerized with maleic anhydride, (poly)maleic anhydride, and low-molecular-weight substances.
  • the mixture was then dried under reduced pressure at 70 °C for 5 hours to obtain a maleic anhydride-modified propylene-butene copolymer (acid-modified resin 1, acid value 367 equivalents/10 6 g, weight-average molecular weight 60,000, Tm 80 °C, ⁇ H 35 J/g).
  • Acid-modified resin 3 Tuftec M1943 (manufactured by Asahi Kasei Corporation, a polymer obtained by hydrogenating the double bond portion of a block copolymer of styrene and butadiene, modified with maleic anhydride, acid value 185 equivalents/10 6 g)
  • epoxy resin (C) was used. N,N-(diglycidyl)-O-toluidine (ADEKA Corporation's "ADEKA RESIN (registered trademark) EP-3980S", epoxy value 8696 equivalents/10 6 g)
  • a1 Phenolic antioxidant (Sumitomo Chemical Co., Ltd.'s "Sumilizer (registered trademark) GA-80", 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl)bis(2-methylpropane-2,1-diyl)bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate])
  • a2 Sulfur-based antioxidant (Sumitomo Chemical Co., Ltd.'s "Sumilizer (registered trademark) TP-D", pentaerythritol tetrakis-(3-laurylthiopropionate))
  • Example 1 100 parts of acid-modified resin 1, 2 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 25%, 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 (S13) 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.
  • Example 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, comparing Example 4 and Example 6, it is clear 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 compositions of Comparative Examples 1 to 3 did not contain the heavy metal deactivator (B), and therefore showed poor appearance and adhesion after the long-term heat resistance test.
  • the adhesive composition of Comparative Example 4 did not contain the antioxidant (A), and therefore showed poor appearance, adhesion, and dielectric properties after the long-term heat resistance test.
  • the adhesive compositions of Comparative Examples 5 and 6 contained large amounts of antioxidant (A) or heavy metal deactivator (B), and therefore exhibited poor dielectric properties after long-term heat resistance tests.
  • the adhesive compositions of Comparative Examples 5 and 6 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)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (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 modifiée par un acide, un antioxydant (A), un désactivateur de métaux lourds (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 métaux lourds (B) étant de 1,0 partie en masse ou moins par rapport à 100 parties en masse de la résine modifiée par un acide.
PCT/JP2025/005269 2024-03-27 2025-02-18 Composition adhésive, feuille adhésive, stratifié et carte de circuit imprimé les comprenant Pending WO2025204276A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5095046A (en) * 1990-02-06 1992-03-10 Exxon Chemical Patents Inc. Hot melt adhesive of ethylene/unsaturated acid copolymer and epoxy crosslinker
WO2008004376A1 (fr) * 2006-07-04 2008-01-10 Yasuhara Chemical Co., Ltd. Adhésif thermofusible durcissable de type caoutchouc
JP2008088302A (ja) * 2006-10-02 2008-04-17 Shin Etsu Chem Co Ltd 難燃性接着剤組成物、ならびにそれを用いた接着剤シート、カバーレイフィルムおよびフレキシブル銅張積層板
WO2018116967A1 (fr) * 2016-12-22 2018-06-28 東亞合成株式会社 Composition adhésive, et film de revêtement, feuille de liaison, stratifié cuivré et matériau de blindage électromagnétique, chacun utilisant ladite composition adhésive

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5095046A (en) * 1990-02-06 1992-03-10 Exxon Chemical Patents Inc. Hot melt adhesive of ethylene/unsaturated acid copolymer and epoxy crosslinker
WO2008004376A1 (fr) * 2006-07-04 2008-01-10 Yasuhara Chemical Co., Ltd. Adhésif thermofusible durcissable de type caoutchouc
JP2008088302A (ja) * 2006-10-02 2008-04-17 Shin Etsu Chem Co Ltd 難燃性接着剤組成物、ならびにそれを用いた接着剤シート、カバーレイフィルムおよびフレキシブル銅張積層板
WO2018116967A1 (fr) * 2016-12-22 2018-06-28 東亞合成株式会社 Composition adhésive, et film de revêtement, feuille de liaison, stratifié cuivré et matériau de blindage électromagnétique, chacun utilisant ladite composition adhésive

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