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
  • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
  • C09J109/02—Copolymers with acrylonitrile
• • 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
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/08—Macromolecular additives
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/10—Adhesives in the form of films or foils without carriers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J7/00—Adhesives in the form of films or foils
  • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
  • C09J7/35—Heat-activated
• • 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
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/22—Secondary treatment of printed circuits
  • H05K3/28—Applying non-metallic protective coatings
• • 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
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
• • 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
  • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
  • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors

Definitions

• the present invention relates to an adhesive composition using a resin having an imide bond and a phosphorus compound, and relates to an adhesive film, a coverlay film, a copper-clad laminate, and a flexible printed wiring board using the adhesive composition.
• Flexible printed wiring boards are electronic equipment parts that require flexibility and space saving, such as device boards for display devices such as liquid crystal displays and plasma displays, and board relay cables for mobile phones, digital cameras, and portable game machines. , Are widely used for operation switch substrates and the like, and further expansion of applications is expected.
• Adhesives used for flexible printed wiring boards are used in flexible wiring boards, such as adhesive films, coverlay films, and copper-clad laminates, and are used for their adhesiveness, heat resistance, flame resistance, and insulation reliability. Is required.
• epoxy-based resins acrylic-based resins, urethane resins, etc. have been used as adhesives used in flexible printed wiring boards.
• Polyimide resins are being studied as adhesives having insufficient heat resistance and replacing them.
• a method of blending a phosphorus compound containing no halogen element such as bromine is widely used.
• phosphinic acid derivatives having a chemical structure represented by the general formula (5) are widely used from the viewpoint of heat resistance, flame retardancy and compatibility.
• phosphinic acid derivative examples include, for example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide represented by chemical formula (6), and 9,10-dioxide represented by chemical formula (7).
• 10-oxide or the like for example, see Patent Documents 1 and 2.
• 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide represented by the chemical formula (6) has a low molecular weight and therefore has a low thermogravimetric loss temperature, and a part thereof remains uncured. Then, there was a problem that heat resistance was reduced. Further, 9,10-dihydro-10-benzyl-9-oxa-10-phosphaphenanthrene-10-oxide represented by the chemical formula (7) does not have a reactive functional group, and thus can be used in a high-temperature and high-humidity environment. There is a problem that bleed-out easily occurs and insulation reliability is reduced.
• 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide represented by the chemical formula (8) has low solubility in a solvent, and therefore, has poor handleability. There was a problem to do.
• the present invention has been made to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide an adhesive having excellent adhesiveness, heat resistance, flame retardancy, handleability, and high insulation reliability. It is to provide a composition.
• the present inventors have conducted intensive studies to achieve the above object, and as a result, completed the present invention by combining a resin having an imide bond and a specific phosphorus compound.
• the present invention comprises the following constitutions.
• R 1 to R 4 in the general formula (1) are any of the following general formulas (2) to (4), and at least one of R 1 to R 4 is a general formula (2)
• * represents a site directly bonded to the aromatic ring in the general formula (1)
• a plurality of Xs in the general formulas (1) and (3) represent Each independently represents CH 2 or C (CH 3 ) 2
• a plurality of Ys in the general formulas (1) and (3) each independently represent hydrogen or a hydroxyl group, provided that the general formula (1) , At least one of the plurality of Y is a hydroxyl group, and R 5 in the general formula (4) is hydrogen or an alkyl group having 1 to 10 carbon atoms.
• the resin having an imide bond is preferably a polyimide resin, a polyamide imide resin, a polyether imide resin, a polyether ether ketone resin, a polyester imide resin or a polycarbonate imide resin. Further, it is preferable to contain trimellitic anhydride or acrylonitrile-butadiene rubber modified with carboxyl groups at both terminals as a copolymerization component of the resin having an imide bond.
• the epoxy resin further contains an epoxy resin, and the properties of the epoxy resin are liquid at 25 ° C. and have two or more epoxy groups in one molecule.
• an adhesive composition having excellent adhesiveness, heat resistance, flame retardancy, handleability, and high insulation reliability by combining a resin having an imide bond and a specific phosphorus compound, an adhesive composition having excellent adhesiveness, heat resistance, flame retardancy, handleability, and high insulation reliability, and An adhesive film, a coverlay film, a copper-clad laminate, and a flexible printed wiring board using this can be obtained.
• the resin having an imide bond used in the adhesive composition of the present invention has at least one imide bond in a repeating unit of the resin, and includes, for example, a polyimide resin, a polyamideimide resin, a polyetherimide resin, and a polyetherether. Ketone resin, polyester imide resin, polycarbonate imide resin and the like can be mentioned.
• the imide bond preferably has two or more imide bonds in the repeating unit of the resin.
• the resin having an imide bond preferably has an acid component and a diisocyanate component or a diamine component as a copolymerization component.
• the diisocyanate component or the diamine component is also collectively referred to as an amine component.
• the acid component may be any of an acid component having an aromatic ring (aromatic acid component), an aliphatic acid component and an alicyclic acid component, but is preferably a polycarboxylic acid component having an aromatic ring.
• the amine component (diisocyanate component or diamine component) may be any of an amine component having an aromatic ring, an aliphatic amine component, or an alicyclic amine component, but is preferably an amine component having an aromatic ring. That is, it is preferable that the polymer be composed of a structural unit derived from a polycarboxylic acid component having an aromatic ring and a structural unit derived from a diisocyanate component having an aromatic ring or a diamine component having an aromatic ring.
• the resin having an imide bond used in the adhesive composition of the present invention preferably has a carboxyl group or an acid anhydride group as a reactive functional group.
• the acid value of the resin having an imide bond is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and further preferably 20 mgKOH / g or more. Further, it is preferably at most 150 mgKOH / g, more preferably at most 120 mgKOH / g, even more preferably at most 100 mgKOH / g.
• the acid component of the resin having an imide bond of the present invention it is preferable to use a polycarboxylic acid component having an aromatic ring.
• the aromatic polycarboxylic acid component is preferably an aromatic polycarboxylic acid anhydride, and more preferably, trimellitic anhydride (TMA).
• trimellitic anhydride trimellitic anhydride
• an amide bond can be formed in addition to the imide bond, and the solvent solubility of the resin can be improved.
• Trimellitic anhydride is preferably at least 30 mol%, more preferably at least 40 mol%, even more preferably at least 50 mol%, when the total acid component is 100 mol%.
• the upper limit is not limited, and may be 100 mol%, but is preferably 90 mol% or less, more preferably 80 mol% or less, and further preferably 70 mol% or less.
• polycarboxylic acid component having an aromatic ring other than trimellitic anhydride examples include pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (BTDA) , 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), ethylene glycol bisanhydrotrimellitate (TMEG), propylene glycol bisanhydrotrimellitate, 1,4-butanediol bis Alkylene glycol bisanhydrotrimellitates such as anhydrotrimellitate, hexamethylene glycol bisanhydrotrimellitate, polyethylene glycol bisanhydrotrimellitate, polypropylene glycol bisanhydrotrimellitate, 1,2,5, 6-naphthalenetetracarbo Acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinet
• aliphatic or alicyclic acid anhydrides and aromatic, aliphatic or alicyclic dicarboxylic acids can be used.
• those obtained by hydrogenating any of the components described in the preceding section can be used.
• 1,4-cyclohexanedicarboxylic acid 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, meso-butane-1,2,3,4-tetracarboxylic acid Dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohex-1-ene-2,3,5 6-tetracarboxylic dianhydride, 3-ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3- ( 1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic
• Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, and stilbene dicarboxylic acid.
• Examples of the aliphatic dicarboxylic acid include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decandioic acid, dodecandioic acid, eicosantioic acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedicarboxylic acid, 2-methyloctanedicarboxylic acid, 3,8-dimethyldecanedicarboxylic acid, 3,7-dimethyldecanedicarboxylic acid, 9,12-dimethyleicosanediacid, fumaric acid And maleic acid.
• the total acid component is preferably at least 5 mol%, more preferably at least 100 mol%. Is at least 10 mol%, more preferably at least 20 mol%. Further, it is preferably at most 60 mol%, more preferably at most 50 mol%, further preferably at most 45 mol%.
• an amine component having an aromatic ring (aromatic diisocyanate or aromatic diamine) is preferable.
• the diisocyanate having an aromatic ring include diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3 ' -Or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2 '-Or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3, 3'- or 4,2'- or 4,3'- or
• the amine component having an aromatic ring is preferably at least 80 mol%, more preferably at least 90 mol%, even more preferably at least 95 mol%, when the total amine component is 100 mol%. It may be mol%. When the content is in the above range, a resin having an imide bond excellent in adhesiveness and heat resistance can be obtained.
• a diisocyanate component having an aromatic ring may be used alone, a diamine component having an aromatic ring may be used alone, or both may be used in combination. Among them, it is preferable to use a diisocyanate component having an aromatic ring alone.
• An aliphatic amine component (aliphatic diisocyanate or aliphatic diamine) or an alicyclic amine component (alicyclic diisocyanate or alicyclic diamine) may be used as another amine component within a range that does not impair the effects of the present invention. it can.
• a diisocyanate or a diamine obtained by hydrogenating any of the components described in the preceding section can be used.
• these components are preferably 20 mol% or less, more preferably 10 mol%, when the total amine component is 100 mol%. Or less, more preferably 5 mol% or less, and even 0 mol%.
• the resin having an imide bond of the present invention has three functional groups for the purpose of improving the heat resistance of the obtained adhesive composition by increasing the number of reaction points with the epoxy resin as long as the effects of the present invention are not impaired. It is possible to copolymerize the above compounds. For example, polyfunctional carboxylic acids such as trimesic acid, dicarboxylic acids having a hydroxyl group such as 5-hydroxyisophthalic acid, dicarboxylic acids having an amino group such as 5-aminoisophthalic acid, and three or more hydroxyl groups such as glycerin and polyglycerin. And those having three or more amino groups such as tris (2-aminoethyl) amine.
• polyfunctional carboxylic acids such as trimesic acid
• dicarboxylic acids having a hydroxyl group such as 5-hydroxyisophthalic acid
• dicarboxylic acids having an amino group such as 5-aminoisophthalic acid
• three or more hydroxyl groups such as glycerin and polygly
• a polyfunctional carboxylic acid such as trimesic acid is preferable, and its amount is preferably 10 mol% or less, and preferably 5 mol% or less, when the total acid component is 100 mol%. Is more preferable. If it exceeds 10 mol%, gelation may occur during polymerization, or insolubles may be generated.
• acrylonitrile-butadiene rubber modified with a carboxyl group at both ends polyester diol, polyether diol, polycarbonate diol, dimer acid, hydrogenated dimer acid, dimer acid as a component for imparting flexibility or adhesion.
• Copolymerization of flexible components such as diol, both terminal carboxyl group-modified polysiloxane, both terminal acid anhydride group-modified polysiloxane, both terminal carboxyl group-modified polybutadiene, both terminal carboxyl group-modified hydrogenated polybutadiene, polybutadiene diol, and hydrogenated polybutadiene diol
• flexible components such as diol, both terminal carboxyl group-modified polysiloxane, both terminal acid anhydride group-modified polysiloxane, both terminal carboxyl group-modified polybutadiene, both terminal carboxyl group-modified hydrogenated polybutadiene, polybutadiene diol, and hydrogenated polybutadiene diol
• acrylonitrile-butadiene rubber modified with a carboxyl group at both terminals is preferred from the viewpoint of flexibility and adhesiveness.
• the content is preferably 10% by mass or more, more preferably 20% by mass or more, when the
• flexibility can be imparted to the resin without impairing the effects of adhesiveness, heat resistance, and flame retardancy.
• the resin having an imide bond of the present invention can be produced from an acid component and a diisocyanate component (isocyanate method), or by reacting an acid component with a diamine component to form an amic acid, followed by ring closure (direct method). ) Or a method of reacting a compound having an acid anhydride and an acid chloride with a diamine (acid chloride method). Industrially, the isocyanate method is advantageous.
• the polymerization reaction of the resin having an imide bond of the present invention can be carried out by stirring the acid component and the diisocyanate component in a solvent while heating them at 60 ° C to 200 ° C as conventionally known.
• the molar ratio of the acid component / diisocyanate component is preferably in the range of 85/100 to 100/100.
• the content of the acid component and the diisocyanate component in the resin having an imide bond is the same as the ratio of each component at the time of polymerization.
• alkali metals such as sodium fluoride, potassium fluoride, sodium methoxide, triethylenediamine, triethylamine, 1,8-diazabicyclo [5,4,0] -7-undecene, Amines such as 5-diazabicyclo [4,3,0] -5-nonene and catalysts such as dibutyltin dilaurate can be used. If the amount of these catalysts is too small, the catalytic effect cannot be obtained, and if the amount is too large, a side reaction may occur. It is preferable to use ⁇ 5 mol%, more preferably 0.1 to 3 mol%.
• the resin having an imide bond preferably has a molecular weight corresponding to a logarithmic viscosity of 0.1 to 0.8 (dl / g) at 30 ° C., and more preferably 0.2 to 0.7 (dl / g). / G), and more preferably a molecular weight corresponding to a logarithmic viscosity of 0.25 to 0.65 (dl / g).
• dl / g logarithmic viscosity of 0.1 to 0.8 (dl / g) at 30 ° C., and more preferably 0.2 to 0.7 (dl / g). / G), and more preferably a molecular weight corresponding to a logarithmic viscosity of 0.25 to 0.65 (dl / g).
• the resin having an imide bond has a glass transition temperature of preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 120 ° C. or higher.
• the upper limit is not particularly limited, but is preferably 300 ° C. or lower, more preferably 290 ° C. or lower, and further preferably 285 ° C. or lower. When the content is in the above range, excellent adhesiveness and heat resistance can be exhibited.
• Examples of the solvent that can be used for polymerization of the resin having an imide bond of the present invention include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, dimethylimidazolidinone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, cyclohexanone, and cyclopentane.
• dimethylacetamide is preferred because of its low boiling point and good polymerization efficiency.
• the concentration of the nonvolatile components and the viscosity of the solution can be adjusted by diluting with the solvent used for the polymerization or another low boiling point solvent.
• the low boiling solvent examples include aromatic solvents such as toluene and xylene, aliphatic solvents such as hexane, heptane and octane, alcohol solvents such as methanol, ethanol, propanol, butanol and isopropanol, acetone, methyl ethyl ketone and methyl isobutyl ketone.
• ketone solvents such as cyclohexanone and cyclopentanone
• ether solvents such as diethyl ether and tetrahydrofuran
• ester solvents such as ethyl acetate, butyl acetate and isobutyl acetate.
• the content of the resin having an imide bond in the nonvolatile component of the adhesive composition of the present invention is preferably 40% by mass or more, more preferably 45% by mass or more, and still more preferably 50% by mass or more. is there. Further, the content is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less. When the content is within the above range, excellent adhesiveness and heat resistance of the adhesive composition can be exhibited.
• the adhesive composition of the present invention contains a phosphorus compound represented by the general formula (1) (hereinafter, also referred to as a phosphorus compound of the general formula (1)).
• a phosphorus compound of the general formula (1) By containing the phosphorus compound of the general formula (1), an adhesive composition having excellent adhesiveness, heat resistance, flame retardancy and insulation reliability can be obtained.
• R 1 to R 4 are any of Formulas (2) to (4), and at least one of R 1 to R 4 is Formula (2).
• the preferred position in the case of two general formulas (2) is not particularly limited, and may be R 1 and R 2 or R 1 and R 3 .
• a plurality of Xs are each independently “* —CH 2 — *” or “* —C (CH 3 ) 2 — *” (* is a general formula ( 1) or a site directly bonded to the aromatic ring of the general formula (3), hereinafter simply referred to as CH 2 or C (CH 3 ) 2 .
• X in either the general formula (1) or the general formula (3) is C (CH 3 ) 2
• X in both the general formula (1) and the general formula (3) is C (CH 3) 3 ) 2 .
• a plurality of Ys are each independently hydrogen or a hydroxyl group.
• At least one of the plurality of Ys is a hydroxyl group, and preferably two of the Ys are a hydroxyl group.
• the phosphorus compound of the general formula (1) since at least one of Y is a hydroxyl group, the phosphorus compound of the general formula (1) has a reactive functional group, and suppresses bleed-out in a high-temperature and high-humidity environment and has excellent insulation. Reliability can be exhibited.
• the position of the hydroxyl group may be ortho or para to X, but it is preferable that at least one hydroxyl group is para to X, and that both of the two hydroxyl groups are para to X. More preferred.
• the number of hydroxyl groups is preferably one or more, and more preferably two.
• the position may be ortho or para to X, but it is preferred that at least one hydroxyl group is para to X, more preferably both hydroxyl groups are para to X. preferable.
• R 5 is hydrogen or an alkyl group having 1 to 10 carbon atoms. It is preferably an alkyl group having 2 to 8 carbon atoms, and more preferably an alkyl group having 3 to 5 carbon atoms.
• the alkyl group may be linear or branched.
• the phosphorus compound of the general formula (1) may be a single compound or a mixture of a plurality of compounds having different substituents.
• the content of the phosphorus compound of the general formula (1) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and still more preferably 15 parts by mass, based on 100 parts by mass of the resin having an imide bond. Parts or more, particularly preferably 20 parts by mass or more. Further, it is preferably at most 100 parts by mass, more preferably at most 90 parts by mass, further preferably at most 80 parts by mass, particularly preferably at most 70 parts by mass. Within the above range, excellent adhesiveness, heat resistance, flame retardancy and insulation reliability can be exhibited.
• any of the phosphorus compounds having the structures represented by the chemical formulas (9) to (11) (hereinafter, also referred to as the phosphorus compounds of the chemical formulas (9) to (11), respectively). And particularly preferably a phosphorus compound of the chemical formula (9).
• the ratio of the total amount of the phosphorus compounds of the chemical formulas (9) to (11) in the phosphorus compound of the general formula (1) is preferably at least 30% by mass, more preferably at least 50% by mass, even more preferably. Is 80% by mass or more, particularly preferably 90% by mass or more, and may be 100% by mass. Excellent insulation reliability can be exhibited by containing the above ratio.
• the ratio of the phosphorus compound of the chemical formula (9) to the total amount of the phosphorus compounds of the chemical formulas (9) to (11) is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably It is 80% by mass or more, particularly preferably 90% by mass or more, and may be 100% by mass.
• the ratio of the phosphorus compound of the chemical formula (9) to the total amount of the phosphorus compounds of the chemical formulas (9) to (11) is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably It is 80% by mass or more, particularly preferably 90% by mass or more, and may be 100% by mass.
• the handleability is good even after preparing the adhesive composition.
• the solvent include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, dimethylimidazolidinone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, cyclohexanone, cyclopentanone and the like.
• the low-boiling solvent examples include aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane, heptane and octane; alcohol solvents such as methanol, ethanol, propanol, butanol and isopropanol; acetone, methyl ethyl ketone and methyl isobutyl.
• ketone solvents such as ketone, cyclohexanone and cyclopentanone
• ether solvents such as diethyl ether and tetrahydrofuran
• ester solvents such as ethyl acetate, butyl acetate and isobutyl acetate.
• the phosphorus compound of the general formula (1) is preferably dissolved in the solvent at room temperature (25 ° C.) at 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more.
• phosphorus compound other than the phosphorus compound of the general formula (1) can be added as long as the effects of the present invention are not impaired.
• phosphinic acid derivatives such as BCA, HCA (registered trademark), BzHCA, M-Acid, M-Ester, HCA-HQ, and HCA-NQ (trade names, manufactured by Sanko Co., Ltd.), and products manufactured by Daihachi Chemical Co., Ltd. CR-733S, CR-741, PX-200, PX-202, trade name ADK STAB (registered trademark) FP-600 manufactured by ADEKA Corporation, condensed phosphate compound such as PFR, manufactured by Otsuka Chemical Co., Ltd.
• the preferred phosphorus content in the non-volatile component of the adhesive composition of the present invention is 1.0 to 5.0% by mass, more preferably 1.0 to 3.0% by mass. If the phosphorus content is low, good flame retardancy cannot be obtained, while if it is high, the adhesiveness, heat resistance, and insulation reliability tend to decrease.
• a phosphorus-free flame retardant can be added as long as the effects of the present invention are not impaired.
• aluminum hydroxide such as Hygilite (registered trademark) H-42, H-42M, H-43, H-43M (trade name, manufactured by Showa Denko KK), Kisuma (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.) (Registered trademark) magnesium hydroxide such as 5, 8, 5Q-S, 200-06H and the like, and melamine cyanurate compounds such as MC-4000, MC-4500 and MC-6000 (trade names, manufactured by Nissan Chemical Industries, Ltd.). These may be used alone or in combination of two or more.
• An epoxy resin can be blended in the adhesive composition of the present invention.
• the content of the epoxy resin is preferably at least 10 parts by mass, more preferably at least 20 parts by mass, further preferably at least 25 parts by mass, based on 100 parts by mass of the resin having an imide bond. Further, it is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 70 parts by mass or less.
• the content is not more than the upper limit, the content of the resin having an imide bond can be maintained at a certain amount or more. Therefore, the epoxy resin does not remain uncured, and the heat resistance of the adhesive composition after curing is improved.
• the amount is not less than the lower limit, a sufficient crosslinking reaction can be formed with the resin having an imide bond, and the heat resistance and the insulation reliability of the adhesive composition after curing can be improved.
• the epoxy resin used in the adhesive composition of the present invention may be liquid at 25 ° C., semi-solid or solid, but is liquid at 25 ° C. and has two or more per molecule. Epoxy resins having epoxy groups are preferred.
• the epoxy resin may be modified, or may contain a sulfur atom, a nitrogen atom, a phosphorus atom, etc. in the molecular skeleton.
• bisphenol A epoxy resin bisphenol F epoxy resin, or a hydrogenated product thereof, phenol novolak epoxy resin, naphthalene epoxy resin, dicyclopentadiene epoxy resin, NBR (acrylonitrile butadiene rubber modified with carboxyl groups at both ends) )
• Modified epoxy resin dimer acid-modified epoxy resin, polybutadiene-modified epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin and the like.
• Examples of commercially available products include jER (registered trademark) 825, jER827, jER828, and YL980 (trade names, manufactured by Mitsubishi Chemical Corporation), Epicron (trademark) 840, 840-S, manufactured by DIC Corporation.
• 850, 850-S, EXA-850CRP, 850-LC trade names YD-127, YD-128, YD-128G, YD-128S, YD-128CA, YD-8125, YD- manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
• Bisphenol A type liquid epoxy resin such as 825GS, YD-825GHS, etc., trade names jER806, jER806H, jER807, YL983U, manufactured by Mitsubishi Chemical Corporation, Epicron 830, 830-S, 835, EXA-, manufactured by DIC Corporation 830CRP, EXA-830LVP, EXA-835LV, Nippon Steel & Sumikin Chemical Co., Ltd.
• Bisphenol F type liquid epoxy resin such as YDF-170, YDF-170N, YDF-8170C, YDF-870GS manufactured by Mitsubishi Chemical Corporation, YX8000, YX8034 manufactured by Mitsubishi Chemical Corporation, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
• Phenol novolak type liquid epoxy resin such as hydrogenated bisphenol A type liquid epoxy resin such as ST-3000, trade name jER152 manufactured by Mitsubishi Chemical Corporation, and Epicron N-730A trade name manufactured by DIC Corporation; DIC Corporation Naphthalene-type liquid epoxy resin such as Epicron HP-4032D (trade name), didecapentadiene-type liquid epoxy resin such as Adekaresin (registered trademark) EP-4088S, EP-4088L (trade name) manufactured by ADEKA Corporation, DIC Corporation ) Manufactured by Epicron TSR-960, TSR-601, etc.
• BR-modified epoxy resin dimer acid-modified epoxy resin such as jER871, jER872 (trade name, manufactured by Mitsubishi Chemical Corporation), Epototo (registered trademark) YD-172 (trade name, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), manufactured by Nippon Soda Co., Ltd.
• Butadiene-modified epoxy resins such as JP-100, JP-200, and JP-400; alicyclic epoxy resins such as Celoxide (registered trademark) 2021P and 2081 manufactured by Daicel Chemical Industries, Ltd .; Triglycidyl isocyanurate such as TEPIC (registered trademark) manufactured by Co., Ltd., trade names Denacol (registered trademark) EX-1000 series, denacol L series, denacol DLC series, denalex (registered trademark) manufactured by Nagase ChemteX Corp. Series, EX991, etc., which may be used alone or in combination. A combination of numbers may be used.
• a semi-solid or solid epoxy resin at 25 ° C. can be used as the epoxy resin.
• the semi-solid or solid epoxy resin at 25 ° C. may be modified, and may contain a sulfur atom, a nitrogen atom, a phosphorus atom, etc. in the molecular skeleton.
• Examples of these commercially available products include jER1001, jER1004, jER1007, and jER1010 (trade names, manufactured by Mitsubishi Chemical Corporation), and Epototos YD-134, YD-011, YD-014, and YD-trade names (trade names, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.).
• bisphenol A epoxy resin such as Epicron 860, 1055, 2050, 3050, 4050, 7050 (trade names, manufactured by DIC Corporation), jER4004P, jER4005P, jER4007P, jER4010P (trade names, manufactured by Mitsubishi Chemical Corporation)
• Bisphenol F epoxy resin such as Epototo YDF-2001 and YDF-2004 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .
• hydrogenated bisphenol A epoxy resin such as ST-4000D manufactured by Nippon Steel & Sumikin Chemical Co., Ltd .
• ER154 trade names Epicron N-740, N-770, N-775, manufactured by DIC Corporation, trade names EPPN (registered trademark) -201, EPPN-501H, EPPN-501HY, EPPN, manufactured by Nippon Kayaku Co., Ltd. -502H, NC-2000L, phenol novolak type epoxy resin such as DEN-438 (trade name, manufactured by Dow Chemical Company), and Epicron N-660, N-665, N-670, N-673 (trade name, manufactured by DIC Corporation) N-680, N-690, N-695, Nippon Steel & Sumikin Chemical Co., Ltd. product name Epototo YDCN-700-7, YDCN-700-10, Nippon Kayaku Co., Ltd.
• EOCN registered trademark
• Cresol novolak type epoxy resin such as -1020, EOCN-102S, EOCN-103S, EOCN-104S, manufactured by Mitsubishi Chemical Corporation Biphenyl-type epoxy resins such as YX4000 and YX4000H, trade names NC-3000, NC-3000L, NC-3000H, and NC-3100, manufactured by Nippon Kayaku Co., Ltd., and Epicron HP-4700, manufactured by DIC Corporation , HP-4710, HP-4770, HP-5000, HP-6000, Nippon Kayaku Co., Ltd., trade names NC-7000L, NC-7300L, etc., naphthalene type epoxy resin, DIC Corporation trade name, Epicron Dicyclopentadiene type epoxy resin such as HP-7200L, HP-7200, HP-7200H, HP-7200HH, HP-7200HHH, trade name XD-1000 manufactured by Nippon Kayaku Co., Ltd., manufactured by Daicel Chemical Industries, Ltd. Alicyclic epoxy
• the total chlorine content in the non-volatile component of the adhesive composition is preferably 500 ppm or less, more preferably 300 ppm or less.
• An organic solvent having a surface tension of 33 dyn / cm or less can be added to the adhesive composition of the present invention, in addition to the above-described solvent, in order to enhance coating stability, within a range that does not impair the effects of the present invention. .
• aromatic solvents such as toluene and xylene
• aliphatic solvents such as hexane, heptane and octane
• alcohol solvents such as methanol, ethanol, propanol, butanol and isopropanol
• acetone methyl ethyl ketone, methyl isobutyl ketone
• cyclohexanone and cyclohexane examples thereof include ketone solvents such as pentanone, ether solvents such as diethyl ether and tetrahydrofuran, ester solvents such as ethyl acetate, butyl acetate and isobutyl acetate, and acetate solvents such as diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.
• the amount of the solvent is not particularly limited as long as the resin having an imide bond is dissolved, and is preferably at least 50 parts by mass, more preferably at least 100 parts by mass, based on 100 parts by mass of the resin having an imide bond. And more preferably 200 parts by mass or more. Moreover, it is preferable that it is 2000 mass parts or less, More preferably, it is 1500 mass parts or less, More preferably, it is 1000 mass parts or less.
• a surface conditioner can be added to the adhesive composition of the present invention in order not to impair the effects of the present invention in order to enhance coating stability.
• the surface conditioner preferably has a boiling point of 150 ° C. or lower, and more preferably has a boiling point of 120 ° C. or lower.
• the compounding amount of these surface conditioners is preferably 0.01 to 0.5% by mass, more preferably 0.01 to 0.5% by mass, based on the total mass of the resin having an imide bond and the epoxy resin in the adhesive composition. It is 0.05 to 0.3% by mass. If the amount of the surface conditioner is small, coating stability may not be easily obtained, and if the amount is large, adhesion may not be easily exhibited.
• a high heat-resistant resin can be added in order not to impair the effects of the present invention, in order to enhance insulation reliability under a high-temperature, high-humidity environment at a higher level.
• the high heat-resistant resin is preferably a resin having a glass transition temperature of 200 ° C. or higher, more preferably a resin having a glass transition temperature of 250 ° C. or higher. Specific examples include, but are not limited to, a polyimide resin, a polyamideimide resin, a polyetherimide resin, and a polyetheretherketone resin. Further, the high heat resistant resin is preferably dissolved in a solvent.
• a resin satisfying these conditions a resin in which the anhydride of a polycarboxylic acid having an aromatic ring is 90 mol% or more when a constitutional unit derived from all acid components is 100 mol% is preferable, and a polyamideimide resin is particularly preferable. Is most preferred. Specific raw materials are as described above.
• the adhesive composition of the present invention may further include a glycidylamine-type epoxy resin in addition to the above-described epoxy resin in order to accelerate curing, as long as the effects of the present invention are not impaired.
• the addition amount of the glycidylamine type epoxy resin is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 5% by mass with respect to the total mass of the resin having an imide bond and the epoxy resin in the adhesive composition. 2% by mass is more preferred. If the amount of the glycidylamine type epoxy resin is small, the effect of accelerating the curing may not be obtained.
• glycidylamine type epoxy resins include TETRAD (registered trademark) -X and TETRAD-C (trade names, manufactured by Mitsubishi Gas Chemical Co., Ltd.), jER630, jER604 (trade names, manufactured by Mitsubishi Chemical Corporation), and Nippon Steel & Sumitomo Metal Corporation.
• a curing agent or a curing accelerator for an epoxy resin can be added to the adhesive composition of the present invention as long as the effects of the present invention are not impaired.
• the curing agent is not particularly limited as long as it is a compound that reacts with the epoxy resin, and examples thereof include an amine-based curing agent, a compound having a phenolic hydroxyl group, a compound having a carboxylic acid, and a compound having an acid anhydride.
• the curing catalyst is not particularly limited as long as it promotes the reaction between the epoxy resin and the resin having an imide bond and the above-mentioned curing agent. For example, trade names 2MZ, 2E4MZ, C11Z, manufactured by Shikoku Chemicals Co., Ltd.
• silane coupling agent can be added to the adhesive composition of the present invention for the purpose of improving adhesiveness, as long as the effects of the present invention are not impaired.
• the silane coupling agent is not particularly limited as long as it is conventionally known. Specific examples thereof include amino silane, mercapto silane, vinyl silane, epoxy silane, methacryl silane, isocyanate silane, ketimine silane or a mixture or reaction product thereof, or a compound obtained by reacting these with a polyisocyanate.
• silane coupling agents include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, bistrimethoxysilylpropylamine , Bistriethoxysilylpropylamine, bismethoxydimethoxysilylpropylamine, bisethoxydiethoxysilylpropylamine, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3- Aminosilane such as aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylethyldiethoxysilane,
• epoxysilane has a reactive epoxy group and can react with a resin having an imide bond, and is therefore preferable in terms of improving heat resistance and wet heat resistance.
• the amount of the silane coupling agent to be added is preferably 0 to 3% by mass, more preferably 0.1 to 2% by mass, based on the nonvolatile content of the resin composition. If the amount is too large, the heat resistance may decrease.
• An organic / inorganic filler can be added to the adhesive composition of the present invention for the purpose of improving the solder heat resistance as long as the effects of the present invention are not impaired.
• the organic filler include powders of a heat-resistant resin such as polyimide and polyamideimide.
• the inorganic filler include silica (SiO 2 ), alumina (Al 2 O 3 ), titania (TiO 2 ), tantalum oxide (Ta 2 O 5 ), zirconia (ZrO 2 ), and silicon nitride (Si 3 N).
• silica is preferred from the viewpoint of the ease of dispersion and the effect of improving heat resistance.
• These may be used alone or in combination of two or more.
• the addition amount of these organic / inorganic fillers is preferably 1 to 30% by mass, more preferably 3 to 15% by mass, based on the nonvolatile components of the adhesive composition. If the amount is too large, the adhesive coating film becomes brittle, and if the amount is too small, a sufficient effect of improving heat resistance may not be obtained.
• a solvent solution of a resin having an imide bond (hereinafter also referred to as a resin varnish having an imide bond), a solvent solution of an epoxy resin (hereinafter also referred to as an epoxy resin varnish), a phosphorus compound of the general formula (1), and the like are blended. And stir so that the system becomes uniform.
• a filler a slurry obtained by the above-mentioned solvent is added as a filler, followed by further stirring. Thereby, the adhesive composition of the present invention is obtained.
• a diluting solvent or a curing accelerator for adjusting the viscosity may be added as necessary.
• the adhesive composition of the present invention can be used as an adhesive composition suitable for a flexible printed wiring board.
• the layer of the adhesive composition after the adhesive composition is applied to a substrate such as a film and dried is referred to as an adhesive layer, and is used as a portion of the flexible printed wiring board where the adhesive composed of the adhesive composition is used.
• Examples include an adhesive film for a reinforcing plate, an adhesive film for an interlayer, a coverlay film, and a copper-clad laminate.
• the adhesive film is a film composed of “protective film / adhesive layer” or “protective film / adhesive layer / protective film”. In some cases, an insulating film layer is provided in the adhesive layer, and the configuration is “protective film / adhesive layer / insulating film / adhesive layer / protective film layer”. Flexible printed wiring boards are often used as adhesive films for reinforcing plates and adhesive films for interlayer use.
• the insulating film is a film having a thickness of 1 to 200 ⁇ m made of a plastic such as polyimide, polyamide imide, polyester, polyphenylene sulfide, polyether sulfone, polyether ether ketone, aramid, polycarbonate, and polyarylate. May be laminated.
• the protective film is not particularly limited as long as it can be peeled off without impairing the properties of the adhesive.
• Films, films obtained by coating these with silicone, fluoride or other release agents, paper laminated with these, paper impregnated or coated with a releasable resin, and the like can be given.
• the coverlay film is a film composed of “insulating film / adhesive layer” or “insulating film / adhesive layer / protective film”.
• the copper-clad laminate is a laminate composed of “copper foil / adhesive layer / insulating film” or “copper foil / adhesive layer / insulating film / adhesive layer / copper foil”.
• the copper foil is not particularly limited, but rolled copper foil or electrolytic copper foil conventionally used for flexible printed wiring boards can be used.
• the adhesive composition is obtained by applying the adhesive composition on a film or copper foil as a substrate, drying the solvent, and performing thermocompression bonding and thermosetting with the adherend.
• a reaction containing a resin having an imide bond and a phosphorus compound of the general formula (1) and a heat treatment by performing a heat treatment after drying with a solvent for the purpose of adjusting the fluidity of the adhesive composition during thermocompression bonding
• the phosphorus compound having a group may be partially reacted with the epoxy resin.
• the state before the thermocompression bonding is called a B stage.
• thermosetting adhesiveness, heat resistance, and insulation reliability are required after thermosetting, and it is preferable that the resin has flame retardancy.
• processing such as winding, storage, cutting, and punching in the B-stage state, and flexibility in the B-stage state is also required.
• thermocompression bonding and thermosetting are generally performed immediately after the formation of the B-stage state, and flexibility in the B-stage state is not required as much as a coverlay film and an adhesive film.
• the amount of the residual solvent in the adhesive layer in the B-stage state is preferably less than 1.5% by mass. More preferably, the content is 1.0% by mass or less.
• the residual solvent is a solvent used in the adhesive composition that could not be removed in the B-stage forming step. When a plurality of solvents are used in combination, a solvent having a higher boiling point remains. If the amount of the residual solvent is large, the insulation reliability may be reduced. Therefore, as described above, the amount of the residual solvent in the adhesive layer in the B-stage state may be less than 1.5% by mass. Preferably, it is 1.0% by mass or less.
• the adhesive composition containing the resin having an imide bond of the present invention and the phosphorus compound of the general formula (1) is excellent in adhesiveness, heat resistance, flame retardancy, and insulation reliability.
• the phosphorus compound of the general formula (1) is excellent in solvent solubility and therefore excellent in handleability.
• the phosphorus compound of the general formula (1) since the phosphorus compound of the general formula (1) has excellent compatibility with a resin having an imide bond and has a reactive functional group, it is incorporated into a crosslink by thermosetting, and hardly bleeds out under a high temperature and high humidity environment. There is. Therefore, the adhesive composition containing the resin having an imide bond of the present invention and the phosphorus compound of the general formula (1) exhibits high insulation reliability.
• V1 indicates a resin solution viscosity measured by an Ubbelohde type viscosity tube
• V2 indicates a solvent viscosity measured by an Ubbelohde type viscosity tube.
• V1 and V2 were determined from the time when the resin solution and the solvent (N-methyl-2-pyrrolidone) passed through the capillary of the viscosity tube.
• V3 is the resin concentration (g / dl).
• Acid value 0.1 g of a resin having an imide bond is dissolved in 20 ml of N-methyl-2-pyrrolidone, and titrated with a 0.1 N KOH ethanol solution using thymolphthalein as an indicator to obtain a carboxyl group per 10 6 g of the resin.
• the equivalent value (eq / ton) was measured, and the acid value was calculated according to the following equation.
• Acid value (mgKOH / g) [carboxyl group equivalent (eq / ton) ⁇ 56.12] / 1000
• Glass-transition temperature A solution of a resin having an imide bond was applied to the glossy surface of the copper foil, and dried at 140 ° C. for 3 minutes using a hot air drier. Thereafter, the resin-coated copper foil was obtained by drying under a nitrogen atmosphere at 250 ° C. for 30 minutes. Thereafter, the copper foil was etched to produce a resin film having a thickness of 20 ⁇ m. The glass transition point of the resin film thus produced was measured by a TMA (thermomechanical analyzer) tensile method under the conditions of a load of 50 mN and a temperature rising rate of 10 ° C./min.
• TMA thermomechanical analyzer
• Adhesiveness The solution of the adhesive composition is applied to a polyimide (PI) film (Apical (registered trademark) 12.5 NPI manufactured by Kaneka) so that the adhesive layer has a thickness of 20 ⁇ m after drying, and dried at 140 ° C. for 3 minutes with hot air circulation.
• the sample was dried in an oven to obtain a sample (PI film / adhesive layer) in a B-stage state.
• the adhesive-coated surface of the sample (PI film / adhesive layer) in the B-stage state and the rolled copper foil (BHY-13FT made of JX Metal: 18 ⁇ m in thickness) were heated at 160 ° C. and 20 kgf using a vacuum press laminating machine. Thermocompression bonding under reduced pressure for 60 seconds.
• Solder heat resistance A sample (PI film / adhesive layer / rolled copper foil) cured by heating in the same manner as in the evaluation of adhesion was prepared, cut into 20 mm squares, and floated in a 300 ° C. solder bath with the polyimide surface up for 1 minute. Was. The appearance was evaluated. ⁇ : no swelling or peeling ⁇ : swelling or peeling
• the solution of the adhesive composition was applied to a polyimide film (Kaneka Apical 12.5 NPI) so that the thickness of the adhesive layer was 20 ⁇ m after drying, and dried at 140 ° C. for 3 minutes in a hot air circulating drier to obtain a B-stage.
• a sample (PI film / adhesive layer) in a state was obtained.
• the adhesive-coated surface of the sample (PI film / adhesive layer) in the B-stage state and a polyimide film (Kaneka Apical 12.5 NPI) were placed under reduced pressure at 160 ° C. and 20 kgf for 60 seconds using a vacuum press laminator. Thermocompression bonding was performed. Then, it was cured by heating at 170 ° C. for 3 hours.
• Samples after curing (PI film / adhesive layer / PI film) were evaluated for flame retardancy in accordance with UL-94 VTM standard. :: Equivalent to VTM-0 ⁇ : Does not satisfy VTM-0
• the solution of the adhesive composition was applied to a polyimide film (Kaneka Apical 12.5 NPI) so that the thickness of the adhesive layer was 20 ⁇ m after drying, and dried at 140 ° C. for 3 minutes in a hot air circulating drier to obtain a B-stage.
• a sample (PI film / adhesive layer) in a state was obtained.
• the resistance value after 250 hours is 1 ⁇ 10 10 ⁇ or more and no dendrites
• the resistance value after 250 hours is 1 ⁇ 10 9 ⁇ or more and less than 1 ⁇ 10 10 ⁇ and no dendrites are generated
• ⁇ The resistance value after 250 hours is less than 1 ⁇ 10 9 ⁇ or dendrites are generated.
• XX Short circuit within 250 hours.
• Synthesis Example 1 A four-necked flask equipped with a stirrer, a solvent recovery device equipped with a cooling tube, a nitrogen inlet tube and a thermometer was charged with HCA (9,10-dihydro-9-oxa-10-phos trade name, manufactured by Sanko Co., Ltd.). 558.3 g of faphenanthrene-10-oxide) and 391.6 g of Phenodur® PR411 (trade name: 75% solid content in butanol) manufactured by Allnex Co. were added, and the mixture was stirred and subjected to nitrogen flow. The temperature was raised to 199 ° C over 180 minutes.
• Phosphorus compound A has the structure of chemical formula (9).
• Polymerization of resins 1-2 having imide bonds Polymerization of a resin having an imide bond was carried out using the resin composition (mol%) of the raw materials shown in Table 1. Specifically, polymerization was performed as follows.
• the adhesive compositions of Examples 1 to 7 satisfying the conditions of the present invention show excellent results in adhesiveness, solder heat resistance, flame retardancy, and insulation reliability.
• Comparative Example 1 not containing a phosphorus compound Comparative Examples 2 and 3 not containing a phosphorus compound of the general formula (1), and Comparative Example 4 not containing a resin having an imide bond, the properties were unsatisfactory. there were.
• the adhesive composition of the present invention is excellent in adhesiveness, heat resistance, flame retardancy, handleability, insulation reliability by combining a resin having an imide bond and a specific phosphorus compound, and has an adhesive film and a coverlay film. It is suitable for a copper-clad laminate or the like, and is extremely useful.

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