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WO2024009969A1 - Composition adhésive, film de liaison, stratifié comprenant une couche de composition adhésive, stratifié et film de protection contre les ondes électromagnétiques - Google Patents

Composition adhésive, film de liaison, stratifié comprenant une couche de composition adhésive, stratifié et film de protection contre les ondes électromagnétiques Download PDF

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Publication number
WO2024009969A1
WO2024009969A1 PCT/JP2023/024689 JP2023024689W WO2024009969A1 WO 2024009969 A1 WO2024009969 A1 WO 2024009969A1 JP 2023024689 W JP2023024689 W JP 2023024689W WO 2024009969 A1 WO2024009969 A1 WO 2024009969A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive composition
carbon atoms
acid
polyester
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/024689
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English (en)
Japanese (ja)
Inventor
勝 安藤
雅弘 鳥居
愛 岩田
真 平川
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.)
Toagosei Co Ltd
Original Assignee
Toagosei Co Ltd
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 Toagosei Co Ltd filed Critical Toagosei Co Ltd
Priority to JP2024532132A priority Critical patent/JPWO2024009969A1/ja
Priority to KR1020257000837A priority patent/KR20250030475A/ko
Priority to CN202380050685.8A priority patent/CN119452058A/zh
Publication of WO2024009969A1 publication Critical patent/WO2024009969A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C09J177/12—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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
    • H05K9/00—Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073—Shielding materials
    • H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding

Definitions

  • the present invention relates to an adhesive composition, a bonding film, a laminate with an adhesive composition layer, a laminate, and an electromagnetic shielding film.
  • flexible printed wiring boards can be mounted three-dimensionally and with high density even in a limited space, their uses are expanding.
  • products related to flexible printed wiring boards have diversified and the demand for them has increased.
  • Such related products include flexible copper-clad laminates made by bonding copper foil to polyimide film, flexible printed wiring boards with electronic circuits formed on flexible copper-clad laminates, and flexible printed wiring boards made by bonding flexible printed wiring boards with reinforcing plates. Examples include a flexible printed wiring board with a reinforcing plate, a flexible copper-clad laminate, and a multilayer board made by stacking and bonding flexible printed wiring boards.
  • an adhesive is usually used to bond the polyimide film and the copper foil.
  • Patent Document 1 describes an adhesive.
  • the adhesive described in Patent Document 1 consists of a polyesteramide resin (A) and an epoxy compound (B) having an acid value of 100 to 2000 equivalents/t.
  • Patent Document 2 describes an adhesive tape for TAB.
  • the adhesive tape described in Patent Document 2 includes an adhesive layer containing at least a polyamide resin, an epoxy resin, and a phenol resin on an organic insulating film.
  • the adhesive layer has an elastic modulus of 200 to 500 MPa at 100°C, and an elastic modulus of 10 to 100 MPa at 180°C.
  • Patent Document 3 describes an adhesive resin composition.
  • the adhesive resin composition described in Patent Document 3 includes (A) a curing component containing an epoxy resin and a curing agent, (B) a polyamide soluble in an aprotic solvent, (C) a flame retardant, and (D ) solvent.
  • the epoxy resin includes a phenol aralkyl type epoxy resin.
  • the solvent is comprised of an aprotic solvent.
  • the weight fraction of the component (A) based on the total weight of the component (A) and the component (B) is 41 to 70% by weight.
  • Patent Document 4 describes a thermosetting adhesive composition.
  • the thermosetting adhesive composition described in Patent Document 4 includes a (meth)acrylic polymer having a glass transition temperature of 5° C. or higher, a liquid epoxy resin, a solid resin, and a polyamide elastomer having a reactive functional group at the end. , and an epoxy resin curing agent.
  • the solid resin is one or more selected from solid epoxy resins and solid phenol resins.
  • the solid resin is compatible with the liquid epoxy resin.
  • the solid resin has a softening point of 50°C or more and 100°C or less.
  • Patent Document 5 describes a polyesteramide resin composition.
  • the polyesteramide resin composition described in Patent Document 5 contains 1 to 50 parts by weight of a polyesteramide resin having a polyamide repeating unit with a specific structure and 99 to 50 parts by weight of a positive or negative electrode active material.
  • Patent Document 6 describes an adhesive composition.
  • the adhesive composition described in Patent Document 6 contains a styrene-isobutylene-styrene olefin elastomer, a styrene-ethylene-butylene-styrene olefin elastomer, and a maleic anhydride-modified product thereof based on 100 parts by weight of polyether ester amide. It contains one or more of these in a total amount of 1 to 300 parts by weight.
  • Patent Document 1 JP-A-2006-152015 Patent Document 2: JP-A-2009-40814 Patent Document 3: JP-A-2012-25888 Patent Document 4: JP-A-2015-193683 Patent Document 5: JP-A-2015-193683 2010-31099 Publication Patent Document 6: International Publication No. 2012/011265
  • the problem to be solved by the present invention is to provide an adhesive composition in which the obtained cured product has excellent solder heat resistance even in a normal humidity environment and also has excellent long-term moist heat resistance.
  • Another problem to be solved by the present invention is to provide a bonding film, a laminate with an adhesive composition layer, a laminate, or an electromagnetic shielding film using the adhesive composition.
  • Means for solving the above problems include the following aspects.
  • the polyester portion of the polyester polyamide resin (A) is an aliphatic dicarboxylic acid having 6 to 22 carbon atoms, an aromatic dicarboxylic acid having 6 to 22 carbon atoms, and/or an alicyclic dicarboxylic acid having 6 to 22 carbon atoms.
  • the polyamide portion of the polyester polyamide resin (A) is an aliphatic dicarboxylic acid having 6 to 22 carbon atoms, an aromatic dicarboxylic acid having 6 to 22 carbon atoms, and/or an alicyclic dicarboxylic acid having 6 to 22 carbon atoms, and/or an alicyclic dicarboxylic acid having 6 to 22 carbon atoms.
  • a polycondensate of a dicarboxylic acid containing a dimerized aliphatic diacid having 20 to 48 carbon atoms and a diamine having an aromatic and/or alicyclic skeleton having 6 to 44 carbon atoms The adhesive composition according to ⁇ 1> or ⁇ 2> above.
  • ⁇ 4> The adhesive composition according to any one of ⁇ 1> to ⁇ 3>, further comprising a polyurethane resin (C).
  • C polyurethane resin
  • the content of the conductive filler (D) is the polyester polyamide resin (A), the epoxy resin (B), and the polyester urethane resin (C) that may be included as an optional component in the adhesive composition.
  • the adhesive composition according to the above ⁇ 6> which is 10 parts by mass to 350 parts by mass based on 100 parts by mass of the total amount.
  • ⁇ 9> The adhesive composition according to any one of ⁇ 1> to ⁇ 8>, further comprising an inorganic filler (F) having no conductivity.
  • F inorganic filler
  • ⁇ 10> The adhesive composition according to any one of ⁇ 1> to ⁇ 9>, further comprising an organic filler (G) having no conductivity.
  • G organic filler
  • a bonding film comprising a release film in contact with the surface of the bonding film.
  • ⁇ 12> Comprising an adhesive composition layer and a base film in contact with at least one surface of the adhesive composition layer,
  • the adhesive composition layer is formed of an uncured adhesive composition according to any one of ⁇ 1> to ⁇ 10>, wherein a portion of the adhesive composition is cured.
  • a laminate with an adhesive composition layer which is a B-stage adhesive composition layer formed by curing the adhesive composition layer, or a cured layer formed by curing the adhesive composition.
  • a laminate comprising a cured layer obtained by curing the adhesive composition according to any one of ⁇ 1> to ⁇ 10>.
  • An electromagnetic shielding film comprising a cured layer formed by curing the adhesive composition according to any one of ⁇ 1> to ⁇ 10>.
  • an adhesive composition in which the obtained cured product has excellent solder heat resistance even in a normal humidity environment and also has excellent long-term moist heat resistance.
  • a bonding film, a laminate with an adhesive composition layer, a laminate, or an electromagnetic shielding film using the adhesive composition can be provided.
  • the present disclosure is not limited to such embodiments.
  • " ⁇ " is used to include the numerical values described before and after it as a lower limit value and an upper limit value.
  • the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step. good.
  • the upper limit or lower limit of the numerical range may be replaced with the values shown in the examples.
  • the amount of each component in the composition means the total amount of the multiple substances present in the composition. do.
  • the term “step” is included not only in an independent step but also in the case where the intended purpose of the step is achieved even if the step cannot be clearly distinguished from other steps.
  • “mass %” and “weight %” have the same meaning
  • “mass parts” and “weight parts” have the same meaning.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • “(meth)acrylic” represents both or either acrylic and methacrylic.
  • a hydrocarbon chain may be described by a simplified structural formula in which symbols for carbon (C) and hydrogen (H) are omitted. Below, the content of the present disclosure will be explained in detail.
  • the adhesive composition of the present disclosure includes a polyester polyamide resin (A) having a polyester portion and a polyamide portion, and an epoxy resin (B).
  • the amount of the epoxy resin (B) is 1 part by mass to 60 parts by mass relative to 100 parts by mass of the polyester polyamide resin (A).
  • the adhesive composition of the present disclosure can be suitably used as an adhesive composition for adhering polyimide or for adhering metal, and can be particularly suitably used as an adhesive composition for adhesion between polyimide and metal.
  • the present inventors have discovered that cured products of conventional adhesive compositions do not have sufficient soldering heat resistance in a normal humidity environment. As mentioned above, there is a need for an adhesive composition that does not lose its strength even after long-term storage under high temperature and high humidity conditions. As a result of intensive studies by the present inventors, it was found that the epoxy resin (B) contains a polyester polyamide resin (A) having a polyester part and a polyamide part, and an epoxy resin (B). ) is 1 part by mass to 60 parts by mass, the resulting cured product can provide an adhesive composition that has excellent soldering heat resistance even in a normal humidity environment and also has excellent long-term moist heat resistance. I found it.
  • the polyester polyamide resin (A) and the epoxy resin (B) act in concert with each other and complement each other. Furthermore, the polyester portion constituting the polyester polyamide resin (A) improves the hydrophobicity of the resin and improves its moisture resistance. Therefore, the obtained cured product has a low moisture absorption rate. Water absorption of the obtained cured product is suppressed over a long period of time even under high temperature and high humidity conditions. The adhesive properties of the resulting cured product are also maintained over a long period of time. The obtained cured product has excellent solder heat resistance even in a normal humidity environment, and also has excellent long-term moist heat resistance.
  • the adhesive composition of the present disclosure includes a polyester polyamide resin (A) having a polyester portion and a polyamide portion, and an epoxy resin (B).
  • the amount of the epoxy resin (B) is 1 part by mass to 60 parts by mass relative to 100 parts by mass of the polyester polyamide resin (A).
  • the adhesive composition of the present disclosure has the above-mentioned structure and thus has excellent adhesive properties and storage stability.
  • polyester polyamide resin (A) etc. are also referred to as “component (A)” etc.
  • the adhesive composition of the present disclosure contains a polyester polyamide resin (A).
  • the polyester polyamide resin (A) contains a polyester portion and a polyamide portion.
  • the polyester portion has two or more ester bonds.
  • the polyamide portion has two or more amide bonds.
  • the polyester portion and the polyamide portion may be bonded via an ester bond or an amide bond.
  • the polyester polyamide resin (A) may be any resin as long as it has two or more ester bonds and two or more amide bonds.
  • the polyester polyamide resin (A) is preferably a resin having a polyester chain and two or more amide bonds, a resin having a polyamide chain and two or more ester bonds, a resin having a polyester chain and a polyamide chain, or the like.
  • the weight average molecular weight of the polyester chains may be 1,000 or more.
  • the weight average molecular weight of the polyamide chains may be 1,000 or more.
  • the upper limit of the weight average molecular weight of each of the polyester chain and the polyamide chain is not particularly limited, and may be, for example, 150,000 or less.
  • the polyester polyamide resin (A) is preferably a resin formed by reacting at least a polycarboxylic acid, a polyol, and a polyamine as its raw materials, and a resin formed by reacting at least a dicarboxylic acid, a diol, and a diamine. More preferably, it is a resin. It is preferable that the polyester polyamide resin (A) is a linear resin. It is preferable that the polyester polyamide resin (A) does not have an aromatic ring. By using a polyester polyamide resin (A) that is linear and does not have an aromatic ring, processability in hot pressing or hot lamination can be improved.
  • the polyester portion in the polyester polyamide resin (A) is preferably formed from an acid component and an alcohol component.
  • the acid component polyvalent carboxylic acid compounds are preferred, and dicarboxylic acid compounds are more preferred.
  • the acid component sulfocarboxylic acid compounds and the like can also be used.
  • the acid component aliphatic acids are preferably mentioned.
  • the alcohol component polyhydric alcohol compounds are preferred, and diol compounds are more preferred.
  • the polyester portion may be formed from a hydroxycarboxylic acid compound.
  • aromatic acids include aromatic dicarboxylic acids and aromatic oxycarboxylic acids.
  • aromatic dicarboxylic acid include aromatic dicarboxylic acids that do not have at least one of a sulfonic acid group and a sulfonic acid group, and aromatic dicarboxylic acids that have a sulfonic acid group or a sulfonic acid group.
  • aromatic dicarboxylic acids that do not have at least one of a sulfonic acid group and a sulfonic acid group include terephthalic acid, isophthalic acid, orthophthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, and 5-hydroxyisophthalic acid.
  • Examples of the sulfonic acid group or aromatic dicarboxylic acid having a sulfonic acid group include sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5-(4- Examples include sulfophenoxy)isophthalic acid, sulfoterephthalic acid, metal salts thereof, and ammonium salts thereof.
  • aromatic oxycarboxylic acids include p-hydroxybenzoic acid, p-hydroxyphenylpropionic acid, p-hydroxyphenylacetic acid, 6-hydroxy-2-naphthoic acid, and 4,4-bis(p-hydroxyphenyl). Examples include valeric acid.
  • the acid component may be a derivative of an acid compound such as an ester during resin synthesis.
  • Examples of the aliphatic acid component include alicyclic dicarboxylic acids and aliphatic dicarboxylic acids.
  • Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,2-cyclohexanedicarboxylic acid and its acid anhydride.
  • Examples of aliphatic dicarboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, and dimer acid.
  • the acid component preferably includes azelaic acid and/or dimer acid, and it is particularly preferable to include azelaic acid.
  • the acid component is an aliphatic dicarboxylic acid having 6 to 22 carbon atoms, an aromatic dicarboxylic acid having 6 to 22 carbon atoms, or an alicyclic dicarboxylic acid having 6 to 22 carbon atoms. are preferred, and aliphatic dicarboxylic acids having 6 to 22 carbon atoms or alicyclic dicarboxylic acids having 6 to 22 carbon atoms are more preferred.
  • Preferred examples of the polyhydric alcohol component include aliphatic diol compounds, alicyclic diol compounds, aromatic-containing diol compounds, and ether bond-containing diol compounds.
  • aliphatic diol compounds include ethylene glycol, 1,2-propylene diol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexane.
  • diol 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2-butyl-2-ethyl-1,3-propanediol, hydroxypivalic acid neopentyl glycol ester, dimethylolheptane, and 2, Examples include 2,4-trimethyl-1,3-pentanediol.
  • examples of the alicyclic diol compound include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecanediol, tricyclodecanedimethylol, spiroglycol, hydrogenated bisphenol A, hydrogenated bisphenol A, and ethylene.
  • Examples include oxide adducts and propylene oxide adducts.
  • aromatic-containing diol compounds include para-xylene glycol, meta-xylene glycol, ortho-xylene glycol, 1,4-phenylene glycol, ethylene oxide adduct of 1,4-phenylene glycol, bisphenol A, and ethylene of bisphenol A.
  • Examples include glycols obtained by adding one to several moles of ethylene oxide or propylene oxide to two phenolic hydroxyl groups of bisphenols, such as oxide adducts and propylene oxide adducts.
  • Examples of the ether bond-containing diol compound include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, neopentyl glycol ethylene oxide adduct, and neopentyl glycol propylene oxide adduct. It will be done.
  • diols diols having side chains (for example, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, etc.) are preferred for reasons of compatibility with epoxy resins and solution stability. .
  • the diol component constituting the polyester polyamide resin (A) contains a diol having a side chain from the viewpoint of compatibility with an epoxy resin and the like and solution stability.
  • the side chain in the diol having a side chain is preferably an alkyl group, and the number of carbon atoms in the alkyl group may be, for example, any one of 1, 2, 3, 4, and 5. This also applies to diols having side chains described below. Examples of the diol having a side chain include neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, and 2,2-dimethylolpropionic acid.
  • a hydroxycarboxylic acid compound having a hydroxy group and a carboxy group in its molecular structure can be used.
  • the hydroxycarboxylic acid compounds include 5-hydroxyisophthalic acid, p-hydroxybenzoic acid, p-hydroxyphenyl alcohol, p-hydroxyphenylpropionic acid, p-hydroxyphenylacetic acid, and 6-hydroxy-2-naphthoic acid. , and 4,4-bis(p-hydroxyphenyl)valeric acid.
  • trifunctional or higher functional polycarboxylic acids and/or polyols may be copolymerized with the components constituting the polyester portion of the polyester polyamide resin (A) for the purpose of introducing a branched skeleton.
  • the amount of trifunctional or higher-functional polycarboxylic acids and/or polyols is approximately 0.1 mol % to 5 mol % based on the total acid component or the total polyhydric alcohol component constituting the polyester portion.
  • the concentration of end groups (reaction points) of the resin increases, and a cured layer with a high crosslinking density can be obtained.
  • trifunctional or higher-functional polycarboxylic acids examples include trimellitic acid, trimesic acid, ethylene glycol bis(anhydrotrimellitate), glycerol tris(anhydrotrimellitate), trimellitic anhydride, and pyromellitic anhydride ( PMDA), oxydiphthalic dianhydride (ODPA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 3,3',4,4'-diphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA), 2,2' -bis[(dicarboxyphenoxy)phenyl]propane dianhydride (BSAA) and the like.
  • ODPA oxydiphthalic dianhydride
  • trifunctional or higher functional polyols examples include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
  • the amount of the trifunctional or higher functional polycarboxylic acid and/or polyol is preferably from 0.1 mol% to 5 mol%, more preferably from 0.1 mol% to the total acid component or the total polyhydric alcohol component. It is 3 mol%.
  • the polyester part of the polyester polyamide resin (A) is made of aliphatic dicarboxylic acids having 6 to 22 carbon atoms, aromatic dicarboxylic acids having 6 to 22 carbon atoms, and/or carbon atoms, from the viewpoint of soldering heat resistance and adhesive properties.
  • It is preferably a polycondensate of an alicyclic dicarboxylic acid having 6 to 22 carbon atoms and an aliphatic diol having 2 to 54 carbon atoms, an aromatic diol having 2 to 54 carbon atoms, or an alicyclic diol having 2 to 54 carbon atoms. .
  • aliphatic dicarboxylic acid having 6 to 22 carbon atoms, aromatic dicarboxylic acid having 6 to 22 carbon atoms, and/or alicyclic dicarboxylic acid having 6 to 22 carbon atoms is an aliphatic dicarboxylic acid having 6 to 22 carbon atoms, an aromatic dicarboxylic acid having 6 to 22 carbon atoms, and an alicyclic dicarboxylic acid having 6 to 22 carbon atoms; an aliphatic dicarboxylic acid having 6 to 22 carbon atoms and an aromatic dicarboxylic acid having 6 to 22 carbon atoms; an aliphatic dicarboxylic acid having 6 to 22 carbon atoms and an alicyclic dicarboxylic acid having 6 to 22 carbon atoms; Aromatic dicarboxylic acid having 6 to 22 carbon atoms and alicyclic dicarboxylic acid having 6 to 22 carbon atoms, an aliphatic dicarboxylic acid having 6 to 22 carbon atoms; aromatic
  • aliphatic diol having 2 to 54 carbon atoms, aromatic diol having 2 to 54 carbon atoms, or alicyclic diol having 2 to 54 carbon atoms is an aliphatic diol having 2 to 54 carbon atoms; an aromatic diol having 2 to 54 carbon atoms; an alicyclic diol having 2 to 54 carbon atoms; includes.
  • the polyester portion of the polyester polyamide resin (A) may be subjected to acid addition for the purpose of introducing a carboxyl group, if necessary.
  • the amount of acid addition is approximately 0.1 mol % to 10 mol % based on the total acid component or the total polyhydric alcohol component constituting the polyester portion. If a monocarboxylic acid, dicarboxylic acid, or polyfunctional carboxylic acid compound is used for acid addition, there is a risk that the molecular weight will decrease due to transesterification. Therefore, it is preferable to use an acid anhydride for acid addition.
  • acid anhydrides examples include succinic anhydride, maleic anhydride, orthophthalic acid, 2,5-norbornenedicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride (PMDA), and oxydiphthalic anhydride.
  • Anhydride 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 3,3',4,4'-diphenyltetracarboxylic dianhydride (BPDA), 3, 3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA), 2,2'-bis[(dicarboxylic dianhydride), Examples include phenoxy)phenyl]propane dianhydride (BSAA).
  • Examples of the acid addition method include a method in which the acid is added directly after polyester polycondensation in a bulk state, and a method in which the polyester is dissolved and added.
  • the reaction rate in the bulk state is fast.
  • gelation may occur if a large amount of acid is added to the polyester portion of the polyester polyamide resin (A), and the reaction temperature in the bulk state is high. Therefore, when reacting in bulk, care must be taken to prevent oxidation by blocking oxygen gas.
  • the reaction is slow in acid addition in a solution state, a large amount of carboxyl groups can be stably introduced into the polyester portion of the polyester polyamide resin (A).
  • the polyamide portion in the polyester polyamide resin (A) is preferably formed from an acid component and an amine component.
  • the acid component polyvalent carboxylic acid compounds are preferred, and dicarboxylic acid compounds are more preferred.
  • the acid component sulfocarboxylic acid compounds and aliphatic acids can be used.
  • the acid component those mentioned above as the acid component of the polyester portion are preferably mentioned.
  • the polyamide part of the polyester polyamide resin (A) is made of an aliphatic dicarboxylic acid having 6 to 22 carbon atoms, an aromatic dicarboxylic acid having 6 to 22 carbon atoms, or an aromatic dicarboxylic acid having 6 to 22 carbon atoms, from the viewpoint of soldering heat resistance and adhesive properties.
  • alicyclic dicarboxylic acids and/or dimeric aliphatic diacids having 20 to 48 carbon atoms It is more preferable to include a dicarboxylic acid including a cyclic dicarboxylic acid and/or a dimerized aliphatic diacid having 20 to 48 carbon atoms, and it is particularly preferable to include azelaic acid.
  • the aliphatic, aromatic or alicyclic dicarboxylic acid preferably has 6 to 12 carbon atoms, more preferably 8 to 10 carbon atoms.
  • the number of carbon atoms in the dimerized aliphatic diacid is preferably 30 to 48, more preferably 32 to 40.
  • polyamine compounds are preferred, and diamine compounds are more preferred.
  • the polyamide portion may be formed of an aminocarboxylic acid compound.
  • diamine compounds include diaminocyclohexane, piperidine, isophorone diamine, 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, o-(or m-, p-)phenylenediamine, o-(or m-, p-)xylenediamine, 3,3' -(or 3,4'-)diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-(or 3,4'-)diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-( or 3,4
  • the amine component preferably contains a diamine having an aromatic skeleton having 6 to 44 carbon atoms or an alicyclic skeleton having 6 to 44 carbon atoms, and an alicyclic skeleton having 6 to 44 carbon atoms. It is more preferable to include a diamine having a formula skeleton, and it is particularly preferable to include isophorone diamine.
  • the diamine preferably has 8 to 30 carbon atoms, more preferably 10 to 24 carbon atoms.
  • the polyamide part of the polyester polyamide resin (A) is made of aliphatic dicarboxylic acids having 6 to 22 carbon atoms, aromatic dicarboxylic acids having 6 to 22 carbon atoms, and aliphatic dicarboxylic acids having 6 to 22 carbon atoms, from the viewpoint of solder heat resistance, adhesiveness, and conductivity. /or an alicyclic dicarboxylic acid having 6 to 22 carbon atoms and/or a dicarboxylic acid containing a dimerized aliphatic diacid having 20 to 48 carbon atoms, and an aromatic acid having 6 to 44 carbon atoms and/or an aromatic acid having 6 to 44 carbon atoms.
  • It is preferably a polycondensate with a diamine having an alicyclic skeleton of 6 to 22 carbon atoms or an alicyclic dicarboxylic acid having 6 to 22 carbon atoms and/or a diamine having 20 to 48 carbon atoms. More preferably, it is a polycondensate of a dicarboxylic acid containing a dimerized aliphatic diacid and a diamine having an alicyclic skeleton having 6 to 44 carbon atoms.
  • aliphatic dicarboxylic acids having 6 to 22 carbon atoms aromatic dicarboxylic acids having 6 to 22 carbon atoms, and/or alicyclic dicarboxylic acids having 6 to 22 carbon atoms, and/or dicarboxylic acids having 20 to 48 carbon atoms
  • Quantified aliphatic diacids are an aliphatic dicarboxylic acid having 6 to 22 carbon atoms, an aromatic dicarboxylic acid having 6 to 22 carbon atoms, an alicyclic dicarboxylic acid having 6 to 22 carbon atoms, and a dimerized aliphatic diacid having 20 to 48 carbon atoms; an aliphatic dicarboxylic acid having 6 to 22 carbon atoms and a dimerized aliphatic diacid having 20 to 48 carbon atoms; An aromatic dicarboxylic acid having 6 to 22 carbon atoms and a dimerized aliphatic diacid having 20 to 48 carbon atoms, an alicyclic
  • the polyester portion of the polyester polyamide resin (A) is an aliphatic dicarboxylic acid having 6 to 22 carbon atoms, an aromatic dicarboxylic acid having 6 to 22 carbon atoms, and/or an alicyclic dicarboxylic acid having 6 to 22 carbon atoms, A polycondensate with an aliphatic diol having 2 to 54 carbon atoms, an aromatic diol having 2 to 54 carbon atoms, or an alicyclic diol having 2 to 54 carbon atoms,
  • the polyamide portion of the polyester polyamide resin (A) is an aliphatic dicarboxylic acid having 6 to 22 carbon atoms, an aromatic dicarboxylic acid having 6 to 22 carbon atoms, and/or an alicyclic dicarboxylic acid having 6 to 22 carbon atoms, and/or an alicyclic dicarboxylic acid having 6 to 22 carbon atoms.
  • a polycondensate of a dicarboxylic acid containing a dimerized aliphatic diacid having 20 to 48 carbon atoms and a diamine having an aromatic and/or alicyclic skeleton having 6 to 44 carbon atoms is preferable. This makes it possible to provide an adhesive composition with low water absorption and excellent long-term heat and humidity resistance.
  • a chain extender may be used if necessary.
  • the chain extender include the diol compounds already described as constituent components of the polyester moiety, and compounds having one carboxy group and two hydroxy groups (e.g., dimethylolpropionic acid, dimethylolbutanoic acid, etc.). Can be mentioned.
  • diol compounds are preferred, diol compounds having a side chain are more preferred, and diol compounds having a branched chain are particularly preferred.
  • the diol compound having a side chain was selected from the group consisting of neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, and 2,2-dimethylolpropionic acid from the viewpoint of electrical conductivity. Preferably, it contains at least one compound.
  • the diol compound having a side chain includes at least one compound selected from the group consisting of neopentyl glycol and 2-butyl-2-ethyl-1,3-propanediol, and 2,2-dimethylolpropionic acid. It is particularly preferred to include.
  • Polyamine compounds may be used as chain extenders.
  • the polycarboxylic acid, polyol, polyamine, and, if necessary, the chain extender may be charged into the reaction vessel all at once, or may be charged in portions.
  • the ratio of the carboxyl group/hydroxyl group and amino group to the total of the hydroxyl value and amine value of the polyol and polyamine in the system and the total of the carboxy group of the polycarboxylic acid is preferably It is 0.9 or more and 1.1 or less, more preferably 0.98 or more and 1.02 or less, particularly preferably 1.
  • This reaction can be carried out in the presence or absence of a solvent.
  • solvents examples include ester solvents (e.g., ethyl acetate, butyl acetate, ethyl butyrate, etc.), ether solvents (e.g., dioxane, tetrahydrofuran, diethyl ether, etc.), and ketone solvents (e.g., cyclohexanone, methyl ethyl ketone, methyl isobutyl). ketones, etc.), aromatic hydrocarbon solvents (eg, benzene, toluene, xylene, etc.), and mixed solvents thereof.
  • ester solvents e.g., ethyl acetate, butyl acetate, ethyl butyrate, etc.
  • ether solvents e.g., dioxane, tetrahydrofuran, diethyl ether, etc.
  • ketone solvents e.g., cyclohexanone, methyl
  • the reaction device is not limited to a reaction vessel equipped with a stirring device, but also a mixing and kneading device such as a kneader or a twin-screw extruder can be used.
  • a catalyst eg, tetrabutoxy titanate, etc.
  • a condensing agent or the like may also be used.
  • the glass transition temperature (Tg) of the polyester part in the polyester polyamide resin (A) is preferably 40°C to 150°C, and 45°C to 120°C from the viewpoint of adhesiveness, conductivity, and heat resistance.
  • the temperature is more preferably 50°C to 90°C, even more preferably 60°C to 70°C.
  • the glass transition temperature (Tg) of the polyester polyamide resin (A) is preferably 30°C to 150°C, more preferably 40°C to 140°C, from the viewpoint of adhesiveness, conductivity, and heat resistance.
  • the temperature is preferably 50°C to 90°C, more preferably 60°C to 70°C.
  • the weight average molecular weight (Mw) of the polyester polyamide resin (A) is preferably 5,000 to 150,000, and 10,000 to 100,000 from the viewpoint of soldering heat resistance, conductivity, and heat resistance. It is more preferably 30,000 to 80,000, and particularly preferably 40,000 to 60,000.
  • the number average molecular weight (Mn) of the polyester polyamide resin (A) is preferably 1,500 to 50,000, and 10,000 to 25,000 from the viewpoint of soldering heat resistance, conductivity, and heat resistance. More preferably, it is 13,000 to 20,000.
  • the values of the number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin in the present disclosure are the molecular weight measured by gel permeation chromatography (hereinafter also referred to as "GPC") under the following conditions in terms of polystyrene. means value.
  • GPC gel permeation chromatography
  • the amine value of the polyester polyamide resin (A) is preferably 1.0 mgKOH/g to 12.0 mgKOH/g, and 3.0 mgKOH/g to 11 It is more preferably .0 mgKOH/g, even more preferably 6.0 mgKOH/g to 10.0 mgKOH/g, and particularly preferably 7.0 mgKOH/g to 8.0 mgKOH/g.
  • the amine value of the resin in the present disclosure is measured and calculated by potentiometry in accordance with JIS K 7237 (1995).
  • the adhesive composition of the present disclosure may contain one type of polyester polyamide resin (A) alone, or may contain two or more types of polyester polyamide resins (A).
  • the content of the polyester polyamide resin (A) is preferably 5% by mass to 98% by mass, based on the total solid content of the adhesive composition, from the viewpoints of adhesiveness, conductivity, and heat resistance. It is more preferably from 20% to 90% by weight, even more preferably from 30% to 85% by weight.
  • the adhesive composition of the present disclosure contains an epoxy resin (B).
  • the epoxy resin (B) is a component that provides adhesive properties and heat resistance in the cured portion after adhesion.
  • the epoxy resin (B) in the present disclosure includes not only a high molecular compound having an epoxy group but also a low molecular compound having an epoxy group.
  • the number of epoxy groups in the epoxy resin (B) is preferably 2 or more.
  • Examples of the epoxy resin (B) include glycidyl esters, glycidyl ethers, novolac type epoxy resins, and the like.
  • glycidyl ester examples include orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, p-hydroxybenzoic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, and adipic acid diglycidyl ester.
  • examples include glycidyl ester, sebacic acid diglycidyl ester, trimellitic acid triglycidyl ester, and the like.
  • glycidyl ethers include bisphenol A diglycidyl ether and its oligomers, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, Examples include trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, tetraphenylglycidyl ether ethane, triphenylglycidyl ether ethane, polyglycidyl ether of sorbitol, polyglycidyl ether of polyglycerol, and the like.
  • Examples of the novolac type epoxy resin include phenol novolac epoxy resin, o-cresol novolac epoxy resin, and bisphenol A novolac epoxy resin.
  • Examples of the epoxy resin (B) include brominated bisphenol A type epoxy resin with flame retardancy, phosphorus-containing epoxy resin, trisphenolmethane skeleton-containing epoxy resin, dicyclopentadiene skeleton-containing epoxy resin, naphthalene skeleton-containing epoxy resin, anthracene Type epoxy resins, tert-butylcatechol type epoxy resins, biphenyl type epoxy resins, bisphenol S type epoxy resins, etc. can also be used.
  • the epoxy resin (B) preferably contains an epoxy resin containing a trisphenolmethane skeleton from the viewpoints of adhesiveness and soldering heat resistance.
  • the epoxy resin (B) in order to exhibit high heat resistance after curing, preferably contains a compound having three or more epoxy groups in one molecule.
  • the polyester urethane resin (A) and the resin having a carboxy group or carboxylic acid anhydride structure (C ), and sufficient heat resistance can be obtained.
  • the content of the compound having three or more epoxy groups in one molecule in the epoxy resin (B) is preferably 15% by mass or more based on the total mass of the epoxy resin (B). , more preferably 20% by mass or more, particularly preferably 25% by mass or more.
  • the adhesive composition of the present disclosure may contain one type of epoxy resin (B) alone, or may contain two or more types of epoxy resin (B).
  • the content of the epoxy resin (B) is 1% by mass to 60% by mass based on 100 parts by mass of the polyester polyamide resin (A) in the adhesive composition, and the content is 1% by mass to 60% by mass, and From the viewpoint of conductivity, the content is preferably 2% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 10% by mass to 40% by mass.
  • the total amount of polyester polyamide resin (A) and epoxy resin (B) is preferably 50 mass based on the total solid content excluding filler of the adhesive composition from the viewpoint of soldering heat resistance, adhesiveness, and conductivity. % or more, more preferably 80% by mass or more, and may be 100% by mass.
  • the adhesive composition of the present disclosure further includes a polyurethane resin (C). Thereby, the water absorption rate can be further lowered. It is more preferable that the polyurethane resin (C) further includes a polyester polyurethane resin.
  • the polyurethane resin (C) is not particularly limited, and any known polyurethane resin can be used.
  • the polyurethane resin (C) is preferably a polyester polyurethane resin from the viewpoints of solder heat resistance, adhesiveness, and conductivity.
  • the diisocyanate component constituting the polyester polyurethane resin preferably contains a diisocyanate compound having a hydrocarbon group having 8 to 14 carbon atoms.
  • the polyester polyurethane resin may be any resin having two or more ester bonds and two or more urethane bonds, and is preferably a resin having a polyester chain and two or more urethane bonds.
  • the polyester polyurethane resin is preferably a resin formed by reacting at least a polyester polyol, a polyisocyanate, and a chain extender. It is more preferable that the polyester polyurethane resin is a resin formed by reacting at least a polyester polyol, a polyisocyanate, and a diol compound.
  • the polyester portion in the polyester polyurethane resin is preferably formed from an acid component and an alcohol component.
  • the acid component polyvalent carboxylic acid compounds are preferred, and dicarboxylic acid compounds are more preferred.
  • the acid component sulfocarboxylic acid compounds and the like can also be used.
  • aromatic acids are preferably mentioned.
  • Specific examples of the acid component include those mentioned above for the polyester polyamide resin (A).
  • the alcohol component polyhydric alcohol compounds are preferred, and diol compounds are more preferred.
  • Specific examples of the alcohol component include those mentioned above for the polyester polyamide resin (A).
  • the polyester portion may be formed from a hydroxycarboxylic acid compound.
  • the amount of aromatic acid relative to the total amount of 100 mol% of all acid components constituting the polyester portion of the polyester polyurethane resin is preferably 30 mol% or more, and 45 mol% from the viewpoint of adhesiveness, heat resistance, and moist heat resistance. % or more, and particularly preferably 60 mol% or more.
  • trifunctional or higher functional polycarboxylic acids and/or polyols may be copolymerized, if necessary.
  • the amount of trifunctional or higher-functional polycarboxylic acids and/or polyols is approximately 0.1 mol % to 5 mol % based on the total acid component or the total polyhydric alcohol component constituting the polyester portion.
  • trifunctional or higher-functional polycarboxylic acids examples include trimellitic acid, trimesic acid, ethylene glycol bis(anhydrotrimellitate), glycerol tris(anhydrotrimellitate), trimellitic anhydride, and pyromellitic anhydride ( PMDA), oxydiphthalic dianhydride (ODPA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 3,3',4,4'-diphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA), 2,2' -bis[(dicarboxyphenoxy)phenyl]propane dianhydride (BSAA) and the like.
  • ODPA oxydiphthalic dianhydride
  • trifunctional or higher functional polyols examples include glycerin, trimethylol-ethane, trimethylolpropane, and pentaerythritol.
  • the amount of the trifunctional or higher functional polycarboxylic acid and/or polyol is preferably from 0.1 mol% to 5 mol%, more preferably from 0.1 mol% to the total acid component or the total polyhydric alcohol component. It is 3 mol%.
  • acid addition may be performed to the polyester portion of the polyester polyurethane resin for the purpose of introducing a carboxy group.
  • the amount of acid addition is approximately 0.1 mol % to 10 mol % based on the total acid component or the total polyhydric alcohol component constituting the polyester portion. If a monocarboxylic acid, dicarboxylic acid, or polyfunctional carboxylic acid compound is used for acid addition, there is a risk that the molecular weight will decrease due to transesterification. Therefore, it is preferable to use an acid anhydride for acid addition.
  • acid anhydrides examples include succinic anhydride, maleic anhydride, orthophthalic acid, 2,5-norbornenedicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride (PMDA), and oxydiphthalic anhydride.
  • Anhydride 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 3,3',4,4'-diphenyltetracarboxylic dianhydride (BPDA), 3, 3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA), 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA), 2,2'-bis[(dicarboxylic dianhydride), Examples include phenoxy)phenyl]propane dianhydride (BSAA).
  • Examples of the acid addition method include a method in which the acid is added directly after polyester polycondensation in a bulk state, and a method in which the polyester is dissolved and added.
  • the reaction rate in the bulk state is fast.
  • gelation may occur if a large amount of acid is added to the polyester portion of the polyester polyamide resin (A), and the reaction temperature in the bulk state is high. Therefore, when reacting in bulk, care must be taken to prevent oxidation by blocking oxygen gas.
  • the reaction is slow in acid addition in a solution state, a large amount of carboxyl groups can be stably introduced into the polyester portion of the polyester polyamide resin (A).
  • the polyurethane portion of the polyester polyurethane resin is composed of at least a diisocyanate component.
  • the diisocyanate component includes a diisocyanate compound having a hydrocarbon group having 8 to 14 carbon atoms.
  • the methylene group in the hydrocarbon group may be replaced with a non-reactive bond (eg, -O-, -S-, -CO-, -COO-, -OCO-, etc.).
  • the amount of the diisocyanate compound having a hydrocarbon group having 8 to 14 carbon atoms in the diisocyanate component is usually 70 mol% or more, preferably 90 mol% or more, and may be 100 mol%.
  • the polyurethane portion of the polyester polyurethane resin may be composed of a monofunctional or trifunctional or more functional isocyanate component in addition to the diisocyanate component.
  • the number of carbon atoms in the hydrocarbon group in the diisocyanate compound having a hydrocarbon group having 8 to 14 carbon atoms is 8 to 14 carbon atoms, from the viewpoint of conductivity of the obtained cured product after soldering, after long-term reliability test, and after thermal cycle test. It is preferably 12, more preferably 8-10.
  • the diisocyanate compound having a hydrocarbon group having 8 to 14 carbon atoms preferably has an alicyclic structure from the viewpoint of conductivity of the obtained cured product after soldering, after a long-term reliability test, and after a thermal cycle test. .
  • the amount of the diisocyanate component per 1 molar equivalent of the polyester portion is preferably 5 molar equivalents to 50 molar equivalents.
  • the amount of urethane bonds per 1 molar equivalent of the polyester portion is preferably 10 molar equivalents to 100 molar equivalents.
  • the polyisocyanate used in the production of polyester polyurethane resin is one type of diisocyanate, its dimer (uretdione), its trimer (isocyanurate, triol adduct, biuret), or a mixture of two or more thereof. It may be.
  • the diisocyanate component include diphenylmethane diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 4,4'-diisocyanate diphenyl ether, and m-xylene diisocyanate.
  • Examples include diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, methylenebis(4-cyclohexyl diisocyanate), isophorone diisocyanate, norbornane diisocyanate, and norbornene diisocyanate.
  • diisocyanate 1,3-bis(isocyanatomethyl)cyclohexane
  • 1,4-bis(isocyanatomethyl)cyclohexane methylenebis(4-cyclohexyl diisocyanate)
  • isophorone diisocyanate norbornane diisocyanate
  • norbornene diisocyanate norbornene diisocyanate
  • norbornene diisocyanate aliphatic or alicyclic diisocyanate compounds are preferable, and alicyclic diisocyanate compounds are particularly preferable, from the viewpoint of transparency and conductivity
  • 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, methylenebis(4-cyclohexyldiisocyanate) or norbornane diisocyanate is preferred, and 1,3-bis(isocyanatomethyl)cyclohexane is particularly preferred.
  • a chain extender When producing a polyester polyurethane resin, a chain extender may be used if necessary.
  • the chain extender include the diol compounds already described as constituent components of the polyester moiety, compounds having one carboxy group and two hydroxy groups (e.g., dimethylolpropionic acid, dimethylolbutanoic acid, etc.), and the like. It will be done.
  • diol compounds are preferred, diol compounds having a side chain are more preferred, and diol compounds having a branched chain are particularly preferred.
  • the diol compound having a side chain was selected from the group consisting of neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, and 2,2-dimethylolpropionic acid from the viewpoint of electrical conductivity. Preferably, it contains at least one compound.
  • the diol compound having a side chain includes at least one compound selected from the group consisting of neopentyl glycol and 2-butyl-2-ethyl-1,3-propanediol, and 2,2-dimethylolpropionic acid. It is particularly preferred to include.
  • Polyamino compounds may be used as chain extenders.
  • the polyester polyurethane resin may preferably be free of urea bonds.
  • the polyester polyol, polyisocyanate, and if necessary the chain extender may be charged into the reaction vessel all at once, or may be charged in portions.
  • the ratio of isocyanate groups/hydroxyl functional groups is preferably 0.9 or more based on the total hydroxyl value of the polyester polyol and chain extender in the system and the total isocyanate group of the polyisocyanate. It is 1.1 or less, more preferably 0.98 or more and 1.02 or less, particularly preferably 1.
  • This reaction can be carried out in the presence or absence of a solvent inert to isocyanate groups.
  • the solvent include ester solvents (e.g.
  • the reaction device is not limited to a reaction vessel equipped with a stirring device, but also a mixing and kneading device such as a kneader or a twin-screw extruder can be used.
  • a catalyst used in normal urethane reactions may be used.
  • catalysts include tin-based catalysts (e.g., trimethyltin laurate, dimethyltin dilaurate, trimethyltin hydroxide, dimethyltin dihydroxide, stannath octoate, etc.), lead-based catalysts (e.g., red oleate, Red-2-ethylhexoate, etc.) amine catalysts (eg, triethylamine, tributylamine, morpholine, diazabicyclooctane, diazabicycloundecene, etc.), etc. can be used.
  • tin-based catalysts e.g., trimethyltin laurate, dimethyltin dilaurate, trimethyltin hydroxide, dimethyltin dihydroxide, stannath octoate, etc.
  • lead-based catalysts e.g., red oleate,
  • the glass transition temperature (Tg) of the polyester part in the polyester polyurethane resin is preferably 40°C to 150°C, more preferably 45°C to 120°C, from the viewpoint of adhesiveness, conductivity, and heat resistance.
  • the temperature is preferably 50°C to 90°C, more preferably 60°C to 70°C.
  • the glass transition temperature (Tg) of the polyester polyurethane resin is preferably 30° C. to 150° C., more preferably 40° C. to 140° C., and 50° C. from the viewpoint of adhesiveness, conductivity, and heat resistance.
  • the temperature is more preferably from 0.degree. C. to 90.degree. C., and particularly preferably from 60.degree. C. to 70.degree.
  • the number average molecular weight (Mn) of the polyester polyurethane resin is preferably from 5,000 to 100,000, more preferably from 10,000 to 80,000, from the viewpoints of conductivity and heat resistance. It is more preferably 20,000 to 60,000, particularly preferably 25,000 to 50,000.
  • the weight average molecular weight (Mw) of the polyester polyurethane resin is preferably from 20,000 to 400,000, more preferably from 40,000 to 320,000, from the viewpoints of conductivity and heat resistance. More preferably, it is 80,000 to 240,000.
  • the molecular weight per urethane bond in the polyester polyurethane resin is preferably 200 to 8,000, more preferably 200 to 5,000, and more preferably 300 to 2 ,000 is more preferable, 400 to 1,500 is particularly preferable, and 700 to 1,000 is most preferable.
  • the polyester polyurethane resin has X urethane bonds per molecule and the number average molecular weight is Y, the molecular weight per urethane bond in the polyester polyurethane resin is Y/X.
  • the number of moles of isocyanate groups reacted with 1 mole of polyester polyol which is the raw material of polyester polyurethane resin (C)
  • the number of urethane bonds in the polyester polyurethane resin can also be regarded as "the number of urethane bonds in the polyester polyurethane resin.”
  • the acid value of the polyurethane resin (C) (preferably the acid value of the polyester polyurethane resin) is preferably from 0 mgKOH/g to 50 mgKOH/g, and from 0.1 mgKOH/g to 0.1 mgKOH/g from the viewpoint of adhesiveness and conductivity. It is more preferably 20 mgKOH/g, even more preferably 0.1 mgKOH/g to 5 mgKOH/g, and particularly preferably 1.0 mgKOH/g to 5.0 mgKOH/g. From the viewpoint of heat resistance, the acid value of the polyester polyurethane resin (C) is preferably 20 mgKOH/g or less, particularly preferably 5.0 mgKOH/g or less.
  • the method for measuring the acid value of a resin in the present disclosure is to use a phenolphthalein solution as an indicator and neutralize and titrate a sample with a potassium hydroxide benzyl alcohol solution to determine the acid value.
  • the polyester polyurethane resin preferably contains a polyester polyurethane resin having a polyester structure with a number average molecular weight of 1,000 to 50,000 from the viewpoint of adhesiveness, conductivity, and heat resistance. It is more preferable to include a polyester polyurethane resin having a polyester structure with a number average molecular weight of 3,000 to 40,000, and even more preferably to include a polyester polyurethane resin having a polyester structure with a number average molecular weight of 3,000 to 30,000.
  • polyester polyurethane resin having a polyester structure with a molecular weight of 8,000 to 30,000, and most preferably a polyester polyurethane resin having a polyester structure with a number average molecular weight of 15,000 to 30,000.
  • the adhesive composition of the present disclosure may contain a polyurethane resin (C).
  • the polyurethane resin (C) may be used alone or in combination of two or more.
  • the content of the polyurethane resin (C) (preferably the content of the polyester polyurethane resin) is from 1% by mass to the total solid content of the adhesive composition from the viewpoints of soldering heat resistance, adhesiveness, and conductivity. It is preferably 50% by weight, more preferably 5% to 40% by weight, and particularly preferably 15% to 35% by weight.
  • the adhesive composition of the present disclosure preferably further contains a conductive filler (G) from the viewpoints of conductivity and solder heat resistance.
  • the volume resistivity of the conductive filler is preferably less than 1.0 ⁇ 10 11 ⁇ cm.
  • Preferred examples of the conductive filler (D) include metal particles made of conductive metals (eg, gold, platinum, silver, copper, nickel, etc.) or alloys thereof. From the viewpoint of cost reduction, the conductive filler (D) may be particles other than particles of a single composition. Particles that are not particles of a single composition (hereinafter also referred to as "coated particles”) have a core and a coating layer attached to the core.
  • the core body is made of metal or resin.
  • the covering layer is made of a highly conductive material.
  • the core is preferably made of at least one material selected from the group consisting of nickel, silica, copper, and resin, and more preferably made of a conductive metal or an alloy thereof.
  • the coating layer is preferably a layer made of a material with excellent electrical conductivity, and is preferably a layer made of a conductive metal or a conductive polymer.
  • the conductive metal include gold, platinum, silver, tin, manganese, indium, and alloys thereof.
  • Examples of the conductive polymer include polyaniline and polyacetylene. Among these, silver is preferred from the viewpoint of conductivity. Also included are conductive metal oxides such as indium tin oxide, carbon black, and the like.
  • the ratio of the coating layer of the coated particles is preferably 1 part by mass to 40 parts by mass, more preferably 5 parts by mass to 30 parts by mass, based on 100 parts by mass of the core.
  • the coated particles are preferably particles in which the coating layer completely covers the core.
  • a part of the nuclear body may be exposed.
  • the ratio of the area covered by the coating layer of the nuclear body to the surface area of the nuclear body is preferably 70% or more from the viewpoint of easily maintaining conductivity. .
  • the shape of the conductive filler (D) is not limited as long as desired conductivity is obtained.
  • the shape of the conductive filler (D) is preferably spherical, flaky, leaf-like, dendritic, plate-like, needle-like, rod-like, or grape-like.
  • the average particle diameter of the conductive filler (D) is preferably 1 ⁇ m to 100 ⁇ m, more preferably 3 ⁇ m to 50 ⁇ m, and preferably 4 ⁇ m to 15 ⁇ m, from the viewpoint of conductivity and storage stability. Particularly preferred.
  • the average particle diameter of the filler in this specification is based on the volume obtained by measuring the filler with a Tornado Dry Powder Sample Module using a laser diffraction/scattering method particle size distribution analyzer LS 13320 (manufactured by Beckman Coulter). This is the D50 average particle diameter in the particle size distribution.
  • the D50 average particle diameter indicates the average particle diameter of a particle size in which the integrated value of particles from the fine particle side of the volume-based particle size distribution is 50% by volume.
  • the adhesive composition of the present disclosure further includes a conductive filler (D).
  • a conductive filler (D) may be used alone or in combination of two or more types.
  • the content of the conductive filler (D) is determined from the viewpoints of conductivity, heat resistance, and storage stability, when it is included in the polyester polyamide resin (A), the epoxy resin (B), and as an optional component in the adhesive composition. It is preferably 1 part by mass to 500 parts by mass, more preferably 10 parts by mass to 350 parts by mass, and 10 parts by mass, based on the total amount of 100 parts by mass of the polyester polyurethane resin (C) which may be It is particularly preferred that the amount is 200 parts by mass.
  • the total amount of polyester polyamide resin (A), epoxy resin (B), and polyester polyurethane resin (C) that may be contained as an optional component in the adhesive composition is 100 parts by mass
  • the adhesive composition contains a polyester polyurethane resin (C)
  • the total amount of the polyester polyamide resin (A), epoxy resin (B) and polyester polyurethane resin (C) is 100 parts by mass
  • the adhesive composition does not contain the polyester polyurethane resin (C)
  • the total amount of the polyester polyamide resin (A) and the epoxy resin (B) is 100 parts by mass.
  • the adhesive composition of the present disclosure preferably further contains an imidazole silane compound (E) from the viewpoints of conductivity and adhesiveness.
  • the imidazole silane compound (E) indicates a compound having one or more imidazole ring structures and one or more silane structures. It is presumed that the imidazole silane compound (E) acts as a curing agent for the epoxy resin (B).
  • the imidazole silane compound (E) is preferably a compound having one imidazole ring structure and one silyl group from the viewpoint of conductivity and adhesiveness.
  • a compound represented by the following formula (E) or an acid adduct thereof is preferably mentioned.
  • R 1 and R 2 each independently represent a hydrogen atom, a saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aryl group, and each of the groups may have a substituent.
  • R 3 and R 4 each independently represent a hydrogen atom or an alkyl group. At least one of R 3 is an alkyl group, and the alkyl group may have a substituent.
  • n represents an integer from 1 to 3.
  • R 5 represents an alkylene group or a group in which a part of the alkylene group is substituted with at least one of formulas (E2) to (E5).
  • R 6 represents a hydrogen atom or a hydroxy group.
  • R 7 represents a hydrogen atom, an alkyl group, or an aryl group.
  • R 8 and R 9 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and each of the groups may have a substituent.
  • the wavy line portion represents the bonding position with another structure.
  • the adhesive composition contains the imidazole silane compound (E) (particularly the compound represented by the formula (E) above), the adhesiveness to metals (particularly gold-plated copper foil) is improved. This is because the silane structure and imidazole ring structure exhibit high affinity with metal surfaces. Therefore, it is presumed that this interaction improves adhesiveness. Furthermore, the imidazole ring structure can also react with the epoxy resin (B). Therefore, it is presumed that this adhesion-improving effect can be maintained even in the reflow process described below.
  • the imidazole silane compound (E) is preferably a compound having both an imidazole ring structure and an alkoxysilyl group in one molecule.
  • the adhesive composition of the present disclosure further includes an imidazole silane compound (E) having an alkoxysilyl group, the soldering heat resistance can be further improved.
  • the imidazole ring in the imidazole ring structure may have a substituent (for example, a saturated hydrocarbon group, an unsaturated hydrocarbon group, etc.).
  • R 1 , R 2 , R 3 and R 4 are alkyl groups, the number of carbon atoms thereof is preferably 1 to 3.
  • Examples of the imidazole ring structure constituting the imidazole silane compound (E) include an imidazole ring structure, a 2-alkylimidazole ring structure, a 2,4-dialkylimidazole ring structure, and a 4-vinylimidazole ring structure.
  • the alkoxysilyl group and the imidazole ring structure are connected to each other via an alkylene group or a group in which a part of the alkylene group is substituted with one of formulas (E2) to (E5). It is preferable that the two be bonded together.
  • the alkylene group in R 5 of formula (E) preferably has 1 to 10 carbon atoms, more preferably 3 to 7 carbon atoms.
  • the imidazole silane compound (E) can be suitably synthesized, for example, by reacting an imidazole compound with a 3-glycidoxyalkyl silane compound.
  • the imidazole silane compound (E) may be a silanol compound produced by hydrolysis of an alkoxysilyl group, a polyorganosiloxane compound produced by a dehydration condensation reaction of a silanol compound, or a mixture thereof. good.
  • Examples of the acid added to the compound represented by formula (E) include acetic acid, lactic acid, salicylic acid, benzoic acid, adipic acid, phthalic acid, citric acid, tartaric acid, maleic acid, trimellitic acid, phosphoric acid, and isocyanuric acid. etc. These can be used alone or in combination of two or more.
  • the imidazole silane compound (E) is preferably a compound represented by the following formula (E6) or formula (E7), or an acid adduct thereof, from the viewpoints of conductivity and adhesiveness.
  • R 1 and R 2 each independently represent a hydrogen atom, a saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aryl group, and each of the groups has a substituent. You can leave it there.
  • R 3 and R 4 each independently represent a hydrogen atom or an alkyl group. At least one of R 3 is an alkyl group, and the alkyl group may have a substituent.
  • n represents an integer from 1 to 3.
  • R 5' represents an alkylene group.
  • R 6 represents a hydrogen atom or a hydroxy group.
  • the number of carbon atoms in the alkylene group at R 5' in formulas (E6) and (E7) is preferably 1 to 10, more preferably 3 to 7.
  • Examples of the imidazole silane compound (E) include 1-(2-hydroxy-3-trimethoxysilylpropoxypropyl)imidazole, 1-(2-hydroxy-3-triethoxysilylpropoxypropyl)imidazole, 1-(2- Hydroxy-3-tripropoxysilylpropoxypropyl)imidazole, 1-(2-hydroxy-3-tributoxysilylpropoxypropyl)imidazole, 1-(2-hydroxy-3-triethoxysilylpropoxypropyl)-2-methylimidazole, 1-(2-hydroxy-3-triethoxysilylpropoxypropyl)-4-methylimidazole, 1-(3-oxo-4-trimethoxysilylpropoxypropyl)imidazole, and 1-(3-trimethoxysilylpropylamino) Examples include imidazole.
  • the compound represented by formula (E6) or formula (E7) or its acid adduct has good heat resistance and from the viewpoint of improving solubility in solvents, the compound represented by formula (D6) is preferred. Acid adducts are more preferred.
  • the compound represented by the formula (E6) can be suitably obtained by reacting an imidazole compound and a 3-glycidoxypropylsilane compound.
  • the imidazole compound include imidazole, 2-alkylimidazole, 2,4 dialkylimidazole, and 4-vinylimidazole.
  • the 3-glycidoxypropylsilane compound include 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyldialkoxyalkylsilane, and 3-glycidoxypropylalkoxydialkylsilane. Particularly preferred among these is a reaction product of imidazole and 3-glycidoxypropyltrimethoxysilane.
  • the compound represented by the formula (E7) can be suitably obtained by reacting an imidazole compound with 3-methacryloyloxypropyltrimethoxysilane or the like.
  • the adhesive composition of the present disclosure may contain one type of imidazole silane compound (E) alone, or may contain two or more types of imidazole silane compounds (E).
  • the content of the imidazole silane compound (E) is determined from the viewpoint of conductivity and adhesiveness, even if it is contained in the polyester polyamide resin (A), the epoxy resin (B), and optionally in the adhesive composition.
  • the amount is preferably 0.05 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, and 1 part by mass based on the total amount of 100 parts by mass of the good polyester polyurethane resin (C). Parts to 5 parts by weight are particularly preferred.
  • the adhesive composition of the present disclosure may further include an inorganic filler (F) that does not have electrical conductivity (hereinafter also simply referred to as "inorganic filler (F)"). is preferable, and it is more preferable to further include an inorganic filler (F) that does not have conductivity and an organic filler (G) that does not have conductivity, which will be described later.
  • the non-conductive inorganic filler (F) and the non-conductive organic filler (G) described below are inorganic fillers or organic fillers other than the above-mentioned conductive filler (D).
  • the inorganic filler (F) is not particularly limited, and examples include non-conductive inorganic fillers and conductive inorganic fillers.
  • Examples of the non-conductive inorganic filler include calcium carbonate particles, titanium oxide particles, aluminum oxide particles, zinc oxide particles, talc particles, and silica particles.
  • Examples of the conductive inorganic filler include carbon black particles.
  • the inorganic filler (F) is selected from the group consisting of talc particles and silica particles, from the viewpoint of conductivity in the initial stage of the obtained cured product, after soldering, after long-term reliability tests, and after cold/heat cycle tests. At least one kind of particles are preferred, and talc particles are more preferred.
  • the average particle diameter of the inorganic filler (F) is not particularly limited, but it is suitable for the conductivity, coating properties, and coating thickness adjustment properties of the resulting cured product at the initial stage, after soldering, after long-term reliability tests, and after cold/heat cycle tests. From this point of view, it is preferably 0.001 ⁇ m to 50 ⁇ m, more preferably 0.005 ⁇ m to 30 ⁇ m, and particularly preferably 0.01 ⁇ m to 10 ⁇ m.
  • the inorganic filler (F) may be used alone or in combination of two or more. From the viewpoints of solder heat resistance and conductivity, the inorganic filler (F) is preferably two or more types, and more preferably two types.
  • the content of the inorganic filler (F) is determined based on the content of the polyester polyamide resin (A), epoxy resin (B), and optionally contained in the adhesive composition from the viewpoint of adhesiveness, conductivity, and curability. It is preferably 0.1 parts by mass to 50 parts by mass, more preferably 0.5 parts by mass to 20 parts by mass, based on the total amount of 100 parts by mass of the optional polyester polyurethane resin (C). Particularly preferably from 1 part by weight to 10 parts by weight.
  • Organic filler (G) that does not have electrical conductivity (hereinafter also simply referred to as "organic filler (G)") from the viewpoint of soldering heat resistance, electrical conductivity, and moist heat resistance. It is preferable to contain.
  • organic filler (G) include (meth)acrylic resin particles, polybutadiene particles, nylon particles, polyolefin particles, polyester particles, polycarbonate particles, polyvinyl alcohol particles, polyvinyl ether particles, polyvinyl butyral particles, silicone rubber particles, and polyurethane particles. , phenolic resin particles, and polytetrafluoroethylene particles.
  • the organic filler When the organic filler is dissolved in the polyester polyamide resin (A), the epoxy resin (B), and the optionally contained polyester polyurethane resin (C), it can increase the compatibility of these resins. . Furthermore, from the viewpoint of further improving the compatibility and liquid stability of these resins, silicone particles, polybutadiene particles, (meth)acrylic resin particles, or polyurethane particles are particularly preferred.
  • the average particle diameter of the organic filler (G) is not particularly limited, but from the viewpoint of coating properties and coating thickness controllability, it is preferably 0.5 ⁇ m to 50 ⁇ m, more preferably 1 ⁇ m to 30 ⁇ m.
  • the adhesive composition of the present disclosure may contain an organic filler (G).
  • the organic filler (G) may be used alone or in combination of two or more.
  • the content of the organic filler (G) is determined based on the content of the polyester polyamide resin (A), epoxy resin (B), and optionally contained in the adhesive composition from the viewpoint of adhesiveness, conductivity, and curability.
  • the amount is preferably 1 part by mass to 50 parts by mass, more preferably 5 parts to 40 parts by mass, and 10 parts by mass to 100 parts by mass of the optional polyester polyurethane resin (C). Particularly preferred is 20 parts by mass.
  • the resin composition of the present disclosure may contain other additives other than the above-mentioned components to the extent that the functions of the adhesive composition are not affected.
  • additives include, for example, thermoplastic resins other than those mentioned above, tackifiers, flame retardants, curing agents, curing accelerators, coupling agents, heat aging inhibitors, leveling agents, antifoaming agents, and solvents. etc.
  • thermoplastic resins examples include phenoxy resins, polyester resins, polyamide resins, polycarbonate resins, polyphenylene oxide resins, polyurethane resins, polyacetal resins, polyethylene resins, polypropylene resins, and polyvinyl resins. These thermoplastic resins may be used alone or in combination of two or more.
  • tackifiers examples include coumaron-indene resin, terpene resin, terpene-phenol resin, rosin resin, pt-butylphenol-acetylene resin, phenol-formaldehyde resin, xylene-formaldehyde resin, petroleum hydrocarbon resin, Examples include hydrogenated hydrocarbon resins and turpentine resins. These tackifiers may be used alone or in combination of two or more.
  • the flame retardant may be either an organic flame retardant or an inorganic flame retardant.
  • organic flame retardants include phosphorus flame retardants, nitrogen flame retardants, and silicon flame retardants.
  • phosphorus flame retardants include melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium phosphate, ammonium polyphosphate, carbamate phosphate, carbamate polyphosphate.
  • nitrogen-based flame retardants include triazine compounds such as melamine, melam, and melamine cyanurate, cyanuric acid compounds, isocyanuric acid compounds, triazole compounds, tetrazole compounds, diazo compounds, and urea.
  • silicon-based flame retardants include silicone compounds and silane compounds.
  • inorganic flame retardants include metal hydroxides, metal oxides, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, and hydrated glass.
  • the metal hydroxide include aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, and calcium hydroxide.
  • metal oxides include tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, and nickel oxide. These flame retardants may be used alone or in combination of two or more.
  • the curing agent is a component for forming a crosslinked structure by reaction with the epoxy resin (B).
  • the curing agent include acid-based curing agents, basic active hydrogen-based curing agents, polymercaptan-based curing agents, novolac resin-based curing agents, urea resin-based curing agents, and melamine resin-based curing agents.
  • acidic curing agents include amine-based curing agents (e.g., aliphatic diamines, aliphatic polyamines, cycloaliphatic diamines, aromatic diamines, etc.), polyamide amine-based curing agents, aliphatic polycarboxylic acids, and fatty acids.
  • Examples include cyclic polycarboxylic acids, aromatic polycarboxylic acids, and acid anhydrides thereof.
  • Examples of the basic active hydrogen curing agent include dicyandiamide and organic acid dihydrazide. These curing agents may be used alone or in combination of two or more.
  • aliphatic diamine curing agents include ethylene diamine, 1,3-diaminopropane, 1,4-diaminobutane, hexamethylene diamine, polymethylene diamine, polyether diamine, 2,5-dimethylhexamethylene diamine, and trimethyl. Examples include hexamethylene diamine.
  • aliphatic polyamine curing agents examples include diethylenetriamine, iminobis(hexamethylene)triamine, trihexatetramine, tetraethylenepentamine, aminoethylethanolamine, tri(methylamino)hexane, dimethylaminopropylamine, diethylaminopropylamine, and methyliminobispropylamine.
  • Examples of the cycloaliphatic diamine curing agent include menzendiamine, isophoronediamine, bis(4-amino-3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, N-ethylaminopiperazine, Examples include hydrogenated products of 3,9-bis(3-aminopropyl)2,4,8,10-tetraoxaspiro[5.5]undecane and metaxylylenediamine.
  • aromatic diamine curing agent examples include metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, and metaxylylenediamine.
  • aliphatic polycarboxylic acid curing agents and acid anhydride curing agents include succinic acid, adipic acid, dodecenyl succinic anhydride, polyadipic anhydride, polyazelaic anhydride, and polysebacic anhydride. Can be mentioned.
  • Examples of the alicyclic polycarboxylic acid curing agent and acid anhydride curing agent include methyltetrahydrophthalic acid, methylhexahydrophthalic acid, methylhimic acid, hexahydrophthalic acid, tetrahydrophthalic acid, and trialkyltetrahydrophthalic acid. Examples include phthalic acid, methylcyclodicarboxylic acid, and acid anhydrides thereof.
  • aromatic polycarboxylic acid curing agents and acid anhydride curing agents include phthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, ethylene glycol glycol bistrimellitic acid, glycerol tristrimellitic acid, and Examples include acid anhydrides thereof.
  • polymercaptan curing agent examples include mercaptated epoxy resins and mercaptopropionic acid esters.
  • novolak curing agent examples include a phenol novolac curing agent, a cresol novolac curing agent, and the like.
  • the content of the curing agent is such that the functional group equivalent thereof is 1 mole of epoxy groups of the epoxy resin (B) from the viewpoint of adhesiveness and heat resistance.
  • the amount is preferably 0.2 molar equivalent to 2.5 molar equivalent, more preferably 0.4 molar equivalent to 2.0 molar equivalent.
  • the curing accelerator is a component used for the purpose of accelerating the reaction of the epoxy resin (B), and includes a tertiary amine curing accelerator, a tertiary amine salt curing accelerator, an imidazole curing accelerator, etc. can be used. These curing accelerators may be used alone or in combination of two or more.
  • tertiary amine curing accelerator examples include benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, tetramethylguanidine, triethanolamine, N,N '-dimethylpiperazine, triethylenediamine, and 1,8-diazabicyclo[5.4.0]undecene.
  • tertiary amine salt curing accelerator examples include formate, octylate, p-toluenesulfonate, o-phthalate, and phenol salt of 1,8-diazabicyclo[5.4.0]undecene. or phenol novolac resin salt, formate, octylate, p-toluenesulfonate, o-phthalate, phenol salt, and phenol novolac resin salt of 1,5-diazabicyclo[4.3.0]nonene, etc. can be mentioned.
  • imidazole-based curing accelerators examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 1,2-dimethylimidazole, 2-methyl-4-ethylimidazole, 2-phenylimidazole, 2- Phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s- Triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl- (1')]-ethyl-s-triazine, 2,4-diamino-6-[2'
  • the content of the curing accelerator is preferably determined based on 100 parts by mass of the epoxy resin (B) from the viewpoint of adhesiveness and heat resistance.
  • the amount is 1 part by weight to 10 parts by weight, more preferably 2 parts to 5 parts by weight.
  • Examples of the coupling agent include silane coupling agents, titanate coupling agents, aluminate coupling agents, and zirconium coupling agents.
  • Examples of the silane coupling agent include vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxylane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxy
  • Examples include silane and imidazole silane. These may be used alone or in combination of two or more.
  • Examples of the heat aging inhibitor include phenolic antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.
  • phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol, n-octadecyl-3-(3',5'-di-tert-butyl-4'- Examples include hydroxyphenyl)propionate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, and the like.
  • Examples of the sulfur-based antioxidant include dilauryl-3,3'-thiodipropionate and dimyristyl-3,3'-dithiopropionate.
  • Examples of the phosphorus antioxidant include trisnonylphenyl phosphite and tris(2,4-di-tert-butylphenyl) phosphite. These may be used alone or in combination of two or more.
  • the adhesive composition of the present disclosure can be prepared by mixing a polyester polyamide resin (A), an epoxy resin (B), and, if necessary, other components.
  • the adhesive composition of the present disclosure is preferably used in the form of a solution or dispersion, and therefore preferably contains a solvent.
  • the solvent include alcohols, ketones, aromatic hydrocarbons, esters, and aliphatic hydrocarbons.
  • alcohols include methanol, ethanol, isopropyl alcohol, n-propyl alcohol, isobutyl alcohol, n-butyl alcohol, benzyl alcohol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, and diacetone alcohol. Can be mentioned.
  • ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, and isophorone.
  • aromatic hydrocarbons include toluene, xylene, ethylbenzene, and mesitylene.
  • esters include methyl acetate, ethyl acetate, ethylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate.
  • aliphatic hydrocarbons include hexane, heptane, cyclohexane, methylcyclohexane, and the like.
  • the polyester polyamide resin (A) is easily dissolved in protic solvents, and among these, solvents containing alcohols are preferred. These solvents may be used alone or in combination of two or more.
  • solvents may be used alone or in combination of two or more.
  • the solid content concentration of the solvent is preferably from 3% by mass to 80% by mass, more preferably from 10% by mass from the viewpoint of workability including film forming properties. It is 50% by mass.
  • Suitable materials for the adherend using the adhesive composition of the present disclosure include, for example, polymer materials, metal materials, and the like.
  • the polymeric material include polyimide resin, polyetheretherketone resin, polyphenylene sulfide resin, aramid resin, and liquid crystal polymer.
  • the metal material include copper, aluminum, and stainless steel.
  • the shape of the adherend is not particularly limited. By bonding two members as adherends together using the adhesive composition of the present disclosure, an integrated composite can be manufactured. The materials of the two members may be the same or different.
  • products having an adhesive composition layer having adhesive properties for example, a coverlay film, a bonding sheet, etc.
  • the water absorption rate when the cured product obtained by curing the adhesive composition of the present disclosure is immersed in water at 23° C. for 24 hours is determined by the properties of soldering heat resistance, adhesion, and moisture resistance. From this viewpoint, it is preferably 4% or less, more preferably 3% or less, and particularly preferably 2.7% or less.
  • the lower limit of the water absorption rate is 0%.
  • the water absorption rate of the cured product of the adhesive composition in the present disclosure is calculated as follows. The sheet, adhesive composition layer, and sheet are stacked in this order to obtain a stacked body. The stacked body is heat-pressed at 150° C. and 3 MPa for 5 minutes, and then heat-cured at 160° C.
  • the laminate is formed by laminating a sheet, a cured adhesive composition, and a sheet in this order.
  • JIS K 7114 the water absorption rate when the laminate is immersed in water at 23° C. for 24 hours is defined as the water absorption rate of the cured product of the adhesive composition.
  • the laminate with an adhesive composition layer of the present disclosure is a laminate using the adhesive composition of the present disclosure.
  • the laminate with an adhesive composition layer of the present disclosure includes an adhesive composition layer and a base film in contact with at least one surface of the adhesive composition layer.
  • the adhesive composition layer is an adhesive composition layer made of an uncured adhesive composition of the present disclosure, a B-stage adhesive composition layer formed by partially curing the adhesive composition, or , a cured layer obtained by curing the adhesive composition.
  • uncured adhesive composition refers to an uncured state of the adhesive composition.
  • the adhesive composition layer is in a B-stage state refers to a semi-cured state in which a part of the adhesive composition layer has begun to harden.
  • the B-stage state is a state in which the adhesive composition layer further progresses in curing due to heating or the like.
  • the adhesive composition layer made of an uncured adhesive composition of the present disclosure is a layer obtained by removing at least a part of the solvent from the adhesive composition of the present disclosure. It is preferable that there be.
  • the laminate with an adhesive composition layer of the present disclosure and the laminate of the present disclosure preferably have a base material, and more preferably have a layer made of the adhesive composition of the present disclosure on the base material.
  • the base material is preferably a film-like base material (base film).
  • the base film is preferably a resin film, more preferably a polyimide film or an aramid film, and particularly preferably a polyimide film.
  • the polyimide film or aramid film is not particularly limited as long as it has electrical insulation properties, and examples thereof include a film made only of polyimide resin or aramid resin, a film containing polyimide resin or aramid resin and additives, etc. .
  • the side on which the adhesive composition layer is formed may be surface-treated.
  • the thickness of the base material is not particularly limited, but is preferably 3 ⁇ m to 125 ⁇ m.
  • the thickness of the adhesive composition layer is preferably 5 ⁇ m to 50 ⁇ m, more preferably 10 ⁇ m to 40 ⁇ m.
  • the adhesive composition of the present disclosure containing a solvent is applied to the surface of a base film (for example, a polyimide film, etc.) to form an adhesive layer.
  • a base film for example, a polyimide film, etc.
  • first method a method of removing at least a portion of the solvent from the adhesive composition layer after forming the composition layer.
  • the drying temperature when removing the solvent is preferably 40°C to 250°C, more preferably 70°C to 170°C. Drying is performed by passing the laminate coated with the adhesive composition through an oven.
  • the laminate with an adhesive composition layer of the present disclosure may further include a releasable film on the surface of the adhesive composition layer for storage and the like, if necessary.
  • the release film include polyethylene terephthalate film, polyethylene film, polypropylene film, silicone release-treated paper, polyolefin resin coated paper, polymethylpentene (TPX) film, fluororesin film, and the like.
  • the releasable film may be of any known type.
  • the thickness of the B-stage adhesive composition layer is preferably 5 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 70 ⁇ m, even more preferably 5 ⁇ m to 50 ⁇ m, and preferably 10 ⁇ m to 40 ⁇ m. Particularly preferred.
  • the thickness of the base film and the adhesive composition layer is selected depending on the application, but the base film may be thinner in order to improve electrical properties.
  • the preferred thickness of the base film is the same as the preferred thickness of the base material described above.
  • the ratio (A/B) between the thickness (A) of the adhesive composition layer and the thickness (B) of the base film is 1 to 10. It is preferably 1 to 5, and more preferably 1 to 5. Furthermore, it is preferable that the thickness of the adhesive composition layer is thicker than the thickness of the base film.
  • the laminate of the present disclosure for example, in the case of a laminate with an adhesive composition layer of the present disclosure, after coating the surface of the base film with the adhesive composition of the present disclosure containing a solvent, The adhesive composition layer is dried in the same manner as above, and then the surface of the formed adhesive composition layer and the adherend are brought into surface contact and laminated (for example, thermal lamination at 80° C. to 150° C.). Thereby, a laminate (base film/adhesive composition layer/adherent) is obtained.
  • the laminate base film/adhesive composition layer/adherent
  • the laminate base film/adhesive composition layer/adherent
  • the laminate is formed by laminating a base film, an adhesive composition layer, and an adherend in this order.
  • a method of heat-pressing this laminate base film/adhesive composition layer/adherent) and then curing the adhesive composition layer by after-curing to form a cured layer is preferably mentioned.
  • the conditions for heat compression bonding are not particularly limited as long as compression bonding is possible, but preferably the temperature is 150° C. to 200° C. and the pressure is 1 MPa to 3 MPa for 1 minute to 60 minutes.
  • the conditions for after-cure are not particularly limited, but are preferably 100° C. to 200° C. and 30 minutes to 4 hours.
  • the thickness of the cured layer is preferably 5 ⁇ m to 100 ⁇ m, more preferably 5 ⁇ m to 70 ⁇ m, even more preferably 5 ⁇ m to 50 ⁇ m, and particularly preferably 10 ⁇ m to 40 ⁇ m.
  • the adherend is not particularly limited, and examples include those described above. Among these, metal adherends are preferred, copper foil or plated copper foil is more preferred, and gold-plated copper foil is particularly preferred. There are no particular limitations on the shape, size, etc. of the adherend, and known ones can be used.
  • the laminate of the present disclosure includes a cured layer formed by curing the adhesive composition of the present disclosure.
  • One embodiment of the laminate of the present disclosure includes a flexible copper-clad laminate. That is, the flexible copper-clad laminate of the present disclosure has a cured layer formed by curing an adhesive composition comprising the adhesive composition of the present disclosure.
  • the flexible copper-clad laminate of the present disclosure is preferably a laminate including a polyimide film or an aramid film, a cured layer obtained by curing the adhesive composition of the present disclosure, and copper foil.
  • the cured layer and the copper foil may be formed on both sides of a polyimide film or an aramid film.
  • the adhesive composition of the present disclosure has excellent adhesion to articles containing copper. Therefore, the flexible copper-clad laminate of the present disclosure has excellent stability as an integrated product.
  • the structure of the polyimide film or aramid film is the same as that of the polyimide film or aramid film in the coverlay film of the present disclosure described above.
  • the thickness of the cured layer is preferably 5 ⁇ m to 50 ⁇ m, more preferably 10 ⁇ m to 40 ⁇ m.
  • the copper foil is not particularly limited, and examples thereof include electrolytic copper foil, rolled copper foil, and the like.
  • the copper foil may be plated with a known metal (eg, gold, silver, etc.) or an alloy.
  • An embodiment of the laminate with an adhesive composition layer of the present disclosure includes a bonding film, an electromagnetic shielding film, a coverlay film, etc., which will be described later.
  • the bonding film of the present disclosure uses the adhesive composition of the present disclosure.
  • the bonding film of the present disclosure includes a B-stage adhesive composition layer formed by partially curing the adhesive composition of the present disclosure, and a release film in contact with at least one surface of the adhesive composition layer. It is preferable to have one.
  • the bonding film of the present disclosure is also an embodiment of the laminate with an adhesive composition layer of the present disclosure described above.
  • the bonding film of the present disclosure may include an adhesive composition layer between two releasable films. As the releasable film, the known ones mentioned above can be used.
  • the thickness of the releasable film is preferably 20 ⁇ m to 100 ⁇ m.
  • the thickness of the adhesive composition layer is preferably 5 ⁇ m to 100 ⁇ m, more preferably 10 ⁇ m to 60 ⁇ m.
  • the above-described lamination with the adhesive composition layer of the present disclosure may be performed.
  • Preferred methods include drying in the same manner as for the body.
  • the electromagnetic shielding film of the present disclosure uses the adhesive composition of the present disclosure.
  • the electromagnetic shielding film of the present disclosure preferably has an adhesive composition layer.
  • the adhesive composition layer is an adhesive composition layer made of an uncured adhesive composition of the present disclosure, a B-stage adhesive composition layer formed by partially curing the adhesive composition, or This is a cured layer formed by curing the adhesive composition.
  • the electromagnetic shielding film of the present disclosure more preferably has a cured layer formed by curing the adhesive composition.
  • the electromagnetic shielding film of the present disclosure preferably includes the adhesive composition layer and a protective layer.
  • the protective layer is not particularly limited as long as it is a layer made of an insulating adhesive composition, and any known layer may be used.
  • the protective layer may use the resin component used in the adhesive composition of the present disclosure.
  • the protective layer may be formed of two or more layers having different compositions and hardnesses.
  • the protective layer may optionally contain a curing accelerator, tackifier, antioxidant, pigment, dye, plasticizer, ultraviolet absorber, antifoaming agent, leveling agent, filler, flame retardant, viscosity modifier, and It may also contain an antiblocking agent and the like.
  • the thickness of the adhesive composition layer in the electromagnetic shielding film of the present disclosure is not particularly limited, but from the viewpoint of conductivity and connectivity with a ground circuit, it is preferably 3 ⁇ m to 30 ⁇ m.
  • a protective layer adhesive composition is coated on one side of a releasable film and dried to form a protective layer, and the adhesive composition of the present disclosure is applied on the protective layer.
  • Examples include a method of coating and drying an adhesive composition to form an adhesive composition layer.
  • the adhesive composition layer and the protective layer may be provided by any known coating method.
  • methods for providing the adhesive composition layer and the protective layer include gravure coating, kiss coating, die coating, lip coating, comma coating, blade coating, roll coating, knife coating, spray coating, and bar coating.
  • Examples include a coating method, a spin coating method, and a dip coating method.
  • the electromagnetic shielding film of the present disclosure can be adhered onto a printed wiring board, for example, by heat pressing.
  • the adhesive composition layer is softened by heating and flows into a ground portion provided on the printed wiring board by applying pressure. This electrically connects the ground circuit and the conductive adhesive. As a result, the shielding effect is improved.
  • Polyester polyamide resin (A) Preparation of polyester polyamide resin (a1)> A flask equipped with a stirrer, a reflux dehydrator, and a distillation tube was charged with 7 parts by mass of dimer acid, 406 parts by mass of azelaic acid, 364 parts by mass of isophoronediamine, and 120 parts by mass of distilled water. After the temperature was raised to 120°C to distill water, the temperature was raised to 240°C at a rate of 20°C/hour and held for 1 hour.
  • Polyester polyamide resin (a2) was obtained in the same manner as in the production of polyester polyamide resin (a1), except that the reaction was continued until the amine value reached 4.3 mgKOH/g.
  • Polyamide resin (A') that does not contain polyester ⁇ Production of polyamide resin (a3) not containing polyester>
  • a flask equipped with a stirrer, a reflux dehydrator, and a distillation tube was charged with 65 parts by mass of azelaic acid, 190 parts by mass of dodecanedioic acid, 100 parts by mass of piperazine, and 120 parts by mass of distilled water. After the temperature was raised to 120°C to distill off water, the temperature was raised to 240°C at a rate of 20°C/hour, and the reaction was continued for 3 hours to obtain a polyamide resin (a3).
  • the amine value of this resin was 4.5 mgKOH/g.
  • Epoxy resin (B) Epoxy resin (b1): Trisphenolmethane type epoxy resin “jER 1032H60” (product name) manufactured by Mitsubishi Chemical Corporation Epoxy resin (b2): Bisphenol A novolac type epoxy resin “EPICLON N-865” (product name) manufactured by DIC Corporation Epoxy resin (b3): Bisphenol A epoxy resin “jER 1055” (product name) manufactured by Mitsubishi Chemical Corporation
  • Polyurethane resin (C) ⁇ Preparation of polyurethane resin (c1)>
  • PES-360HVXM30 Aronmelt (registered trademark) manufactured by Toagosei Co., Ltd.) PES-360HVXM30, number average molecular weight: 20,000, glass transition temperature: 65 ° C. ), 100 parts by mass of toluene, and 20 parts by mass of neopentyl glycol.
  • polyester polyurethane resin (c1) was obtained by diluting with toluene/2-propanol to adjust the solid content concentration to 30%.
  • the number average molecular weight of the polyester polyurethane resin (c1) was 36,000, the weight average molecular weight was 140,000, and the acid value was 2 mgKOH/g.
  • polyester polyurethane resin (c2) was obtained by diluting with toluene/2-propanol to adjust the solid content concentration to 30%.
  • the number average molecular weight of the polyester polyurethane resin (c2) was 35,000, the weight average molecular weight was 120,000, and the acid value was 2 mgKOH/g.
  • Conductive filler (D) Copper powder manufactured by Fukuda Metal Foil and Powder Co., Ltd. “FCC-115A” (product name)
  • Inorganic filler (F) without conductivity Inorganic filler (f1): “R972” manufactured by Nippon Aerosil Co., Ltd. (trade name; average particle size 16 nm, silica particles)
  • Organic filler without conductivity (G)
  • Organic filler (g1) Acrylic beads "J-4P” manufactured by Negami Kogyo Co., Ltd. (trade name; average particle size 2.2 ⁇ m, acrylic resin particles)
  • Examples 1 to 16 and Comparative Examples 1 to 4 The above raw materials were added in the proportions shown in Table 1 to a flask equipped with a stirring device, and stirred for 6 hours under heating at 60°C to prepare a polyester polyamide resin (A) or a polyamide resin (A') containing no polyester in the solvent. , an epoxy resin (B), a polyurethane resin (C), an imidazole silane compound (E), and a curing accelerator are dissolved, and a conductive filler (D), an inorganic filler (F), an organic filler (G), and A liquid adhesive composition was prepared by dispersing a flame retardant. Thereafter, a coverlay film, a bonding sheet, and adhesive test pieces A and B were prepared using all of these liquid adhesive compositions, and the following evaluations (i) to (x) were performed. The evaluation results are shown in Table 1.
  • coverlay film A liquid adhesive composition was roll-coated on the surface of a polyimide film with a thickness of 25 ⁇ m so that the thickness after drying was 15 ⁇ m, and dried at 120° C. for 2 minutes. A coverlay film having an adhesive layer was obtained.
  • Adhesion Test Piece A A rolled copper foil with a thickness of 35 ⁇ m manufactured by Fukuda Metal Foil and Powder Industries Co., Ltd. was prepared. The mirror surface was overlapped so as to be in contact with the adhesive layer surface of the coverlay film, and lamination was performed under the conditions of 150 ° C., 0.3 MPa, and 1 m / min to obtain a laminate (polyimide film / adhesive layer / copper foil). Ta. The obtained laminate (polyimide film/adhesive layer/copper foil) is formed by laminating a polyimide film, an adhesive layer, and a copper foil in this order.
  • the obtained laminate (polyimide film/adhesive layer/copper foil) was heated and compressed at 150°C and 3 MPa for 5 minutes, and then after-cured for 2 hours at 160°C in an oven. went. As a result, an adhesive test piece A was obtained.
  • a releasable PET film with a thickness of 35 ⁇ m was prepared.
  • a mixture was prepared in which a liquid adhesive composition and copper powder "FCC-115A" manufactured by Fukuda Metal Foil & Powder Industries Co., Ltd. were blended to have a solid content of 15% by mass based on the total resin.
  • the above mixture was roll coated onto the surface of the releasable PET film so that the thickness after drying was 25 ⁇ m, and dried at 140° C. for 2 minutes to obtain a bonding sheet having an adhesive layer.
  • the flexible printed wiring board is made of a nickel-plated SUS304 board (thickness: 300 ⁇ m), a polyimide film (thickness: 25 ⁇ m), a circuit pattern (material: copper), and a coverlay film (thickness: 37.5 ⁇ m). Equipped with.
  • the SUS304 plate, polyimide film, and circuit pattern are laminated in this order.
  • a coverlay film is laminated onto the circuit pattern.
  • the coverlay film has through holes with a diameter of 1 mm.
  • the nickel-plated surface of the SUS304 plate was placed in contact with the adhesive layer surface of the bonding sheet, and lamination was performed at 150°C, 0.3 MPa, and 1 m/min to form a laminate (SUS plate/adhesive). Agent layer/releaseable PET film) was obtained.
  • the laminate (SUS board/adhesive layer/release PET film) is formed by laminating an SUS304 plate, an adhesive layer, and a release PET film in this order.
  • the releasable PET film is peeled off from the laminate (SUS board/adhesive layer/mold releasable PET film), and a flexible printed wiring board (copper on a 25 ⁇ m thick polyimide film) is applied to the surface of the exposed adhesive layer.
  • a flexible printed wiring board copper on a 25 ⁇ m thick polyimide film
  • the adhesive test piece A was visually evaluated for the presence or absence of appearance abnormalities such as swelling and peeling of the adhesive layer.
  • the evaluation results are shown in Table 1.
  • Table 1 the item "Appearance during soldering” is indicated as "After normal humidity soldering test”. Those in which no abnormalities in appearance such as microvoids, blistering, and peeling were observed were designated as "A.” Those in which microvoids were slightly observed were designated as "B”. Those in which abnormal appearance such as blistering and peeling were confirmed were designated as "C”.
  • the 180° peeling adhesive strength (N/cm) when peeling the polyimide film from the gold-plated copper foil at 23°C was determined according to JIS C 6481. It was measured. The width of the adhesive test piece during measurement was 10 mm, and the tensile speed was 50 mm/min. The width of the adhesive test piece during measurement was 10 mm. The measurement results are shown in Table 1. In Table 1, the item "Peel adhesion strength after soldering" is indicated as "After normal humidity soldering test” of the peel adhesion strength. Those with a measured value of peel strength of 5.0 N/cm or more were designated as "A".
  • the adhesive compositions of Examples 1 to 16 have a higher solderability even in a normal humidity environment than the adhesive compositions of Comparative Examples 1 to 4.
  • the adhesive composition had excellent heat resistance and long-term heat and humidity resistance.
  • the adhesive compositions of Examples 3 to 16 contained the conductive filler (D) and a flame retardant, and the resulting cured products had excellent flame retardancy and conductivity.
  • the amount of epoxy resin (B) added was varied, but in Examples 4 to 6, 35 parts by mass or more of epoxy resin (B) was added to 100 parts by mass of polyester polyamide resin (A). The peel adhesion strength after the normal humidity soldering test was high.
  • Example 5 in which the imidazole compound (E) was added, the resulting adhesive composition also had excellent conductivity after the normal humidity soldering test.
  • Example 11 an inorganic filler (F) was added to the adhesive composition, and the peel adhesion strength after the normal humidity soldering test was improved.
  • Example 12 an inorganic filler (F) and an organic filler (G) were added to the adhesive composition, and the peel adhesion strength and conductivity after the normal humidity soldering test were improved.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)

Abstract

L'invention concerne une composition adhésive comprenant : une résine de polyester polyamide (A) qui présente une partie polyester et une partie polyamide ; et une résine époxy (B). Il y a 1 à 60 parties en masse de résine époxy (B) pour 100 parties en masse de résine de polyester polyamide (A).
PCT/JP2023/024689 2022-07-06 2023-07-03 Composition adhésive, film de liaison, stratifié comprenant une couche de composition adhésive, stratifié et film de protection contre les ondes électromagnétiques Ceased WO2024009969A1 (fr)

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JP2024532132A JPWO2024009969A1 (fr) 2022-07-06 2023-07-03
KR1020257000837A KR20250030475A (ko) 2022-07-06 2023-07-03 접착제 조성물, 본딩 필름, 접착제 조성물층 부착 적층체, 적층체 및 전자파 차폐 필름
CN202380050685.8A CN119452058A (zh) 2022-07-06 2023-07-03 粘接剂组合物、接合膜、带粘接剂组合物层的层叠体、层叠体以及电磁波屏蔽膜

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10338807A (ja) * 1997-04-07 1998-12-22 Hitachi Ltd 樹脂組成物及び接着フィルム
JP2001354938A (ja) * 2000-06-12 2001-12-25 Toray Ind Inc 半導体装置用接着剤組成物およびそれを用いた接着剤シート、半導体接続用基板ならびに半導体装置
JP2009001793A (ja) * 2008-06-06 2009-01-08 Kaneka Corp 接着剤
WO2012011265A1 (fr) * 2010-07-23 2012-01-26 タツタ電線株式会社 Composition d'agent adhésif et film adhésif
CN103923585A (zh) * 2014-04-03 2014-07-16 新纶科技（常州）有限公司 一种导电粘接剂组合物和导电粘接膜
JP2015228457A (ja) * 2014-06-02 2015-12-17 デクセリアルズ株式会社 太陽電池用導電性接着剤、太陽電池モジュール、及び太陽電池モジュールの製造方法
WO2016001949A1 (fr) * 2014-07-02 2016-01-07 東洋インキＳｃホールディングス株式会社 Composition de résine thermo-durcissable, polyamide, feuille adhésive, article durci, et carte de circuits imprimés
WO2022085563A1 (fr) * 2020-10-23 2022-04-28 東亞合成株式会社 Composition de résine, film de liaison, stratifié avec couche de composition de résine, stratifié et film de protection contre les ondes électromagnétiques

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10338807A (ja) * 1997-04-07 1998-12-22 Hitachi Ltd 樹脂組成物及び接着フィルム
JP2001354938A (ja) * 2000-06-12 2001-12-25 Toray Ind Inc 半導体装置用接着剤組成物およびそれを用いた接着剤シート、半導体接続用基板ならびに半導体装置
JP2009001793A (ja) * 2008-06-06 2009-01-08 Kaneka Corp 接着剤
WO2012011265A1 (fr) * 2010-07-23 2012-01-26 タツタ電線株式会社 Composition d'agent adhésif et film adhésif
CN103923585A (zh) * 2014-04-03 2014-07-16 新纶科技（常州）有限公司 一种导电粘接剂组合物和导电粘接膜
JP2015228457A (ja) * 2014-06-02 2015-12-17 デクセリアルズ株式会社 太陽電池用導電性接着剤、太陽電池モジュール、及び太陽電池モジュールの製造方法
WO2016001949A1 (fr) * 2014-07-02 2016-01-07 東洋インキＳｃホールディングス株式会社 Composition de résine thermo-durcissable, polyamide, feuille adhésive, article durci, et carte de circuits imprimés
WO2022085563A1 (fr) * 2020-10-23 2022-04-28 東亞合成株式会社 Composition de résine, film de liaison, stratifié avec couche de composition de résine, stratifié et film de protection contre les ondes électromagnétiques

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JPWO2024009969A1 (fr) 2024-01-11
KR20250030475A (ko) 2025-03-05
CN119452058A (zh) 2025-02-14

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