WO2024009969A1 - Adhesive composition, bonding film, laminate with adhesive composition layer, laminate, and electromagnetic wave shield film - Google Patents

Adhesive composition, bonding film, laminate with adhesive composition layer, laminate, and electromagnetic wave shield film 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
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Prior art keywords
adhesive composition
carbon atoms
acid
polyester
resin
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PCT/JP2023/024689
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French (fr)
Japanese (ja)
Inventor
勝 安藤
雅弘 鳥居
愛 岩田
真 平川
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東亞合成株式会社
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Publication of WO2024009969A1 publication Critical patent/WO2024009969A1/en

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    • 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
    • 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
    • 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

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)
  • Inorganic Chemistry (AREA)
  • Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

This adhesive composition includes: a polyester polyamide resin (A) that has a polyester portion and a polyamide portion; and an epoxy resin (B). There are 1–60 parts by mass of the epoxy resin (B) per 100 parts by mass of the polyester polyamide resin (A).

Description

接着剤組成物、ボンディングフィルム、接着剤組成物層付き積層体、積層体、及び、電磁波シールドフィルムAdhesive composition, bonding film, laminate with adhesive composition layer, laminate, and electromagnetic shielding film
　本発明は、接着剤組成物、ボンディングフィルム、接着剤組成物層付き積層体、積層体、及び、電磁波シールドフィルムに関する。 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.
　フレキシブルプリント配線板は、限られたスペースでも立体的且つ高密度の実装が可能であるため、その用途が拡大しつつある。近年、電子機器の小型化、軽量化等に伴い、フレキシブルプリント配線板の関連製品は多様化して、その需要が増大している。このような関連製品としては、ポリイミドフィルムに銅箔を貼り合わせたフレキシブル銅張積層板、フレキシブル銅張積層板に電子回路を形成したフレキシブルプリント配線板、フレキシブルプリント配線板と補強板を貼り合せた補強板付きフレキシブルプリント配線板、フレキシブル銅張積層板又はフレキシブルプリント配線板を重ねて接合した多層板等がある。フレキシブル銅張積層板を製造する場合、ポリイミドフィルムと銅箔とを接着させるために、通常、接着剤が用いられる。 Since flexible printed wiring boards can be mounted three-dimensionally and with high density even in a limited space, their uses are expanding. In recent years, as electronic devices have become smaller and lighter, 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. When manufacturing a flexible copper-clad laminate, an adhesive is usually used to bond the polyimide film and the copper foil.
　従来の接着剤組成物、又は、従来の積層体としては、特許文献１～６に記載の方法が知られている。
　特許文献１には、接着剤が記載されている。特許文献１に記載の接着剤は、酸価が１００～２０００当量／ｔであるポリエステルアミド樹脂（Ａ）とエポキシ化合物（Ｂ）からなる。 As conventional adhesive compositions or conventional laminates, methods described in Patent Documents 1 to 6 are known.
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.
　特許文献２には、ＴＡＢ用接着テープが記載されている。特許文献２に記載の接着テープは、有機絶縁フィルム上に、少なくとも、ポリアミド樹脂とエポキシ樹脂とフェノール樹脂を含有する接着層を設けてなる。該接着層の１００℃における弾性率が２００～５００ＭＰａであり、且つ、１８０℃における弾性率が１０～１００ＭＰａである。 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.
　特許文献３には、接着剤樹脂組成物が記載されている。特許文献３に記載の接着剤樹脂組成物は、（Ａ）エポキシ樹脂及び硬化剤を含む硬化成分と、（Ｂ）非プロトン性溶媒に可溶なポリアミドと、（Ｃ）難燃剤と、（Ｄ）溶媒とを含む。前記エポキシ樹脂がフェノールアラルキル型のエポキシ樹脂を含む。前記溶媒が非プロトン性溶媒で構成される。前記（Ａ）成分及び前記（Ｂ）成分の合計重量に対する前記（Ａ）成分の重量分率が４１～７０重量％である。 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.
　特許文献４には、熱硬化性接着組成物が記載されている。特許文献４に記載の熱硬化性接着組成物は、ガラス転移温度が５℃以上である（メタ）アクリルポリマーと、液状エポキシ樹脂と、固形樹脂と、末端に反応性官能基を有するポリアミドエラストマーと、エポキシ樹脂硬化剤とを含有する。前記固形樹脂は、固形エポキシ樹脂、固形フェノール樹脂から選択される１種以上である。前記固形樹脂は、前記液状エポキシ樹脂と相溶性を示す。前記固形樹脂は、５０℃以上１００℃以下の軟化点を有する。 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.
　特許文献５には、ポリエステルアミド樹脂組成物が記載されている。特許文献５に記載のポリエステルアミド樹脂組成物は、特定構造のポリアミド繰り返し単位を有するポリエステルアミド樹脂１～５０重量部と、正又は負の電極活物質９９～５０重量部と、を含有する。 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.
　特許文献６には、接着剤組成物が記載されている。特許文献６に記載の接着剤組成物は、ポリエーテルエステルアミド１００重量部に対し、スチレン－イソブチレン－スチレン系オレフィンエラストマー、スチレン－エチレン－ブチレン－スチレン系オレフィンエラストマー及びこれらの無水マレイン酸変性物のうちの１種又は２種以上を総量で１～３００重量部含有してなる。 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.
　　特許文献１：特開２００６－１５２０１５号公報
　　特許文献２：特開２００９－４０８１４号公報
　　特許文献３：特開２０１２－２５８８８号公報
　　特許文献４：特開２０１５－１９３６８３号公報
　　特許文献５：特開２０１０－３１０９９号公報
　　特許文献６：国際公開第２０１２／０１１２６５号 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
　フレキシブルプリント配線板等のはんだリフロー工程では、急激な加熱を行うと、用いられる接着剤の吸湿や分解ガスにより、外観異常（例えば、膨れ等）又は強度低下を生じることがある。そのため、通常、はんだリフロー工程の直前に乾燥処理を行う。しかし近年、生産性向上のために、この乾燥処理を必要としない接着剤が求められている。フレキシブル配線板等の使用環境から、高温高湿下に長期保管後も強度等が低下しない接着剤が求められる。 In the solder reflow process for flexible printed wiring boards, etc., if rapid heating is performed, the adhesive used may absorb moisture or decompose gas, resulting in abnormal appearance (for example, blistering, etc.) or a decrease in strength. Therefore, a drying process is usually performed immediately before the solder reflow process. However, in recent years, in order to improve productivity, there has been a demand for adhesives that do not require this drying process. Due to the usage environment of flexible wiring boards, etc., there is a demand for adhesives that do not lose their strength even after long-term storage under high temperature and high humidity conditions.
　本発明が解決しようとする課題は、得られる硬化物が、常湿環境下においてもはんだ耐熱性に優れ、かつ長期の耐湿熱性にも優れる接着剤組成物を提供することである。
　本発明が解決しようとする他の課題は、前記接着剤組成物を用いたボンディングフィルム、接着剤組成物層付き積層体、積層体又は電磁波シールドフィルムを提供することである。 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.
　前記課題を解決するための手段には、以下の態様が含まれる。
　＜１＞　ポリエステル部分とポリアミド部分を有するポリエステルポリアミド樹脂（Ａ）と、
　エポキシ樹脂（Ｂ）と
を含み、
　前記ポリエステルポリアミド樹脂（Ａ）１００質量部に対し、前記エポキシ樹脂（Ｂ）の量が１質量部～６０質量部である
　接着剤組成物。
　＜２＞　前記ポリエステルポリアミド樹脂（Ａ）のアミン価が、１．０ｍｇＫＯＨ／ｇ～１２．０ｍｇＫＯＨ／ｇである前記＜１＞に記載の接着剤組成物。
　＜３＞　前記ポリエステルポリアミド樹脂（Ａ）の前記ポリエステル部分が、炭素数６～２２の脂肪族ジカルボン酸、炭素数６～２２の芳香族ジカルボン酸及び／又は炭素数６～２２の脂環式ジカルボン酸と、炭素数２～５４の脂肪族ジオール、炭素数２～５４の芳香族ジオール又は炭素数２～５４の脂環式ジオールとの重縮合物であり、
　前記ポリエステルポリアミド樹脂（Ａ）の前記ポリアミド部分が、炭素数６～２２の脂肪族ジカルボン酸、炭素数６～２２の芳香族ジカルボン酸及び／若しくは炭素数６～２２の脂環式ジカルボン酸並びに／又は炭素数２０～４８の二量化脂肪族二酸を含むジカルボン酸と、炭素数６～４４の芳香族及び／又は炭素数６～４４の脂環式骨格を有するジアミンとの重縮合物である前記＜１＞又は＜２＞に記載の接着剤組成物。
　＜４＞　ポリウレタン樹脂（Ｃ）を更に含む前記＜１＞～＜３＞のいずれか１つに記載の接着剤組成物。
　＜５＞　硬化物を２３℃の水に２４時間浸漬させたときの吸水率が、３％以下である前記＜１＞～＜４＞のいずれか１つに記載の接着剤組成物。
　＜６＞　導電性フィラー（Ｄ）を更に含む前記＜１＞～＜５＞のいずれか１つに記載の接着剤組成物。
　＜７＞　前記導電性フィラー（Ｄ）の含有量が、前記接着剤組成物における前記ポリエステルポリアミド樹脂（Ａ）、前記エポキシ樹脂（Ｂ）及び任意成分として含有してもよいポリエステルウレタン樹脂（Ｃ）の合計量１００質量部に対して、１０質量部～３５０質量部である前記＜６＞に記載の接着剤組成物。
　＜８＞　アルコキシシリル基を有するイミダゾール系化合物（Ｅ）を更に含む前記＜１＞～＜７＞のいずれか１つに記載の接着剤組成物。
　＜９＞　導電性を有しない無機フィラー（Ｆ）を更に含む前記＜１＞～＜８＞のいずれか１つに記載の接着剤組成物。
　＜１０＞　導電性を有しない有機フィラー（Ｇ）を更に含む前記＜１＞～＜９＞のいずれか１つに記載の接着剤組成物。
　＜１１＞　前記＜１＞～＜１０＞のいずれか１つに記載の接着剤組成物を一部硬化してなるＢステージ状の接着剤組成物層と、前記接着剤組成物層の少なくとも一方の面に接する離型フィルムとを備えるボンディングフィルム。
　＜１２＞　接着剤組成物層と、前記接着剤組成物層の少なくとも一方の面に接する基材フィルムとを備え、
　前記接着剤組成物層が、前記＜１＞～＜１０＞のいずれか１つに記載の接着剤組成物の未硬化物からなる接着剤組成物層、前記接着剤組成物の一部が硬化してなるＢステージ状の接着剤組成物層、又は前記接着剤組成物が硬化してなる硬化層である、接着剤組成物層付き積層体。
　＜１３＞　前記＜１＞～＜１０＞のいずれか１つに記載の接着剤組成物を硬化してなる硬化層を備える積層体。
　＜１４＞　前記＜１＞～＜１０＞のいずれか１つに記載の接着剤組成物を硬化してなる硬化層を備える電磁波シールドフィルム。 Means for solving the above problems include the following aspects.
<1> A polyester polyamide resin (A) having a polyester part and a polyamide part,
Including epoxy resin (B),
An adhesive composition in which 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).
<2> The adhesive composition according to <1> above, wherein the polyester polyamide resin (A) has an amine value of 1.0 mgKOH/g to 12.0 mgKOH/g.
<3> 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 of an acid 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,
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. Or 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).
<5> The adhesive composition according to any one of <1> to <4>, which has a water absorption rate of 3% or less when the cured product is immersed in water at 23° C. for 24 hours.
<6> The adhesive composition according to any one of <1> to <5>, further comprising a conductive filler (D).
<7> 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.
<8> The adhesive composition according to any one of <1> to <7>, further comprising an imidazole compound (E) having an alkoxysilyl group.
<9> The adhesive composition according to any one of <1> to <8>, further comprising an inorganic filler (F) having no conductivity.
<10> The adhesive composition according to any one of <1> to <9>, further comprising an organic filler (G) having no conductivity.
<11> At least one of a B-stage adhesive composition layer formed by partially curing the adhesive composition according to any one of <1> to <10> and the adhesive composition layer. 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.
<13> A laminate comprising a cured layer obtained by curing the adhesive composition according to any one of <1> to <10>.
<14> An electromagnetic shielding film comprising a cured layer formed by curing the adhesive composition according to any one of <1> to <10>.
　本発明の一実施形態によれば、得られる硬化物が、常湿環境下においてもはんだ耐熱性に優れ、かつ長期の耐湿熱性にも優れる接着剤組成物を提供することができる。
　本発明の一実施形態によれば、前記接着剤組成物を用いたボンディングフィルム、接着剤組成物層付き積層体、積層体又は電磁波シールドフィルムを提供することができる。 According to one embodiment of the present invention, it is possible 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.
According to one embodiment of the present invention, a bonding film, a laminate with an adhesive composition layer, a laminate, or an electromagnetic shielding film using the adhesive composition can be provided.
　以下に記載する構成要件の説明は、本開示の代表的な実施形態に基づいてなされることがあるが、本開示はそのような実施態様に限定されるものではない。本願明細書において「～」とはその前後に記載される数値を下限値及び上限値として含む意味で使用される。
　本明細書中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
　本開示において、組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する前記複数の物質の合計量を意味する。
　本開示において、「工程」との語は、独立した工程だけでなく、他の工程と明確に区別できない場合であっても工程の所期の目的が達成されれば、本用語に含まれる。
　本開示において、「質量％」と「重量％」とは同義であり、「質量部」と「重量部」とは同義である。
　本開示において、２以上の好ましい態様の組み合わせは、より好ましい態様である。
　本明細書において、「（メタ）アクリル」はアクリル及びメタクリルの双方、又は、いずれかを表す。
　本明細書における化合物の一部において、炭化水素鎖を炭素（Ｃ）及び水素（Ｈ）の記号を省略した簡略構造式で記載する場合もある。
　以下において、本開示の内容について詳細に説明する。 Although the description of the constituent elements described below may be made based on typical embodiments of the present disclosure, the present disclosure is not limited to such embodiments. In the present specification, "~" is used to include the numerical values described before and after it as a lower limit value and an upper limit value.
In the numerical ranges described step by step in this specification, 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. In the numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced with the values shown in the examples.
In the present disclosure, when there are multiple substances corresponding to each component in the composition, unless otherwise specified, the amount of each component in the composition means the total amount of the multiple substances present in the composition. do.
In the present disclosure, 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.
In the present disclosure, "mass %" and "weight %" have the same meaning, and "mass parts" and "weight parts" have the same meaning.
In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
In this specification, "(meth)acrylic" represents both or either acrylic and methacrylic.
In some of the compounds in this specification, 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.
（接着剤組成物）
　本開示の接着剤組成物は、ポリエステル部分とポリアミド部分を有するポリエステルポリアミド樹脂（Ａ）と、エポキシ樹脂（Ｂ）とを含む。ポリエステルポリアミド樹脂（Ａ）１００質量部に対し、エポキシ樹脂（Ｂ）の量が１質量部～６０質量部である。
　本開示の接着剤組成物は、ポリイミド接着用又は金属接着用接着剤組成物として好適に用いることができ、ポリイミドと金属との接着用接着剤組成物として特に好適に用いることができる。 (Adhesive composition)
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.
　従来の接着剤組成物の硬化物は、常湿環境下において、はんだ耐熱性が十分でないことを本発明者らは見出した。前述したように、高温高湿下に長期保管後も強度等が低下しない接着剤組成物が求められている。
　本発明者らが鋭意検討した結果、ポリエステル部分とポリアミド部分を有するポリエステルポリアミド樹脂（Ａ）と、エポキシ樹脂（Ｂ）とを含み、ポリエステルポリアミド樹脂（Ａ）１００質量部に対し、エポキシ樹脂（Ｂ）の量が１質量部～６０質量部であることにより、得られる硬化物が、常湿環境下においてもはんだ耐熱性に優れ、かつ長期の耐湿熱性にも優れる接着性組成物を提供できることを見出した。
　この効果の詳細な機構は不明であるが、以下の理由によると推測される。ポリエステルポリアミド樹脂（Ａ）とエポキシ樹脂（Ｂ）とが互いに協奏的に作用し、互いに補完し合う。更に、ポリエステルポリアミド樹脂（Ａ）を構成するポリエステル部分により、樹脂の疎水性が向上し、耐湿性が向上する。そのため、得られる硬化物は、吸湿率が低い。得られる硬化物の吸水は、高温高湿下であっても、長期にわたって抑制される。得られる硬化物の接着性も長期にわたり維持される。得られる硬化物は、常湿環境下においてもはんだ耐熱性に優れ、かつ長期の耐湿熱性にも優れる。 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.
Although the detailed mechanism of this effect is unknown, it is presumed to be due to the following reasons. 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.
　本開示の接着剤組成物は、ポリエステル部分とポリアミド部分を有するポリエステルポリアミド樹脂（Ａ）と、エポキシ樹脂（Ｂ）とを含む。ポリエステルポリアミド樹脂（Ａ）１００質量部に対し、エポキシ樹脂（Ｂ）の量が１質量部～６０質量部である。本開示の接着剤組成物は、上記の構成を有することにより、接着性、及び、貯蔵安定性にも優れる。 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.
　以下、本開示について詳細に説明する。
　本明細書においては、「ポリエステルポリアミド樹脂（Ａ）」等を「成分（Ａ）」等ともいう。 The present disclosure will be described in detail below.
In this specification, "polyester polyamide resin (A)" etc. are also referred to as "component (A)" etc.
＜ポリエステルポリアミド樹脂（Ａ）＞
　本開示の接着剤組成物は、ポリエステルポリアミド樹脂（Ａ）を含有する。
　ポリエステルポリアミド樹脂（Ａ）は、ポリエステル部分とポリアミド部分とを含む。
　ポリエステル部分は、２以上のエステル結合を有する。ポリアミド部分は、２以上のアミド結合を有する。ポリエステル部分とポリアミド部分とは、エステル結合またはアミド結合を介して結合していてよい。ポリエステルポリアミド樹脂（Ａ）は、２以上のエステル結合と２以上のアミド結合とを有する樹脂であればよい。ポリエステルポリアミド樹脂（Ａ）は、ポリエステル鎖と２以上のアミド結合とを有する樹脂、ポリアミド鎖と２以上のエステル結合とを有する樹脂、ポリエステル鎖とポリアミド鎖とを有する樹脂などであることが好ましい。ポリエステル鎖の重量平均分子量は、１，０００以上であってよい。ポリアミド鎖の重量平均分子量は、１，０００以上であってよい。ポリエステル鎖及びポリアミド鎖の各々の重量平均分子量の上限は特に限定されるものではなく、例えば１５０，０００以下であってよい。
　ポリエステルポリアミド樹脂（Ａ）は、その原料として、ポリカルボン酸と、ポリオールと、ポリアミンとを少なくとも反応させてなる樹脂であることが好ましく、ジカルボン酸と、ジオールと、ジアミンとを少なくとも反応させてなる樹脂であることがより好ましい。
　ポリエステルポリアミド樹脂（Ａ）は、直鎖状の樹脂であることが好ましい。
　ポリエステルポリアミド樹脂（Ａ）は、芳香環を有しないことが好ましい。直鎖状で、芳香環を有しないポリエステルポリアミド樹脂（Ａ）を用いることで、熱プレスや熱ラミネートでの加工性を向上できる。 <Polyester polyamide resin (A)>
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.
　ポリエステルポリアミド樹脂（Ａ）におけるポリエステル部分は、酸成分とアルコール成分とから形成されることが好ましい。
　酸成分としては、多価カルボン酸化合物が好ましく、ジカルボン酸化合物がより好ましい。酸成分としては、スルホカルボン酸化合物等も用いることができる。更に、酸成分としては、脂肪族酸が好ましく挙げられる。
　アルコール成分としては、多価アルコール化合物が好ましく、ジオール化合物がより好ましい。
　前記ポリエステル部分は、ヒドロキシカルボン酸化合物により形成されていてもよい。 The polyester portion in the polyester polyamide resin (A) is preferably formed from an acid component and an alcohol component.
As the acid component, polyvalent carboxylic acid compounds are preferred, and dicarboxylic acid compounds are more preferred. As the acid component, sulfocarboxylic acid compounds and the like can also be used. Furthermore, as the acid component, aliphatic acids are preferably mentioned.
As 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.
　芳香族酸としては、例えば、芳香族ジカルボン酸、及び芳香族オキシカルボン酸等が挙げられる。芳香族ジカルボン酸としては、スルホン酸基及びスルホン酸塩基の少なくとも一方を有しない芳香族ジカルボン酸、スルホン酸基又はスルホン酸塩基を有する芳香族ジカルボン酸等が挙げられる。
　スルホン酸基及びスルホン酸塩基の少なくとも一方を有しない芳香族ジカルボン酸としては、例えば、テレフタル酸、イソフタル酸、オルソフタル酸、ナフタレンジカルボン酸、ビフェニルジカルボン酸、及び５－ヒドロキシイソフタル酸等が挙げられる。
　スルホン酸基又はスルホン酸塩基を有する芳香族ジカルボン酸としては、例えば、スルホテレフタル酸、５－スルホイソフタル酸、４－スルホフタル酸、４－スルホナフタレン－２，７－ジカルボン酸、５－（４－スルホフェノキシ）イソフタル酸、スルホテレフタル酸、それらの金属塩、及びそれらのアンモニウム塩等が挙げられる。
　芳香族オキシカルボン酸としては、例えば、ｐ－ヒドロキシ安息香酸、ｐ－ヒドロキシフェニルプロピオン酸、ｐ－ヒドロキシフェニル酢酸、６－ヒドロキシ－２－ナフトエ酸、及び４，４－ビス（ｐ－ヒドロキシフェニル）バレリック酸等を挙げられる。
　前記酸成分は、樹脂合成時においては、エステル等の酸化合物の誘導体であってもよい。 Examples of aromatic acids include aromatic dicarboxylic acids and aromatic oxycarboxylic acids. Examples of the 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.
Examples of 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.
Examples of 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.
　脂肪族酸成分としては、例えば、脂環族ジカルボン酸及び脂肪族ジカルボン酸等が挙げられる。
　脂環族ジカルボン酸としては、例えば、１，４－シクロヘキサンジカルボン酸、１，３－シクロヘキサンジカルボン酸、及び１，２－シクロヘキサンジカルボン酸とその酸無水物などが挙げられる。
　脂肪族ジカルボン酸としては、例えば、コハク酸、アジピン酸、アゼライン酸、セバシン酸、ドデカン二酸、及びダイマー酸など等を挙げられる。
　これらの中でも、はんだ耐久性、及び、接着性の観点から、酸成分としては、アゼライン酸、及び／又は、ダイマー酸を含むことが好ましく、アゼライン酸を含むことが特に好ましい。
　はんだ耐久性、及び、接着性の観点から、酸成分としては、炭素数６～２２の脂肪族ジカルボン酸、炭素数６～２２の芳香族ジカルボン酸又は炭素数６～２２の脂環式ジカルボン酸が好ましく、炭素数６～２２の脂肪族ジカルボン酸又は炭素数６～２２の脂環式ジカルボン酸がより好ましい。 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.
Among these, from the viewpoint of solder durability and adhesion, the acid component preferably includes azelaic acid and/or dimer acid, and it is particularly preferable to include azelaic acid.
From the viewpoint of solder durability and adhesion, 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.
　多価アルコール成分としては、脂肪族ジオール化合物、脂環族ジオール化合物、芳香族含有ジオール化合物、及びエーテル結合含有ジオール化合物などが好ましく挙げられる。
　脂肪族ジオール化合物としては、例えば、エチレングリコール、１，２－プロピレンジオール、１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオ－ル、ネオペンチルグリコール、１，６－ヘキサンジオール、３－メチル－１，５－ペンタンジオール、１，９－ノナンジオール、２－ブチル－２－エチル－１，３－プロパンジオール、ヒドロキシピバリン酸ネオペンチルグリコールエステル、ジメチロールヘプタン、及び２，２，４－トリメチル－１，３－ペンタンジオール等を挙げられる。
　脂環族ジオール化合物としては、例えば、１，４－シクロヘキサンジオール、１，４－シクロヘキサンジメタノール、トリシクロデカンジオール、トリシクロデカンジメチロール、スピログリコール、水素化ビスフェノールＡ、水素化ビスフェノールＡのエチレンオキサイド付加物及びプロピレンオキサイド付加物等を挙げられる。
　芳香族含有ジオール化合物としては、例えば、パラキシレングリコール、メタキシレングリコ－ル、オルトキシレングリコール、１，４－フェニレングリコール、１，４－フェニレングリコールのエチレンオキサイド付加物、ビスフェノールＡ、ビスフェノールＡのエチレンオキサイド付加物及びプロピレンオキサイド付加物等の、ビスフェノール類の２つのフェノール性水酸基にエチレンオキサイド又はプロピレンオキサイドをそれぞれ１～数モル付加して得られるグリコール類等が挙げられる。
　エーテル結合含有ジオール化合物としては、例えば、ジエチレングリコール、トリエチレングリコール、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール、ネオペンチルグリコールエチレンオキサイド付加物、及びネオペンチルグリコールプロピレンオキサイド付加物等が挙げられる。
　これらジオールの中でも、側鎖を有するジオール（例えば、ネオペンチルグリコールや２－ブチル－２－エチル－１，３－プロパンジオール等）が、エポキシ樹脂等との相溶性及び溶液安定性の理由で好ましい。
　すなわち、ポリエステルポリアミド樹脂（Ａ）を構成するジオール成分は、エポキシ樹脂等との相溶性及び溶液安定性の観点から、側鎖を有するジオールを含むことが好ましい。
　側鎖を有するジオールにおける側鎖は、好ましくはアルキル基であり、アルキル基の炭素数は、例えば、１、２、３、４、５の何れかであってよい。これは、以降で記載される側鎖を有するジオールにおいても同様である。
　側鎖を有するジオールとしては、例えば、ネオペンチルグリコール、２－ブチル－２－エチル－１，３－プロパンジオール、及び、２，２－ジメチロールプロピオン酸などが挙げられる。 Preferred examples of the polyhydric alcohol component include aliphatic diol compounds, alicyclic diol compounds, aromatic-containing diol compounds, and ether bond-containing diol compounds.
Examples of 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.
Examples of 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.
Among these 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. .
That is, it is preferable that 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.
　ポリエステル原料として、分子構造の中にヒドロキシ基とカルボキシ基とを有するヒドロキシカルボン酸化合物を使用することができる。当該ヒドロキシカルボン酸化合物としては、例えば、５－ヒドロキシイソフタル酸、ｐ－ヒドロキシ安息香酸、ｐ－ヒドロキシフェニチルアルコール、ｐ－ヒドロキシフェニルプロピオン酸、ｐ－ヒドロキシフェニル酢酸、６－ヒドロキシ－２－ナフトエ酸、及び４，４－ビス（ｐ－ヒドロキシフェニル）バレリック酸等が挙げられる。 As a polyester raw material, a hydroxycarboxylic acid compound having a hydroxy group and a carboxy group in its molecular structure can be used. Examples of 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.
　ポリエステルポリアミド樹脂（Ａ）のポリエステル部分を構成する成分に、必要により分岐骨格を導入する目的で、３官能以上のポリカルボン酸類及び／又はポリオール類を共重合してもよい。３官能以上のポリカルボン酸類及び／又はポリオール類の量は、ポリエステル部分を構成する全酸成分又は全多価アルコール成分に対し、０．１モル％～５モル％程度である。特に硬化剤と反応させて硬化層を得る場合、分岐骨格を導入することにより、樹脂の末端基濃度（反応点）が増え、架橋密度が高い、硬化層を得ることができる。
　３官能以上のポリカルボン酸としては、例えば、トリメリット酸、トリメシン酸、エチレングリコールビス（アンヒドロトリメリテート）、グリセロールトリス（アンヒドロトリメリテート）、無水トリメリット酸、無水ピロメリット酸（ＰＭＤＡ）、オキシジフタル酸二無水物（ＯＤＰＡ）、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物（ＢＴＤＡ）、３，３’，４，４’－ジフェニルテトラカルボン酸二無水物（ＢＰＤＡ）、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物（ＤＳＤＡ）、４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸二無水物（６ＦＤＡ）、２，２’－ビス［（ジカルボキシフェノキシ）フェニル］プロパン二無水物（ＢＳＡＡ）などが挙げられる。３官能以上のポリオールとしては、例えば、グリセリン、トリメチロ－ルエタン、トリメチロールプロパン、ペンタエリスリトール等が挙げられる。
　３官能以上のポリカルボン酸及び／又はポリオ－ルの量は、全酸成分又は全多価アルコール成分に対し、好ましくは０．１モル％～５モル％、より好ましくは０．１モル％～３モル％である。
　中でも、ポリエステルポリアミド樹脂（Ａ）のポリエステル部分は、はんだ耐熱性、及び、接着性の観点から、炭素数６～２２の脂肪族ジカルボン酸、炭素数６～２２の芳香族ジカルボン酸及び／又は炭素数６～２２の脂環式ジカルボン酸と、炭素数２～５４の脂肪族、炭素数２～５４の芳香族又は炭素数２～５４の脂環式ジオールとの重縮合物であることが好ましい。 If necessary, 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. In particular, when a cured layer is obtained by reacting with a curing agent, by introducing a branched skeleton, the concentration of end groups (reaction points) of the resin increases, and a cured layer with a high crosslinking density can be obtained.
Examples of trifunctional or higher-functional polycarboxylic acids 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. Examples of trifunctional or higher functional polyols 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%.
Among these, 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. .
　本開示において、「炭素数６～２２の脂肪族ジカルボン酸、炭素数６～２２の芳香族ジカルボン酸及び／又は炭素数６～２２の脂環式ジカルボン酸」は、
　炭素数６～２２の脂肪族ジカルボン酸、炭素数６～２２の芳香族ジカルボン酸及び炭素数６～２２の脂環式ジカルボン酸と、
　炭素数６～２２の脂肪族ジカルボン酸及び炭素数６～２２の芳香族ジカルボン酸と、
　炭素数６～２２の脂肪族ジカルボン酸及び炭素数６～２２の脂環式ジカルボン酸と、
　炭素数６～２２の芳香族ジカルボン酸及び炭素数６～２２の脂環式ジカルボン酸と、
　炭素数６～２２の脂肪族ジカルボン酸と、
　炭素数６～２２の芳香族ジカルボン酸と、
　炭素数６～２２の脂環式ジカルボン酸と、
を包含する。
　本開示において、「炭素数２～５４の脂肪族ジオール、炭素数２～５４の芳香族ジオール又は炭素数２～５４の脂環式ジオール」は、
　炭素数２～５４の脂肪族ジオールと、
　炭素数２～５４の芳香族ジオールと、
　炭素数２～５４の脂環式ジオールと、
を包含する。 In the present disclosure, "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 dicarboxylic acid having 6 to 22 carbon atoms;
an alicyclic dicarboxylic acid having 6 to 22 carbon atoms;
includes.
In the present disclosure, "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.
　ポリエステルポリアミド樹脂（Ａ）のポリエステル部分には、必要によりカルボキシ基を導入する目的で、酸付加が行われていてもよい。酸付加の量は、ポリエステル部分を構成する全酸成分又は全多価アルコール成分に対し、０．１モル％～１０モル％程度である。酸付加にモノカルボン酸、ジカルボン酸、多官能カルボン酸化合物を用いると、エステル交換により分子量の低下が起こるおそれがある。そのため、酸付加に酸無水物を用いることが好ましい。
　酸無水物としては、例えば、無水コハク酸、無水マレイン酸、オルソフタル酸、２，５－ノルボルネンジカルボン酸無水物、テトラヒドロ無水フタル酸、無水トリメリット酸、無水ピロメリット酸（ＰＭＤＡ）、オキシジフタル酸二無水物（ＯＤＰＡ）、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物（ＢＴＤＡ）、３，３’，４，４’－ジフェニルテトラカルボン酸二無水物（ＢＰＤＡ）、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物（ＤＳＤＡ）、４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸二無水物（６ＦＤＡ）、２，２’－ビス［（ジカルボキシフェノキシ）フェニル］プロパン二無水物（ＢＳＡＡ）などが挙げられる。
　酸付加の方法は、例えば、ポリエステル重縮合後、バルク状態で直接行う方法、及び、ポリエステルを溶液化し付加する方法等が挙げられる。バルク状態での反応速度は、速い。しかしながら、バルク状態での反応では、ポリエステルポリアミド樹脂（Ａ）のポリエステル部分に多量に酸付加を行うとゲル化が起こることがあり、かつバルク状態での反応温度は、高温である。そのため、バルク状態での反応では、酸素ガスを遮断し酸化を防ぐなどの注意が必要である。溶液状態での酸付加では、反応は遅いが、ポリエステルポリアミド樹脂（Ａ）のポリエステル部分に多量のカルボキシ基を安定に導入することができる。 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.
Examples of acid anhydrides include succinic anhydride, maleic anhydride, orthophthalic acid, 2,5-norbornenedicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride (PMDA), and oxydiphthalic anhydride. Anhydride (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[(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. However, in the reaction in the bulk state, 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. Although 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).
　ポリエステルポリアミド樹脂（Ａ）におけるポリアミド部分は、酸成分とアミン成分とから形成されることが好ましい。
　酸成分としては、多価カルボン酸化合物が好ましく、ジカルボン酸化合物がより好ましい。酸成分としては、スルホカルボン酸化合物、及び脂肪族酸を用いることができる。
　酸成分としては、ポリエステル部分の酸成分として前述したものが好ましく挙げられる。
　中でも、ポリエステルポリアミド樹脂（Ａ）のポリアミド部分は、はんだ耐熱性、及び、接着性の観点から、炭素数６～２２の脂肪族ジカルボン酸、炭素数６～２２の芳香族ジカルボン又は炭素数６～２２の脂環式ジカルボン酸及び／又は炭素数２０～４８の二量化脂肪族二酸を含むジカルボン酸を含むことが好ましく、炭素数６～２２の脂肪族ジカルボン酸又は炭素数６～２２の脂環式ジカルボン酸及び／又は炭素数２０～４８の二量化脂肪族二酸を含むジカルボン酸を含むことがより好ましく、アゼライン酸を含むことが特に好ましい。
　前記脂肪族、芳香族又は脂環式ジカルボン酸の炭素数は、６～１２であることが好ましく、８～１０であることがより好ましい。
　前記二量化脂肪族二酸の炭素数は、３０～４８であることが好ましく、３２～４０であることがより好ましい。 The polyamide portion in the polyester polyamide resin (A) is preferably formed from an acid component and an amine component.
As the acid component, polyvalent carboxylic acid compounds are preferred, and dicarboxylic acid compounds are more preferred. As the acid component, sulfocarboxylic acid compounds and aliphatic acids can be used.
As the acid component, those mentioned above as the acid component of the polyester portion are preferably mentioned.
Among them, 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. 22 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.
　アミン成分としては、ポリアミン化合物が好ましく、ジアミン化合物がより好ましい。
　前記ポリアミド部分は、アミノカルボン酸化合物により形成されていてもよい。 As the amine component, polyamine compounds are preferred, and diamine compounds are more preferred.
The polyamide portion may be formed of an aminocarboxylic acid compound.
　ジアミン化合物としては、ジアミノシクロヘキサン、ピぺリジン、イソホロンジアミン、１，２－ジアミノエタン、１，３－ジアミノプロパン、１，４－ジアミノブタン、１，５－ジアミノペンタン、１，６－ジアミノヘキサン、１，７－ジアミノヘプタン、１，８－ジアミノオクタン、１，９－ジアミノノナン、ｏ－（又はｍ－、ｐ－）フェニレンジアミン、ｏ－（又はｍ－、ｐ－）キシレンジアミン、３，３’－（又は３，４’－）ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルエーテル、３，３’－（又は３，４’－）ジアミノジフェニルメタン、４，４’－ジアミノジフェニルメタン、３，３’－（又は３，４’－、４，４’－）ジアミノジフェニルジフルオロメタン、３，３’－（又は３，４’－、４，４’－）ジアミノジフェニルスルホン、３，３’－（又は３，４’－、４，４’－）ジアミノジフェニルスルフィド、３，３’－（又は３，４’－、４，４’－）ジアミノジフェニルケトン、２，２－ビス（３－アミノフェニル）プロパン、２，２’－（３，４’－ジアミノジフェニル）プロパン、２，２－ビス（４－アミノフェニル）プロパン、２，２－ビス（３－アミノフェニル）ヘキサフルオロプロパン、２，２－（３，４’－ジアミノジフェニル）ヘキサフルオロプロパン、２，２－ビス（４－アミノフェニル）ヘキサフルオロプロパン、１，３－（又は１，４－）ビス（３－アミノフェノキシ）ベンゼン、１，４－ビス（４－アミノフェノキシ）ベンゼン、３，３’－（１－フェニレンビス（１－メチルエチレリデン））ビスアニリン、３，４’－（１，４－フェニレンビス（１－メチルエチリデン））ビスアニリン、４，４’－（１，４－フェニレンビス（１－メチルエチリデン））ビスアニリン、２，２－ビス（４－（３－アミノフェノキシ）フェニル）プロパン、２，２－ビス（４－（４－アミノフェノキシ）フェニル）プロパン、及び２，２－ビス（４－（４－アミノフェノキシ）フェニル）ヘキサフルオロプロパンなどが挙げられる。 Examples of 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'-, 4,4'-)diaminodiphenyldifluoromethane, 3,3'-(or 3,4'-,4,4'-)diaminodiphenylsulfone, 3,3'-(or 3, 4'-, 4,4'-) diaminodiphenyl sulfide, 3,3'- (or 3,4'-, 4,4'-) diaminodiphenyl ketone, 2,2-bis(3-aminophenyl)propane, 2,2'-(3,4'-diaminodiphenyl)propane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-(3 , 4'-diaminodiphenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 1,3-(or 1,4-)bis(3-aminophenoxy)benzene, 1,4- Bis(4-aminophenoxy)benzene, 3,3'-(1-phenylenebis(1-methylethylidene))bisaniline, 3,4'-(1,4-phenylenebis(1-methylethylidene))bisaniline, 4,4'-(1,4-phenylenebis(1-methylethylidene))bisaniline, 2,2-bis(4-(3-aminophenoxy)phenyl)propane, 2,2-bis(4-(4- Examples include aminophenoxy)phenyl)propane, and 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane.
　中でも、アミン成分としては、はんだ耐熱性の観点から、炭素数６～４４の芳香族又は炭素数６～４４の脂環式骨格を有するジアミンを含むことが好ましく、炭素数６～４４の脂環式骨格を有するジアミンを含むことがより好ましく、イソホロンジアミンを含むことが特に好ましい。
　前記ジアミンの炭素数は、８～３０であることが好ましく、１０～２４であることがより好ましい。 Among these, from the viewpoint of soldering heat resistance, 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.
　中でも、ポリエステルポリアミド樹脂（Ａ）のポリアミド部分は、はんだ耐熱性、接着性、及び、導電性の観点から、炭素数６～２２の脂肪族ジカルボン酸、炭素数６～２２の芳香族ジカルボン酸及び／若しくは炭素数６～２２の脂環式ジカルボン酸並びに／又は炭素数２０～４８の二量化脂肪族二酸を含むジカルボン酸と、炭素数６～４４の芳香族及び／又は炭素数６～４４の脂環式骨格を有するジアミンとの重縮合物であることが好ましく、炭素数６～２２の脂肪族ジカルボン酸又は炭素数６～２２の脂環式ジカルボン酸及び／又は炭素数２０～４８の二量化脂肪族二酸を含むジカルボン酸と、炭素数６～４４の脂環式骨格を有するジアミンとの重縮合物であることがより好ましい。 Among them, 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.
　本開示において、「炭素数６～２２の脂肪族ジカルボン酸、炭素数６～２２の芳香族ジカルボン酸及び／若しくは炭素数６～２２の脂環式ジカルボン酸並びに／又は炭素数２０～４８の二量化脂肪族二酸」は、
　炭素数６～２２の脂肪族ジカルボン酸、炭素数６～２２の芳香族ジカルボン酸、炭素数６～２２の脂環式ジカルボン酸及び炭素数２０～４８の二量化脂肪族二酸と、
　炭素数６～２２の脂肪族ジカルボン酸及び炭素数２０～４８の二量化脂肪族二酸と、
　炭素数６～２２の芳香族ジカルボン酸及び炭素数２０～４８の二量化脂肪族二酸と、
　炭素数６～２２の脂環式ジカルボン酸及び炭素数２０～４８の二量化脂肪族二酸と、
　炭素数６～２２の脂肪族ジカルボン酸、炭素数６～２２の芳香族ジカルボン酸、炭素数６～２２の脂環式ジカルボン酸と、
　炭素数６～２２の脂肪族ジカルボン酸と、
　炭素数６～２２の芳香族ジカルボン酸と、
　炭素数６～２２の脂環式ジカルボン酸と、
　炭素数２０～４８の二量化脂肪族二酸と、
を包含する。 In the present disclosure, “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 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, 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;
aromatic dicarboxylic acid having 6 to 22 carbon atoms;
an alicyclic dicarboxylic acid having 6 to 22 carbon atoms;
a dimerized aliphatic diacid having 20 to 48 carbon atoms;
includes.
　前記ポリエステルポリアミド樹脂（Ａ）の前記ポリエステル部分が、炭素数６～２２の脂肪族ジカルボン酸、炭素数６～２２の芳香族ジカルボン酸及び／又は炭素数６～２２の脂環式ジカルボン酸と、炭素数２～５４の脂肪族ジオール、炭素数２～５４の芳香族ジオール又は炭素数２～５４の脂環式ジオールとの重縮合物であり、
　前記ポリエステルポリアミド樹脂（Ａ）の前記ポリアミド部分が、炭素数６～２２の脂肪族ジカルボン酸、炭素数６～２２の芳香族ジカルボン酸及び／若しくは炭素数６～２２の脂環式ジカルボン酸並びに／又は炭素数２０～４８の二量化脂肪族二酸を含むジカルボン酸と、炭素数６～４４の芳香族及び／又は炭素数６～４４の脂環式骨格を有するジアミンとの重縮合物であることが好ましい。
　これにより、吸水率が低く、長期の耐湿熱性に優れる接着剤組成物を提供できる。 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. Or 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. It is preferable.
This makes it possible to provide an adhesive composition with low water absorption and excellent long-term heat and humidity resistance.
　ポリエステルポリアミド樹脂（Ａ）を製造する上で、必要により鎖延長剤を使用してもよい。
　鎖延長剤としては、例えば、ポリエステル部分の構成成分として既に記載したジオール化合物、及び１つのカルボキシ基と２つのヒドロキシ基とを有する化合物（例えば、ジメチロールプロピオン酸、ジメチロールブタン酸等）等が挙げられる。
　中でも、鎖延長剤としては、導電性の観点から、ジオール化合物が好ましく、側鎖を有するジオール化合物がより好ましく、分岐鎖を有するジオール化合物が特に好ましい。
　側鎖を有するジオール化合物は、導電性の観点から、ネオペンチルグリコール、２－ブチル－２－エチル－１，３－プロパンジオール、及び、２，２－ジメチロールプロピオン酸よりなる群から選ばれた少なくとも１種の化合物を含むことが好ましい。側鎖を有するジオール化合物は、ネオペンチルグリコール及び２－ブチル－２－エチル－１，３－プロパンジオールよりなる群から選ばれた少なくとも１種の化合物と、２，２－ジメチロールプロピオン酸とを含むことが特に好ましい。
　鎖延長剤として、ポリアミン化合物を使用してもよい。 When producing the polyester polyamide resin (A), a chain extender may be used if necessary.
Examples of 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.
Among these, as the chain extender, from the viewpoint of electrical conductivity, 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.
　ポリエステルポリアミド樹脂（Ａ）の製造方法としては、特に制限はなく、公知の方法を用いることができる。例えば、ポリカルボン酸、ポリオール及びポリアミン、必要により前記鎖延長剤を一括して反応容器に仕込んでもよいし、分割して仕込んでもよい。いずれにしても、系内のポリオール及びポリアミンの水酸基価及びアミン価の合計と、ポリカルボン酸のカルボキシ基の合計に対して、カルボキシ基／ヒドロキシ基及びアミノ基の官能基の比率が、好ましくは０．９以上１．１以下、より好ましくは０．９８以上１．０２以下、特に好ましくは１である。この反応は、溶媒の存在下又は非存在下に反応させることにより製造することができる。溶媒としては、例えば、エステル系溶媒（例えば、酢酸エチル、酢酸ブチル、酪酸エチルなど）、エーテル系溶媒（例えば、ジオキサン、テトラヒドロフラン、ジエチルエーテルなど）、ケトン系溶媒（例えば、シクロヘキサノン、メチルエチルケトン、メチルイソブチルケトンなど）、芳香族炭化水素系溶媒（例えば、ベンゼン、トルエン、キシレンなど）及びこれらの混合溶媒等が挙げられる。溶媒としては、環境負荷の低減の観点から、酢酸エチル又はメチルエチルケトンが好ましい。反応装置としては、撹拌装置の具備した反応缶に限らず、ニーダー、二軸押出機のような混合混練装置も使用できる。
　エステル化又はアミド化反応を促進させるため、通常のエステル化及び／又はアミド化反応において用いられる触媒（例えば、テトラブトキシチタネート等）を使用することができる。必要に応じ、縮合剤等も用いてもよい。 There are no particular restrictions on the method for producing the polyester polyamide resin (A), and known methods can be used. For example, 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. In any case, 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. Examples of solvents 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. As the solvent, ethyl acetate or methyl ethyl ketone is preferable from the viewpoint of reducing environmental load. 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.
In order to promote the esterification or amidation reaction, a catalyst (eg, tetrabutoxy titanate, etc.) used in a normal esterification and/or amidation reaction can be used. If necessary, a condensing agent or the like may also be used.
　ポリエステルポリアミド樹脂（Ａ）におけるポリエステル部分のガラス転移温度（Ｔｇ）は、接着性、導電性、及び、耐熱性の観点から、４０℃～１５０℃であることが好ましく、４５℃～１２０℃であることがより好ましく、５０℃～９０℃であることが更に好ましく、６０℃～７０℃であることが特に好ましい。
　ポリエステルポリアミド樹脂（Ａ）のガラス転移温度（Ｔｇ）は、接着性、導電性、及び、耐熱性の観点から、３０℃～１５０℃であることが好ましく、４０℃～１４０℃であることがより好ましく、５０℃～９０℃であることが更に好ましく、６０℃～７０℃であることが特に好ましい。 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.
　ポリエステルポリアミド樹脂（Ａ）の重量平均分子量（Ｍｗ）は、はんだ耐熱性、導電性、及び、耐熱性の観点から、５，０００～１５０，０００であることが好ましく、１０，０００～１００，０００であることがより好ましく、３０，０００～８０，０００であることが更に好ましく、４０，０００～６０，０００であることが特に好ましい。ポリエステルポリアミド樹脂（Ａ）の数平均分子量（Ｍｎ）は、はんだ耐熱性、導電性、及び、耐熱性の観点から、１，５００～５０，０００であることが好ましく、１０，０００～２５，０００であることがより好ましく、１３，０００～２０，０００であることが更に好ましい。
　本開示における樹脂の数平均分子量（Ｍｎ）、及び、重量平均分子量（Ｍｗ）の値は、下記の条件でゲルパーミエーションクロマトグラフィー（以下、「ＧＰＣ」ともいう）により測定した分子量をポリスチレン換算した値を意味する。
＜測定条件＞
　装置：東ソー（株）製型式名「ＨＬＣ－８３２０」
　カラム：東ソー（株）製ＴＳＫｇｅｌ ＳｕｐｅｒＭｕｌｔｉｐｏｒｅＨＺ－Ｍ×４本
　溶媒：テトラヒドロフラン
　カラム温度：４０℃
　検出器：ＲＩ
　流速：６００μＬ／ｍｉｎ 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.
<Measurement conditions>
Device: Tosoh Corporation model name “HLC-8320”
Column: TSKgel SuperMultiporeHZ-M (manufactured by Tosoh Corporation) x 4 Solvent: Tetrahydrofuran Column temperature: 40°C
Detector: RI
Flow rate: 600μL/min
　ポリエステルポリアミド樹脂（Ａ）のアミン価は、はんだ耐熱性、接着性、及び、導電性の観点から、１．０ｍｇＫＯＨ／ｇ～１２．０ｍｇＫＯＨ／ｇであることが好ましく、３．０ｍｇＫＯＨ／ｇ～１１．０ｍｇＫＯＨ／ｇであることがより好ましく、６．０ｍｇＫＯＨ／ｇ～１０．０ｍｇＫＯＨ／ｇであることが更に好ましく、７．０ｍｇＫＯＨ／ｇ～８．０ｍｇＫＯＨ／ｇであることが特に好ましい。
　本開示における樹脂のアミン価は、ＪＩＳ　Ｋ　７２３７（１９９５）に準拠し、電位差測定法により測定及び算出するものとする。 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).
　本開示の接着剤組成物は、ポリエステルポリアミド樹脂（Ａ）を、１種単独で含有していても、２種以上を含有していてもよい。
　ポリエステルポリアミド樹脂（Ａ）の含有量は、接着性、導電性、及び、耐熱性の観点から、接着剤組成物の全固形分量に対し、５質量％～９８質量％であることが好ましく、１０質量％～９５質量％であることがより好ましく、２０質量％～９０質量％であることが更に好ましく、３０質量％～８５質量％であることが特に好ましい。 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.
＜エポキシ樹脂（Ｂ）＞
　本開示の接着剤組成物は、エポキシ樹脂（Ｂ）を含有する。
　エポキシ樹脂（Ｂ）は、接着性や接着後の硬化部における耐熱性等を与える成分である。本開示におけるエポキシ樹脂（Ｂ）には、エポキシ基を有する高分子化合物だけでなく、エポキシ基を有する低分子化合物も含まれる。エポキシ樹脂（Ｂ）におけるエポキシ基の数は、２以上であることが好ましい。
　エポキシ樹脂（Ｂ）としては、例えば、グリシジルエステル、グリシジルエーテル類、ノボラック型エポキシ樹脂等が挙げられる。
　グリシジルエステルとしては、例えば、オルトフタル酸ジグリシジルエステル、イソフタル酸ジグリシジルエステル、テレフタル酸ジグリシジルエステル、ｐ－ヒドロキシ安息香酸ジグリシジルエステル、テトラヒドロフタル酸ジグリシジルエステル、コハク酸ジグリシジルエステル、アジピン酸ジグリシジルエステル、セバシン酸ジグリシジルエステル、トリメリット酸トリグリシジルエステル等が挙げられる。
　グリシジルエーテル類としては、例えば、ビスフェノールＡのジグリシジルエーテル及びそのオリゴマー、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、１，４－ブタンジオールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ペンタエリスリトールテトラグリシジルエーテル、テトラフェニルグリシジルエーテルエタン、トリフェニルグリシジルエーテルエタン、ソルビトールのポリグリシジルエーテル、ポリグリセロールのポリグリシジルエーテル等が挙げられる。
　ノボラック型エポキシ樹脂としては、例えば、フェノールノボラックエポキシ樹脂、ｏ－クレゾールノボラックエポキシ樹脂、ビスフェノールＡノボラックエポキシ樹脂等が挙げられる。
　エポキシ樹脂（Ｂ）としては、難燃性を付与した臭素化ビスフェノールＡ型エポキシ樹脂、リン含有エポキシ樹脂、トリスフェノールメタン骨格含有エポキシ樹脂、ジシクロペンタジエン骨格含有エポキシ樹脂、ナフタレン骨格含有エポキシ樹脂、アントラセン型エポキシ樹脂、ターシャリーブチルカテコール型エポキシ樹脂、ビフェニル型エポキシ樹脂及びビスフェノールＳ型エポキシ樹脂等も用いることができる。
　中でも、エポキシ樹脂（Ｂ）は、接着性、及び、はんだ耐熱性の観点から、トリスフェノールメタン骨格含有エポキシ樹脂を含むことが好ましい。 <Epoxy resin (B)>
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.
Examples of the glycidyl ester 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.
Examples of 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.
Among these, the epoxy resin (B) preferably contains an epoxy resin containing a trisphenolmethane skeleton from the viewpoints of adhesiveness and soldering heat resistance.
　本開示においては、硬化後における高い耐熱性を発現させるために、エポキシ樹脂（Ｂ）は、１分子中に３個以上のエポキシ基を有する化合物を含むことが好ましい。このような化合物を用いると、１分子中に２個のエポキシ基を有するエポキシ樹脂を用いた場合に比べて、ポリエステルウレタン樹脂（Ａ）と、カルボキシ基又はカルボン酸無水物構造を有する樹脂（Ｃ）との架橋反応性が高くなり、十分な耐熱性が得られる。
　エポキシ樹脂（Ｂ）における１分子中に３個以上のエポキシ基を有する化合物の含有量は、耐熱性の観点から、エポキシ樹脂（Ｂ）の全質量に対し、１５質量％以上であることが好ましく、２０質量％以上であることがより好ましく、２５質量％以上であることが特に好ましい。 In the present disclosure, in order to exhibit high heat resistance after curing, the epoxy resin (B) preferably contains a compound having three or more epoxy groups in one molecule. When such a compound is used, 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.
From the viewpoint of heat resistance, 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.
　本開示の接着剤組成物は、エポキシ樹脂（Ｂ）を、１種単独含有していても、２種以上を含有していてもよい。
　エポキシ樹脂（Ｂ）の含有量は、前記接着剤組成物におけるポリエステルポリアミド樹脂（Ａ）の含有量１００質量部に対して、１質量％～６０質量％であり、はんだ耐熱性、接着性、及び、導電性の観点から、２質量％～５０質量％であることが好ましく、５質量％～４０質量％であることがより好ましく、１０質量％～４０質量％であることが特に好ましい。 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.
　ポリエステルポリアミド樹脂（Ａ）及びエポキシ樹脂（Ｂ）の総量は、はんだ耐熱性、接着性、及び、導電性の観点から、接着剤組成物のフィラーを除く全固形分量に対して、好ましくは５０質量％以上であり、より好ましくは８０質量％以上であり、１００質量％であってもよい。 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.
＜ポリウレタン樹脂（Ｃ）＞
　本開示の接着剤組成物は、ポリウレタン樹脂（Ｃ）を更に含むことが好ましい。これにより、さらに吸水率を低くすることができる。
　ポリウレタン樹脂（Ｃ）として、ポリエステルポリウレタン樹脂を更に含むことがより好ましい。
　ポリウレタン樹脂（Ｃ）としては、特に制限はなく、公知のポリウレタン樹脂を用いることができる。ポリウレタン樹脂（Ｃ）は、はんだ耐熱性、接着性、及び、導電性の観点から、ポリエステルポリウレタン樹脂であることが好ましい。
　ポリエステルポリウレタン樹脂を構成するジイソシアネート成分は、炭素数８～１４の炭化水素基を有するジイソシアネート化合物を含むことが好ましい。
　ポリエステルポリウレタン樹脂は、２以上のエステル結合と２つ以上のウレタン結合とを有する樹脂であればよく、ポリエステル鎖と２以上のウレタン結合とを有する樹脂であることが好ましい。
　ポリエステルポリウレタン樹脂は、ポリエステルポリオールと、ポリイソシアネートと、鎖延長剤とを少なくとも反応させてなる樹脂であることが好ましい。ポリエステルポリウレタン樹脂は、ポリエステルポリオールと、ポリイソシアネートと、ジオール化合物とを少なくとも反応させてなる樹脂であることがより好ましい。 <Polyurethane resin (C)>
It is preferable that 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.
　ポリエステルポリウレタン樹脂におけるポリエステル部分は、酸成分とアルコール成分とから形成されることが好ましい。
　酸成分としては、多価カルボン酸化合物が好ましく、ジカルボン酸化合物がより好ましい。酸成分としては、スルホカルボン酸化合物等も用いることができる。更に、酸成分としては、芳香族酸が好ましく挙げられる。
　酸成分の具体例としては、ポリエステルポリアミド樹脂（Ａ）において前述した酸成分の具体例が挙げられる。
　アルコール成分としては、多価アルコール化合物が好ましく、ジオール化合物がより好ましい。
　アルコール成分の具体例としては、ポリエステルポリアミド樹脂（Ａ）において前述したアルコール成分の具体例が挙げられる。
　前記ポリエステル部分は、ヒドロキシカルボン酸化合物により形成されていてもよい。
　ポリエステルポリウレタン樹脂のポリエステル部分を構成する全酸成分の合計量１００モル％に対する芳香族酸の量は、接着性、耐熱性及び耐湿熱性の観点から、３０モル％以上であることが好ましく、４５モル％以上であることがより好ましく、６０モル％以上であることが特に好ましい。 The polyester portion in the polyester polyurethane resin is preferably formed from an acid component and an alcohol component.
As the acid component, polyvalent carboxylic acid compounds are preferred, and dicarboxylic acid compounds are more preferred. As the acid component, sulfocarboxylic acid compounds and the like can also be used. Furthermore, as the acid component, aromatic acids are preferably mentioned.
Specific examples of the acid component include those mentioned above for the polyester polyamide resin (A).
As 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.
　ポリエステルポリウレタン樹脂のポリエステル部分を構成する成分に、必要により分岐骨格を導入する目的で、３官能以上のポリカルボン酸類及び／又はポリオールを共重合してもよい。３官能以上のポリカルボン酸類及び／又はポリオール類の量は、ポリエステル部分を構成する全酸成分又は全多価アルコール成分に対し、０．１モル％～５モル％程度である。特に硬化剤と反応させて硬化層を得る場合、分岐骨格を導入することにより、樹脂の末端基濃度（反応点）が増え、架橋密度が高い、硬化層を得ることができる。
　３官能以上のポリカルボン酸としては、例えば、トリメリット酸、トリメシン酸、エチレングリコールビス（アンヒドロトリメリテート）、グリセロールトリス（アンヒドロトリメリテート）、無水トリメリット酸、無水ピロメリット酸（ＰＭＤＡ）、オキシジフタル酸二無水物（ＯＤＰＡ）、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物（ＢＴＤＡ）、３，３’，４，４’－ジフェニルテトラカルボン酸二無水物（ＢＰＤＡ）、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物（ＤＳＤＡ）、４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸二無水物（６ＦＤＡ）、２，２’－ビス［（ジカルボキシフェノキシ）フェニル］プロパン二無水物（ＢＳＡＡ）などが挙げられる。３官能以上のポリオールとしては、例えば、グリセリン、トリメチロ－ルエタン、トリメチロールプロパン、ペンタエリスリトール等が挙げられる。
　３官能以上のポリカルボン酸及び／又はポリオ－ルの量は、全酸成分又は全多価アルコール成分に対し、好ましくは０．１モル％～５モル％、より好ましくは０．１モル％～３モル％である。 For the purpose of introducing a branched skeleton into the components constituting the polyester portion of the polyester polyurethane resin, 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. In particular, when a cured layer is obtained by reacting with a curing agent, by introducing a branched skeleton, the concentration of end groups (reaction points) of the resin increases, and a cured layer with a high crosslinking density can be obtained.
Examples of trifunctional or higher-functional polycarboxylic acids 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. Examples of trifunctional or higher functional polyols 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%.
　ポリエステルポリウレタン樹脂のポリエステル部分には、必要によりカルボキシ基を導入する目的で、酸付加が行われていてもよい。酸付加の量は、ポリエステル部分を構成する全酸成分又は全多価アルコール成分に対し、０．１モル％～１０モル％程度である。酸付加にモノカルボン酸、ジカルボン酸、多官能カルボン酸化合物を用いると、エステル交換により分子量の低下が起こるおそれがある。そのため、酸付加に酸無水物を用いることが好ましい。
　酸無水物としては、例えば、無水コハク酸、無水マレイン酸、オルソフタル酸、２，５－ノルボルネンジカルボン酸無水物、テトラヒドロ無水フタル酸、無水トリメリット酸、無水ピロメリット酸（ＰＭＤＡ）、オキシジフタル酸二無水物（ＯＤＰＡ）、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物（ＢＴＤＡ）、３，３’，４，４’－ジフェニルテトラカルボン酸二無水物（ＢＰＤＡ）、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物（ＤＳＤＡ）、４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸二無水物（６ＦＤＡ）、２，２’－ビス［（ジカルボキシフェノキシ）フェニル］プロパン二無水物（ＢＳＡＡ）などが挙げられる。
　酸付加の方法は、ポリエステル重縮合後、バルク状態で直接行う方法、及び、ポリエステルを溶液化し付加する方法等が挙げられる。バルク状態での反応速度は、速い。しかしながら、バルク状態での反応では、ポリエステルポリアミド樹脂（Ａ）のポリエステル部分に多量に酸付加を行うとゲル化が起こることがあり、かつバルク状態での反応温度は、高温である。そのため、バルク状態での反応では、酸素ガスを遮断し酸化を防ぐなどの注意が必要である。溶液状態での酸付加では、反応は遅いが、ポリエステルポリアミド樹脂（Ａ）のポリエステル部分に多量のカルボキシ基を安定に導入することができる。 If necessary, 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.
Examples of acid anhydrides include succinic anhydride, maleic anhydride, orthophthalic acid, 2,5-norbornenedicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride (PMDA), and oxydiphthalic anhydride. Anhydride (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[(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. However, in the reaction in the bulk state, 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. Although 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).
　ポリエステルポリウレタン樹脂のポリウレタン部分は、ジイソシアネート成分から少なくとも構成される。
　前記ジイソシアネート成分は、炭素数８～１４の炭化水素基を有するジイソシアネート化合物を含む。炭化水素基中のメチレン基は非反応性の結合（例えば、は－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－など）で置き換えられてもよい。ジイソシアネート成分における炭素数８～１４の炭化水素基を有するジイソシアネート化合物の量は、通常７０モル％以上であり、好ましくは９０モル％以上であり、１００モル％であってもよい。
　ポリエステルポリウレタン樹脂のポリウレタン部分は、ジイソシアネート成分以外に、１官能又は３官能以上のイソシアネート成分から構成されていてもよい。
　前記炭素数８～１４の炭化水素基を有するジイソシアネート化合物における炭化水素基の炭素数は、得られる硬化物のはんだ後、長期信頼性試験後及び冷熱サイクル試験後の導電性の観点から、８～１２であることが好ましく、８～１０であることがより好ましい。
　前記炭素数８～１４の炭化水素基を有するジイソシアネート化合物は、得られる硬化物のはんだ後、長期信頼性試験後及び冷熱サイクル試験後の導電性の観点から、脂環式構造を有することが好ましい。 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. .
　ポリエステルポリウレタン樹脂においては、接着性の観点から、ポリエステル部分１モル当量に対するジイソシアネート成分の量が５モル当量～５０モル当量であることが好ましい。言い換えると、ポリエステルポリウレタン樹脂においては、接着性の観点から、ポリエステル部分１モル当量に対するウレタン結合の量が１０モル当量～１００モル当量であることが好ましい。 In the polyester polyurethane resin, from the viewpoint of adhesiveness, the amount of the diisocyanate component per 1 molar equivalent of the polyester portion is preferably 5 molar equivalents to 50 molar equivalents. In other words, in the polyester polyurethane resin, from the viewpoint of adhesiveness, the amount of urethane bonds per 1 molar equivalent of the polyester portion is preferably 10 molar equivalents to 100 molar equivalents.
　ポリエステルポリウレタン樹脂の製造に使用するポリイソシアネートは、ジイソシアネート、その二量体（ウレトジオン）、その三量体（イソシアヌレート、トリオール付加物、ビューレット）等の一種、又は、それらの二種以上の混合物であってもよい。ジイソシアネート成分としては、例えば、ジフェニルメタンジイソシアネート、３，３’－ジメトキシ－４，４’－ビフェニレンジイソシアネート、１，５－ナフタレンジイソシアネート、２，６－ナフタレンジイソシアネート、４，４’－ジイソシアネートジフェニルエーテル、ｍ－キシリレンジイソシアネート、１，３－ビス（イソシアナトメチル）シクロヘキサン、１，４－ビス（イソシアナトメチル）シクロヘキサン、メチレンビス（４－シクロヘキシルジイソシアネート）、イソホロンジイソシアネート、ノルボルナンジイソシアネート、及びノルボルネンジイソシアネート等が挙げられる。
　中でも、透明性、得られる硬化物のはんだ後、長期信頼性試験後及び冷熱サイクル試験後の導電性の観点から、脂肪族又は脂環族のジイソシアネート化合物が好ましく、脂環族ジイソシアネート化合物が特に好ましい。入手のし易さ、及び、冷熱サイクル試験後の導電性の観点から、１，３－ビス（イソシアナトメチル）シクロヘキサン、１，４－ビス（イソシアナトメチル）シクロヘキサン、メチレンビス（４－シクロヘキシルジイソシアネート）、又は、ノルボルナンジイソシアネート好ましく、１，３－ビス（イソシアナトメチル）シクロヘキサンが特に好ましい。 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. Examples of 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.
Among these, aliphatic or alicyclic diisocyanate compounds are preferable, and alicyclic diisocyanate compounds are particularly preferable, from the viewpoint of transparency and conductivity of the resulting cured product after soldering, after long-term reliability tests, and after thermal cycle tests. . From the viewpoint of availability and conductivity after thermal cycle test, 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.
　ポリエステルポリウレタン樹脂を製造する上で、必要により鎖延長剤を使用してもよい。
　鎖延長剤としては、例えば、ポリエステル部分の構成成分として既に記載したジオール化合物、１つのカルボキシ基と２つのヒドロキシ基とを有する化合物（例えば、ジメチロールプロピオン酸、ジメチロールブタン酸等）等が挙げられる。
　中でも、鎖延長剤としては、導電性の観点から、ジオール化合物が好ましく、側鎖を有するジオール化合物がより好ましく、分岐鎖を有するジオール化合物が特に好ましい。
　側鎖を有するジオール化合物は、導電性の観点から、ネオペンチルグリコール、２－ブチル－２－エチル－１，３－プロパンジオール、及び、２，２－ジメチロールプロピオン酸よりなる群から選ばれた少なくとも１種の化合物を含むことが好ましい。側鎖を有するジオール化合物は、ネオペンチルグリコール及び２－ブチル－２－エチル－１，３－プロパンジオールよりなる群から選ばれた少なくとも１種の化合物と、２，２－ジメチロールプロピオン酸とを含むことが特に好ましい。
　鎖延長剤として、ポリアミノ化合物を使用してもよい。一実施形態においては、ポリエステルポリウレタン樹脂は、ウレア結合を含まないものが好ましい場合がある。 When producing a polyester polyurethane resin, a chain extender may be used if necessary.
Examples of 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.
Among these, as the chain extender, from the viewpoint of electrical conductivity, 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. In one embodiment, the polyester polyurethane resin may preferably be free of urea bonds.
　ポリエステルポリウレタン樹脂の製造方法としては、特に制限はなく、公知の方法を用いることができる。例えば、ポリエステルポリオール及びポリイソシアネート、必要により前記鎖延長剤を一括して反応容器に仕込んでもよいし、分割して仕込んでもよい。いずれにしても、系内のポリエステルポリオール及び鎖延長剤の水酸基価の合計と、ポリイソシアネートのイソシアネート基の合計に対して、イソシアネート基／ヒドロキシ基の官能基の比率が、好ましくは０．９以上１．１以下、より好ましくは０．９８以上１．０２以下、特に好ましくは１である。この反応は、イソシアネート基に対して不活性な溶媒の存在下又は非存在下に反応させることにより製造することができる。その溶媒としては、エステル系溶媒（例えば、酢酸エチル、酢酸ブチル、酪酸エチルなど）、エーテル系溶媒（例えば、ジオキサン、テトラヒドロフラン、ジエチルエーテルなど）、ケトン系溶媒（例えば、シクロヘキサノン、メチルエチルケトン、メチルイソブチルケトンなど）、芳香族炭化水素系溶媒（例えば、ベンゼン、トルエン、キシレンなど）及びこれらの混合溶媒が挙げられる。溶媒としては、環境負荷の低減の観点から、酢酸エチル又はメチルエチルケトンが好ましい。反応装置としては、撹拌装置の具備した反応缶に限らず、ニーダー、二軸押出機のような混合混練装置も使用できる。 There are no particular restrictions on the method for producing the polyester polyurethane resin, and known methods can be used. For example, 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. In any case, 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. Examples of the solvent 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 ketone). etc.), aromatic hydrocarbon solvents (for example, benzene, toluene, xylene, etc.), and mixed solvents thereof. As the solvent, ethyl acetate or methyl ethyl ketone is preferable from the viewpoint of reducing environmental load. 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.
　ウレタン反応を促進させるため、通常のウレタン反応において用いられる触媒を用いてもよい。このような触媒としては、例えば、錫系触媒（例えば、トリメチルチンラウレート、ジメチルチンジラウレート、トリメチルチンヒドロキサイド、ジメチルチンジヒドロキサイド、スタナスオクトエートなど）、鉛系触媒（例えば、レッドオレート、レッド－２－エチルヘキソエートなど）アミン系触媒（例えば、トリエチルアミン、トリブチルアミン、モルホリン、ジアザビシクロオクタン、ジアザビシクロウンデセンなど）等を使用することができる。 In order to promote the urethane reaction, a catalyst used in normal urethane reactions may be used. Examples of such 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.
　ポリエステルポリウレタン樹脂におけるポリエステル部分のガラス転移温度（Ｔｇ）は、接着性、導電性、及び、耐熱性の観点から、４０℃～１５０℃であることが好ましく、４５℃～１２０℃であることがより好ましく、５０℃～９０℃であることが更に好ましく、６０℃～７０℃であることが特に好ましい。
　ポリエステルポリウレタン樹脂のガラス転移温度（Ｔｇ）は、接着性、導電性、及び、耐熱性の観点から、３０℃～１５０℃であることが好ましく、４０℃～１４０℃であることがより好ましく、５０℃～９０℃であることが更に好ましく、６０℃～７０℃であることが特に好ましい。 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.
　ポリエステルポリウレタン樹脂の数平均分子量（Ｍｎ）は、導電性、及び、耐熱性の観点から、５，０００～１００，０００であることが好ましく、１０，０００～８０，０００であることがより好ましく、２０，０００～６０，０００であることが更に好ましく、２５，０００～５０，０００であることが特に好ましい。ポリエステルポリウレタン樹脂の重量平均分子量（Ｍｗ）は、導電性、及び、耐熱性の観点から、２０，０００～４００，０００であることが好ましく、４０，０００～３２０，０００であることがより好ましく、８０，０００～２４０，０００であることが更に好ましい。 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.
　ポリエステルポリウレタン樹脂におけるウレタン結合１個当たりの分子量は、導電性、及び、耐熱性の観点から、２００～８，０００であることが好ましく、２００～５，０００であることがより好ましく、３００～２，０００であることが更に好ましく、４００～１，５００であることが特に好ましく、７００～１，０００であることが最も好ましい。
　ポリエステルポリウレタン樹脂において、１分子当たり４０個のウレタン結合が存在し、数平均分子量が３２，０００である場合は、ウレタン結合１個あたりの分子量は８００（３２，０００／４０＝８００）である。ポリエステルポリウレタン樹脂が、１分子当たりＸ個のウレタン結合を有し、数平均分子量がＹである場合、ポリエステルポリウレタン樹脂におけるウレタン結合１個当たりの分子量はＹ／Ｘとなる。原料組成から算出する場合に、ポリエステルポリウレタン樹脂（Ｃ）の原料であるポリエステルポリオール１モルに対して反応させたイソシアネート基のモル数を「ポリエステルポリウレタン樹脂におけるウレタン結合の個数」とみなすこともできる。 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.
In a polyester polyurethane resin, when there are 40 urethane bonds per molecule and the number average molecular weight is 32,000, the molecular weight per urethane bond is 800 (32,000/40=800). When 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. When calculating from the raw material composition, the number of moles of isocyanate groups reacted with 1 mole of polyester polyol, which is the raw material of polyester polyurethane resin (C), can also be regarded as "the number of urethane bonds in the polyester polyurethane resin."
　ポリウレタン樹脂（Ｃ）の酸価（好ましくはポリエステルポリウレタン樹脂の酸価）は、接着性、及び、導電性の観点から、０ｍｇＫＯＨ／ｇ～５０ｍｇＫＯＨ／ｇであることが好ましく、０．１ｍｇＫＯＨ／ｇ～２０ｍｇＫＯＨ／ｇであることがより好ましく、０．１ｍｇＫＯＨ／ｇ～５ｍｇＫＯＨ／ｇであることが更に好ましく、１．０ｍｇＫＯＨ／ｇ～５．０ｍｇＫＯＨ／ｇであることが特に好ましい。
　ポリエステルポリウレタン樹脂（Ｃ）の酸価は、耐熱性の観点からは、２０ｍｇＫＯＨ／ｇ以下であることが好ましく、５．０ｍｇＫＯＨ／ｇ以下であることが特に好ましい。
　本開示における樹脂の酸価の測定方法は、フェノールフタレイン溶液を指示薬として用い、試料を水酸化カリウムベンジルアルコール溶液で中和滴定して酸価を求める方法である。 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.
　中でも、ポリエステルポリウレタン樹脂は、接着性、導電性、及び、耐熱性の観点から、数平均分子量が１，０００～５０，０００のポリエステル構造を有するポリエステルポリウレタン樹脂を含むことが好ましく、数平均分子量が２，０００～４０，０００のポリエステル構造を有するポリエステルポリウレタン樹脂を含むことがより好ましく、数平均分子量が３，０００～３０，０００のポリエステル構造を有するポリエステルポリウレタン樹脂を含むことが更に好ましく、数平均分子量が８，０００～３０，０００のポリエステル構造を有するポリエステルポリウレタン樹脂を含むことが特に好ましく、数平均分子量が１５，０００～３０，０００のポリエステル構造を有するポリエステルポリウレタン樹脂が最も好ましい。 Among these, 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. It is particularly preferable to include a 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.
　本開示の接着剤組成物は、ポリウレタン樹脂（Ｃ）を含有してもよい。ポリウレタン樹脂（Ｃ）は、１種単独であってもよいし、２種以上であってもよい。
　ポリウレタン樹脂（Ｃ）の含有量（好ましくはポリエステルポリウレタン樹脂の含有量）は、はんだ耐熱性、接着性、及び、導電性の観点から、接着剤組成物の全固形分量に対し、１質量％～５０質量％であることが好ましく、５質量％～４０質量％であることがより好ましく、１５質量％～３５質量％であることが特に好ましい。 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.
＜導電性フィラー（Ｄ）＞
　本開示の接着剤組成物は、導電性、及び、はんだ耐熱性の観点から、導電性フィラー（Ｇ）を更に含むことが好ましい。
　導電性フィラーの体積抵抗率は、１．０×１０１１Ω・ｃｍ未満であることが好ましい。
　導電性フィラー（Ｄ）としては、導電性金属（例えば、金、白金、銀、銅、ニッケルなど）又はその合金からなる金属粒子が好ましく挙げられる。導電性フィラー（Ｄ）は、コストダウンの観点から、単一組成の粒子ではない粒子であってもよい。単一組成の粒子ではない粒子（以下、「被覆粒子」ともいう）は、核体と、核体に付着した被覆層とを有する。核体は、金属又は樹脂からなる。被覆層は、導電性が高い素材で形成されている。前記核体は、ニッケル、シリカ、銅及び樹脂よりなる群から選択される少なくとも１種の材質からなることが好ましく、導電性の金属又はその合金からなることがより好ましい。前記被覆層は、導電性が優れる材質からなる層であることが好ましく、導電性金属又は導電性ポリマーからなる層であることが好ましい。
　導電性金属は、例えば、金、白金、銀、錫、マンガン、及び、インジウム等、並びにその合金が挙げられる。導電性ポリマーは、ポリアニリン、ポリアセチレン等が挙げられる。これらの中でも、導電性の面から、銀が好ましい。
　酸化インジウムスズ等の導電性金属酸化物、カーボンブラック等も挙げられる。 <Conductive filler (D)>
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 Ω·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.
Examples of 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.
　被覆粒子の被覆層の割合は、コスト及び導電性の観点から、核体１００質量部に対して、１質量部～４０質量部が好ましく、５質量部～３０質量部がより好ましい。 From the viewpoints of cost and conductivity, 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.
　前記被覆粒子は、被覆層が核体を完全に覆っている粒子であることが好ましい。核体の一部が露出していてもよい。核体の一部が露出している場合、核体の表面面積に対する核体の被覆層に被覆されている面積の割合は、導電性が維持されやすい観点から、７０％以上であることが好ましい。 The coated particles are preferably particles in which the coating layer completely covers the core. A part of the nuclear body may be exposed. When a part of the nuclear body is 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. .
　導電性フィラー（Ｄ）の形状は、所望の導電性が得られれば限定されない。導電性フィラー（Ｄ）の形状は、球状、フレーク状、葉状、樹枝状、プレート状、針状、棒状、又は、ブドウ状が好ましい。 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.
　導電性フィラー（Ｄ）の平均粒子径は、導電性、及び、貯蔵安定性の観点から、１μｍ～１００μｍであることが好ましく、３μｍ～５０μｍであることがより好ましく、４μｍ～１５μｍであることが特に好ましい。
　本明細書におけるフィラーの平均粒子径は、レーザー回折・散乱法粒度分布測定装置ＬＳ　１３３２０（ベックマン・コールター社製）を使用し、トルネードドライパウダーサンプルモジュールにて、フィラーを測定して得た体積基準の粒度分布におけるＤ５０平均粒子径である。Ｄ５０平均粒子径は、体積基準の粒度分布の微粒子側からの粒子の積算値が５０体積％である粒度の直径の平均粒子径を示す。 The average particle diameter of the conductive filler (D) is preferably 1 μm to 100 μm, more preferably 3 μm to 50 μm, and preferably 4 μm to 15 μm, 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.
　本開示の接着剤組成物は、導電性フィラー（Ｄ）を更に含むことが好ましい。これにより、導電性を有する接着剤組成物を提供できる。導電性フィラー（Ｄ）は、１種単独であってもよいし、２種以上であってもよい。
　導電性フィラー（Ｄ）の含有量は、導電性、耐熱性、及び、貯蔵安定性の観点から、前記接着剤組成物におけるポリエステルポリアミド樹脂（Ａ）、エポキシ樹脂（Ｂ）及び任意成分として含有されていてもよいポリエステルポリウレタン樹脂（Ｃ）の合計量１００質量部に対して、１質量部～５００質量部であることが好ましく、１０質量部～３５０質量部であることがより好ましく、１０質量部～２００質量部であることが特に好ましい。 It is preferable that the adhesive composition of the present disclosure further includes a conductive filler (D). Thereby, an adhesive composition having electrical conductivity can be provided. The 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.
　本開示において、「前記接着剤組成物におけるポリエステルポリアミド樹脂（Ａ）、エポキシ樹脂（Ｂ）及び任意成分として含有されていてもよいポリエステルポリウレタン樹脂（Ｃ）の合計量１００質量部」とは、
　接着剤組成物がポリエステルポリウレタン樹脂（Ｃ）を含有する場合は、ポリエステルポリアミド樹脂（Ａ）、エポキシ樹脂（Ｂ）及びポリエステルポリウレタン樹脂（Ｃ）の合計量１００質量部を示し、
　接着剤組成物がポリエステルポリウレタン樹脂（Ｃ）を含有しない場合は、ポリエステルポリアミド樹脂（Ａ）及びエポキシ樹脂（Ｂ）の合計量１００質量部を示す。 In the present disclosure, "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",
When 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,
When 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.
＜イミダゾールシラン化合物（Ｅ）＞
　本開示の接着剤組成物は、導電性、及び、接着性の観点から、イミダゾールシラン化合物（Ｅ）を更に含むことが好ましい。
　イミダゾールシラン化合物（Ｅ）は、１以上のイミダゾール環構造と１以上のシラン構造とを有する化合物を示す。イミダゾールシラン化合物（Ｅ）は、エポキシ樹脂（Ｂ）の硬化剤として作用すると推定される。
　イミダゾールシラン化合物（Ｅ）は、導電性、及び、接着性の観点から、１つのイミダゾール環構造と１つのシリル基とを有する化合物であることが好ましい。
　イミダゾールシラン化合物（Ｅ）としては、導電性、及び、接着性の観点から、下記式（Ｅ）で表される化合物、又は、その酸付加物が好ましく挙げられる。 <Imidazole silane compound (E)>
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.
As the imidazole silane compound (E), from the viewpoint of conductivity and adhesiveness, a compound represented by the following formula (E) or an acid adduct thereof is preferably mentioned.
　式（Ｅ）中、Ｒ１及びＲ２は、それぞれ独立に、水素原子、飽和炭化水素基、不飽和炭化水素基又はアリール基を表し、前記各基は置換基を有していてもよい。Ｒ３及びＲ４は、それぞれ独立に、水素原子又はアルキル基を表す。Ｒ３の少なくとも１つは、アルキル基であり、前記アルキル基は置換基を有していてもよい。ｎは、１～３の整数を表す。Ｒ５は、アルキレン基、又は、アルキレン基の一部が式（Ｅ２）～式（Ｅ５）の少なくともいずれかで置換されている基を表す。 In formula (E), 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).
　式（Ｅ２）、式（Ｅ３）及び式（Ｅ５）中、Ｒ６は、水素原子又はヒドロキシ基を表す。Ｒ７は、水素原子、アルキル基又はアリール基を表す。Ｒ８及びＲ９は、それぞれ独立に、水素原子、アルキル基又はアリール基を表し、前記各基は置換基を有していてもよい。波線部分は、他の構造との結合位置を表す。 In formula (E2), formula (E3) and formula (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.
　接着剤組成物がイミダゾールシラン化合物（Ｅ）（特に前記式（Ｅ）で表される化合物）を含有すると、金属（特に金メッキされた銅箔）に対する接着性が向上する。これは、シラン構造及びイミダゾール環構造が金属表面と高い親和性を示す。そのために、その相互作用により接着性が向上すると推定される。更に、イミダゾール環構造は、エポキシ樹脂（Ｂ）とも反応し得る。そのため、後述するリフロー工程でもこの接着性向上作用を維持することができると推定される。 When 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.
　イミダゾールシラン化合物（Ｅ）は、イミダゾール環構造と、アルコキシシリル基とを一分子中に共に有する化合物であることが好ましい。本開示の接着性組成物が、アルコキシシリル基を有するイミダゾールシラン化合物（Ｅ）を更に含むことで、はんだ耐熱性をより高めることができる。
　前記イミダゾール環構造におけるイミダゾール環は、置換基（例えば、飽和炭化水素基、及び不飽和炭化水素基等）を有していてもよい。
　式（Ｅ）において、Ｒ１、Ｒ２、Ｒ３及びＲ４がアルキル基の場合に、その炭素数は１～３であることが好ましい。
　イミダゾールシラン化合物（Ｅ）を構成するイミダゾール環構造としては、イミダゾール環構造、２－アルキルイミダゾール環構造、２，４－ジアルキルイミダゾール環構造及び４－ビニルイミダゾール環構造等が挙げられる。
　イミダゾールシラン化合物（Ｅ）において、前記アルコキシシリル基とイミダゾール環構造とは、アルキレン基、又は、アルキレン基の一部が式（Ｅ２）～式（Ｅ５）のいずれかで置換されている基を介して結合されていることが好ましい。
　式（Ｅ）のＲ５における前記アルキレン基の炭素数は、１～１０であることが好ましく、３～７であることがより好ましい。
　イミダゾールシラン化合物（Ｅ）は、例えば、イミダゾール化合物と３－グリシドキシアルキルシラン化合物等との反応により好適に合成することができる。
　イミダゾールシラン化合物（Ｅ）は、アルコキシシリル基の加水分解により生じるシラノール化合物であってもよいし、シラノール化合物の脱水縮合反応により生じるポリオルガノシロキサン化合物であってもよく、これらの混合物であってもよい。
　式（Ｅ）で表される化合物に付加する酸としては、例えば、酢酸、乳酸、サリチル酸、安息香酸、アジピン酸、フタル酸、クエン酸、酒石酸、マレイン酸、トリメリット酸、リン酸及びイソシアヌル酸等が挙げられる。これらは、１種単独で、又は、２種以上を併せて用いることができる。 The imidazole silane compound (E) is preferably a compound having both an imidazole ring structure and an alkoxysilyl group in one molecule. When 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.).
In formula (E), when 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.
In the imidazole silane compound (E), 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.
　イミダゾールシラン化合物（Ｅ）としては、導電性、及び、接着性の観点から、下記式（Ｅ６）又は式（Ｅ７）で表される化合物、又は、その酸付加物であることがより好ましい。 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.
　式（Ｅ６）及び式（Ｅ７）中、Ｒ１及びＲ２は、それぞれ独立に、水素原子、飽和炭化水素基、不飽和炭化水素基又はアリール基を表し、前記各基は置換基を有していてもよい。Ｒ３及びＲ４は、それぞれ独立に、水素原子又はアルキル基を表す。Ｒ３の少なくとも１つは、アルキル基であり、前記アルキル基は置換基を有していてもよい。ｎは、１～３の整数を表す。Ｒ５’は、アルキレン基を表す。Ｒ６は、水素原子又はヒドロキシ基を表す。 In formula (E6) and formula (E7), 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.
　式（Ｅ６）及び式（Ｅ７）のＲ５’におけるアルキレン基の炭素数は、１～１０であることが好ましく、３～７であることがより好ましい。 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.
　イミダゾールシラン化合物（Ｅ）としては、例えば、１－（２－ヒドロキシ－３－トリメトキシシリルプロポキシプロピル）イミダゾール、１－（２－ヒドロキシ－３－トリエトキシシリルプロポキシプロピル）イミダゾール、１－（２－ヒドロキシ－３－トリプロポキシシリルプロポキシプロピル）イミダゾール、１－（２－ヒドロキシ－３－トリブトキシシリルプロポキシプロピル）イミダゾール、１－（２－ヒドロキシ－３－トリエトキシシリルプロポキシプロピル）－２－メチルイミダゾール、１－（２－ヒドロキシ－３－トリエトキシシリルプロポキシプロピル）－４－メチルイミダゾール、１－（３－オキソ－４－トリメトキシシリルプロポキシプロピル）イミダゾール、及び１－（３－トリメトキシシリルプロピルアミノ）イミダゾール等が挙げられる。 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.
　中でも、前記式（Ｅ６）又は式（Ｅ７）で表される化合物又はその酸付加物は、耐熱性が良好で、溶剤に対する溶解性を向上させる観点から、式（Ｄ６）で表される化合物の酸付加物がより好ましい。 Among these, 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.
　前記式（Ｅ６）で表される化合物は、イミダゾール化合物と、３－グリシドキシプロピルシラン化合物とを反応させる等により好適に得ることができる。
　イミダゾール化合物としては、例えば、イミダゾール、２－アルキルイミダゾール、２，４ジアルキルイミダゾール、及び４－ビニルイミダゾール等が挙げられる。
　３－グリシドキシプロピルシラン化合物としては、例えば、３－グリシドキシプロピルトリアルコキシシラン、３－グリシドキシプロピルジアルコキシアルキルシラン、３－グリシドキシプロピルアルコキシジアルキルシラン等が挙げられる。
　これらのうち特に好ましいのは、イミダゾールと３－グリシドキシプロピルトリメトキシシランとの反応物である。
　前記式（Ｅ７）で表される化合物は、イミダゾール化合物と、３－メタクリロイルオキシプロピルトリメトキシシラン等とを反応させる等により好適に得ることができる。 The compound represented by the formula (E6) can be suitably obtained by reacting an imidazole compound and a 3-glycidoxypropylsilane compound.
Examples of the imidazole compound include imidazole, 2-alkylimidazole, 2,4 dialkylimidazole, and 4-vinylimidazole.
Examples of 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.
　本開示の接着剤組成物は、イミダゾールシラン化合物（Ｅ）を、１種単独で含有していても、２種以上を含有していてもよい。
　イミダゾールシラン化合物（Ｅ）の含有量は、導電性、及び、接着性の観点から、前記接着剤組成物におけるポリエステルポリアミド樹脂（Ａ）、エポキシ樹脂（Ｂ）、及び、任意に含有していてもよいポリエステルポリウレタン樹脂（Ｃ）の合計量１００質量部に対して、０．０５質量部～２０質量部であることが好ましく、０．１質量部～１０質量部であることがより好ましく、１質量部～５質量部であることが特に好ましい。 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.
＜無機フィラー（Ｆ）＞
　本開示の接着剤組成物は、はんだ耐熱性、及び、導電性の観点から、導電性を有しない無機フィラー（Ｆ）（以下、単に「無機フィラー（Ｆ）」ともいう。）を更に含むことが好ましく、導電性を有しない無機フィラー（Ｆ）及び後述する導電性を有しない有機フィラー（Ｇ）を更に含むことがより好ましい。
　本明細書における導電性を有しない無機フィラー（Ｆ）及び後述する導電性を有しない有機フィラー（Ｇ）は、前述した導電性フィラー（Ｄ）以外の無機フィラー又は有機フィラーとする。 <Inorganic filler (F)>
From the viewpoint of soldering heat resistance and electrical conductivity, 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.
In this specification, 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).
　無機フィラー（Ｆ）としては、特に制限はないが、例えば、非導電性無機フィラー、及び導電性無機フィラーが挙げられる。非導電性無機フィラーとしては、例えば、炭酸カルシウム粒子、酸化チタン粒子、酸化アルミニウム粒子、酸化亜鉛粒子、タルク粒子、シリカ粒子等が挙げられる。導電性無機フィラーとしては、例えば、カーボンブラック粒子等が挙げられる。
　中でも、得られる硬化物の初期、はんだ後、長期信頼性試験後及び冷熱サイクル試験後の導電性の観点から、無機フィラー（Ｆ）としては、タルク粒子、及び、シリカ粒子よりなる群から選ばれた少なくとも１種の粒子が好ましく、タルク粒子がより好ましい。 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.
Among these, 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.
　無機フィラー（Ｆ）の平均粒子径は、特に限定されないが、得られる硬化物の初期、はんだ後、長期信頼性試験後及び冷熱サイクル試験後の導電性、塗布性、並びに、塗布厚調整性の観点から、０．００１μｍ～５０μｍであることが好ましく、０．００５μｍ～３０μｍであることがより好ましく、０．０１μｍ～１０μｍであることが特に好ましい。 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 μm to 50 μm, more preferably 0.005 μm to 30 μm, and particularly preferably 0.01 μm to 10 μm.
　無機フィラー（Ｆ）は、１種単独であってもよいし、２種以上であってもよい。無機フィラー（Ｆ）は、はんだ耐熱性、及び、導電性の観点から、２種以上であることが好ましく、２種であることがより好ましい。
　無機フィラー（Ｆ）の含有量は、接着性、導電性、及び、硬化性の観点から、前記接着剤組成物におけるポリエステルポリアミド樹脂（Ａ）、エポキシ樹脂（Ｂ）、及び、任意に含有していてもよいポリエステルポリウレタン樹脂（Ｃ）の合計量１００質量部に対して、０．１質量部～５０質量部であることが好ましく、０．５質量部～２０質量部であることがより好ましく、１質量部～１０質量部であることが特に好ましい。 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.
＜有機フィラー（Ｇ）＞
　本開示の接着剤組成物は、はんだ耐熱性、導電性、及び、耐湿熱性の観点から、導電性を有しない有機フィラー（Ｇ）（以下、単に「有機フィラー（Ｇ）」ともいう。）を含有することが好ましい。
　有機フィラー（Ｇ）としては、例えば、（メタ）アクリル樹脂粒子、ポリブタジエン粒子、ナイロン粒子、ポリオレフィン粒子、ポリエステル粒子、ポリカーボネート粒子、ポリビニルアルコール粒子、ポリビニルエーテル粒子、ポリビニルブチラール粒子、シリコーンゴム粒子、ポリウレタン粒子、フェノール樹脂粒子、及びポリ四弗化エチレン粒子等が挙げられる。
　有機フィラーは、ポリエステルポリアミド樹脂（Ａ）、エポキシ樹脂（Ｂ）、及び、任意に含有していてもよいポリエステルポリウレタン樹脂（Ｃ）と溶解させた場合に、これら樹脂の相溶性を高めることができる。更に、これら樹脂の相溶性及び液安定性をより向上させる観点から、シリコーン粒子、ポリブタジエン粒子、（メタ）アクリル樹脂粒子、又は、ポリウレタン粒子が特に好ましい。 <Organic filler (G)>
The adhesive composition of the present disclosure contains an 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.
Examples of the 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.
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.
　有機フィラー（Ｇ）の平均粒子径は、特に限定されないが、塗布性、及び、塗布厚調整性の観点から、０．５μｍ～５０μｍであることが好ましく、１μｍ～３０μｍであることがより好ましい。 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 μm to 50 μm, more preferably 1 μm to 30 μm.
　本開示の接着剤組成物は、有機フィラー（Ｇ）を含有してもよい。有機フィラー（Ｇ）は、１種単独であってもよいし、２種以上であってもよい。
　有機フィラー（Ｇ）の含有量は、接着性、導電性、及び、硬化性の観点から、前記接着剤組成物におけるポリエステルポリアミド樹脂（Ａ）、エポキシ樹脂（Ｂ）、及び、任意に含有していてもよいポリエステルポリウレタン樹脂（Ｃ）の合計量１００質量部に対して、１質量部～５０質量部であることが好ましく、５質量部～４０質量部であることがより好ましく、１０質量部～２０質量部であることが特に好ましい。 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.
　本開示の樹脂剤組成物は、前述した成分以外の他の添加剤を、接着剤組成物の機能に影響を与えない程度に含有していてもよい。
　他の添加剤としては、例えば、前述した以外の他の熱可塑性樹脂、粘着付与剤、難燃剤、硬化剤、硬化促進剤、カップリング剤、熱老化防止剤、レベリング剤、消泡剤及び溶剤等が挙げられる。 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.
Other 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.
　前記他の熱可塑性樹脂としては、例えば、フェノキシ樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリカーボネート樹脂、ポリフェニレンオキシド樹脂、ポリウレタン樹脂、ポリアセタール樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂及びポリビニル系樹脂等が挙げられる。これらの熱可塑性樹脂は、１種単独で用いてもよいし、２種以上を併用してもよい。 Examples of the other thermoplastic resins 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.
　前記粘着付与剤としては、例えば、クマロン－インデン樹脂、テルペン樹脂、テルペン－フェノール樹脂、ロジン樹脂、ｐ－ｔ－ブチルフェノール－アセチレン樹脂、フェノール－ホルムアルデヒド樹脂、キシレン－ホルムアルデヒド樹脂、石油系炭化水素樹脂、水素添加炭化水素樹脂、及びテレピン系樹脂等を挙げられる。これらの粘着付与剤は、１種単独で用いてもよいし、２種以上を併用してもよい。 Examples of the tackifier 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.
　前記難燃剤は、有機系難燃剤及び無機系難燃剤のいずれでもよい。
　有機系難燃剤としては、例えば、リン系難燃剤、窒素系難燃剤及びケイ素系難燃剤等が挙げられる。
　リン系難燃剤としては、例えば、リン酸メラミン、ポリリン酸メラミン、リン酸グアニジン、ポリリン酸グアニジン、リン酸アンモニウム、ポリリン酸アンモニウム、リン酸アミドアンモニウム、ポリリン酸アミドアンモニウム、リン酸カルバメート、ポリリン酸カルバメート、トリスジエチルホスフィン酸アルミニウム、トリスメチルエチルホスフィン酸アルミニウム、トリスジフェニルホスフィン酸アルミニウム、ビスジエチルホスフィン酸亜鉛、ビスメチルエチルホスフィン酸亜鉛、ビスジフェニルホスフィン酸亜鉛、ビスジエチルホスフィン酸チタニル、テトラキスジエチルホスフィン酸チタン、ビスメチルエチルホスフィン酸チタニル、テトラキスメチルエチルホスフィン酸チタン、ビスジフェニルホスフィン酸チタニル、テトラキスジフェニルホスフィン酸チタン等が挙げられる。
　窒素系難燃剤としては、例えば、メラミン、メラム、メラミンシアヌレート等のトリアジン系化合物や、シアヌル酸化合物、イソシアヌル酸化合物、トリアゾール系化合物、テトラゾール化合物、ジアゾ化合物、尿素等が挙げられる。
　ケイ素系難燃剤としては、例えば、シリコーン化合物、シラン化合物等が挙げられる。
　無機系難燃剤としては、例えば、金属水酸化物、金属酸化物、炭酸亜鉛、炭酸マグネシウム、炭酸カルシウム、炭酸バリウム、ホウ酸亜鉛、水和ガラス等が挙げられる。
　金属水酸化物としては、例えば、水酸化アルミニウム、水酸化マグネシウム、水酸化ジルコニウム、水酸化バリウム、水酸化カルシウム等が挙げられる。
　金属酸化物としては、例えば、酸化スズ、酸化アルミニウム、酸化マグネシウム、酸化ジルコニウム、酸化亜鉛、酸化モリブデン、酸化ニッケル等が挙げられる。
　これらの難燃剤は、１種単独で用いてもよいし、２種以上を併用することができる。 The flame retardant may be either an organic flame retardant or an inorganic flame retardant.
Examples of organic flame retardants include phosphorus flame retardants, nitrogen flame retardants, and silicon flame retardants.
Examples of phosphorus flame retardants include melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium phosphate, ammonium polyphosphate, carbamate phosphate, carbamate polyphosphate. , aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate , titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate, titanium tetrakisdiphenylphosphinate, and the like.
Examples of 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.
Examples of silicon-based flame retardants include silicone compounds and silane compounds.
Examples of inorganic flame retardants include metal hydroxides, metal oxides, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, and hydrated glass.
Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, and calcium hydroxide.
Examples of 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.
　前記硬化剤は、エポキシ樹脂（Ｂ）との反応により架橋構造を形成するための成分である。硬化剤は、例えば、酸系硬化剤、塩基性活性水素系硬化剤、ポリメルカプタン系硬化剤、ノボラック樹脂系硬化剤、ユリア樹脂系硬化剤、及びメラミン樹脂系硬化剤等が挙げられる。
　酸系硬化剤としては、例えば、アミン系硬化剤（例えば、脂肪族ジアミン、脂肪族系ポリアミン、環状脂肪族ジアミン及び芳香族ジアミン等）、ポリアミドアミン系硬化剤、脂肪族多価カルボン酸、脂環式多価カルボン酸、芳香族多価カルボン酸及びそれらの酸無水物等が挙げられる。
　塩基性活性水素系硬化剤としては、例えば、ジシアンジアミド、有機酸ジヒドラジド等が挙げられる。
　これらの硬化剤は、１種単独で用いてもよいし、２種以上を組み合わせて使用することができる。 The curing agent is a component for forming a crosslinked structure by reaction with the epoxy resin (B). Examples of 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.
Examples of 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.
　脂肪族ジアミン系硬化剤としては、例えば、エチレンジアミン、１，３－ジアミノプロパン、１，４－ジアミノブタン、ヘキサメチレンジアミン、ポリメチレンジアミン、ポリエーテルジアミン、２，５－ジメチルヘキサメチレンジアミン、及びトリメチルヘキサメチレンジアミン等が挙げられる。 Examples of 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.
　脂肪族ポリアミン系硬化剤としては、例えば、ジエチレントリアミン、イミノビス（ヘキサメチレン）トリアミン、トリヘキサテトラミン、テトラエチレンペンタミン、アミノエチルエタノールアミン、トリ（メチルアミノ）ヘキサン、ジメチルアミノプロピルアミン、ジエチルアミノプロピルアミン、及びメチルイミノビスプロピルアミン等が挙げられる。 Examples of aliphatic polyamine curing agents include diethylenetriamine, iminobis(hexamethylene)triamine, trihexatetramine, tetraethylenepentamine, aminoethylethanolamine, tri(methylamino)hexane, dimethylaminopropylamine, diethylaminopropylamine, and methyliminobispropylamine.
　環状脂肪族ジアミン系硬化剤としては、例えば、メンセンジアミン、イソホロンジアミン、ビス（４－アミノ－３－メチルジシクロへキシル）メタン、ジアミノジシクロヘキシルメタン、ビス（アミノメチル）シクロヘキサン、Ｎ－エチルアミノピペラジン、３，９－ビス（３－アミノプロピル）２，４，８，１０－テトラオキサスピロ［５．５］ウンデカン、及びメタキシリレンジアミンの水添物等が挙げられる。 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.
　芳香族ジアミン系硬化剤としては、例えば、メタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン、ジアミノジエチルジフェニルメタン、及びメタキシリレンジアミン等が挙げられる。 Examples of the aromatic diamine curing agent include metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, and metaxylylenediamine.
　脂肪族多価カルボン酸系硬化剤及び酸無水物系硬化剤としては、例えば、コハク酸、アジピン酸、ドデセニル無水コハク酸、ポリアジピン酸無水物、ポリアゼライン酸無水物、及びポリセバシン酸無水物等が挙げられる。 Examples of 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.
　脂環式多価カルボン酸系硬化剤及び酸無水物系硬化剤としては、例えば、メチルテトラヒドロフタル酸、メチルヘキサヒドロフタル酸、メチルハイミック酸、ヘキサヒドロフタル酸、テトラヒドロフタル酸、トリアルキルテトラヒドロフタル酸、メチルシクロジカルボン酸及びそれらの酸無水物等が挙げられる。 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.
　芳香族多価カルボン酸系硬化剤及び酸無水物系硬化剤としては、例えば、フタル酸、トリメリット酸、ピロメリット酸、ベンゾフェノンテトラカルボン酸、エチレングリコールグリコールビストリメリット酸、グリセロールトリストリメリット酸及びそれらの酸無水物等が挙げられる。 Examples of 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.
　ポリメルカプタン系硬化剤としては、例えば、メルカプト化エポキシ樹脂、及びメルカプトプロピオン酸エステル等が挙げられる。 Examples of the polymercaptan curing agent include mercaptated epoxy resins and mercaptopropionic acid esters.
　ノボラック系硬化剤としては、例えば、フェノールノボラック系硬化剤、及びクレゾールノボラック系硬化剤等が挙げられる。 Examples of the novolak curing agent include a phenol novolac curing agent, a cresol novolac curing agent, and the like.
　本開示の接着剤組成物が前記硬化剤を含有する場合、硬化剤の含有量は、その官能基当量が、接着性、及び、耐熱性の観点から、エポキシ樹脂（Ｂ）のエポキシ基１モル当量に対して、好ましくは０．２モル当量～２．５モル当量、より好ましくは０．４モル当量～２．０モル当量である。 When the adhesive composition of the present disclosure contains the curing agent, 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.
　前記硬化促進剤は、エポキシ樹脂（Ｂ）の反応を促進させる目的で使用する成分であり、第三級アミン系硬化促進剤、第三級アミン塩系硬化促進剤及びイミダゾール系硬化促進剤等を使用することができる。
　これらの硬化促進剤は、１種単独で用いてもよいし、２種以上を組み合わせて使用することができる。 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.
　第三アミン系硬化促進剤としては、例えば、ベンジルジメチルアミン、２－（ジメチルアミノメチル）フェノール、２，４，６－トリス（ジメチルアミノメチル）フェノール、テトラメチルグアニジン、トリエタノールアミン、Ｎ，Ｎ’－ジメチルピペラジン、トリエチレンジアミン、及び１，８－ジアザビシクロ［５．４．０］ウンデセン等が挙げられる。 Examples of the tertiary amine curing accelerator 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.
　第三アミン塩系硬化促進剤としては、例えば、１，８－ジアザビシクロ［５．４．０］ウンデセンの、ギ酸塩、オクチル酸塩、ｐ－トルエンスルホン酸塩、ｏ－フタル酸塩、フェノール塩又はフェノールノボラック樹脂塩や、１，５－ジアザビシクロ［４．３．０］ノネンの、ギ酸塩、オクチル酸塩、ｐ－トルエンスルホン酸塩、ｏ－フタル酸塩、フェノール塩及びフェノールノボラック樹脂塩等が挙げられる。 Examples of the tertiary amine salt curing accelerator 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.
　イミダゾール系硬化促進剤としては、例えば、２－メチルイミダゾール、２－ウンデシルイミダゾール、２－ヘプタデシルイミダゾール、１，２－ジメチルイミダゾール、２－メチル－４－エチルイミダゾール、２－フェニルイミダゾール、２－フェニル－４－メチルイミダゾール、１－ベンジル－２－メチルイミダゾール、１－ベンジル－２－フェニルイミダゾール、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２’－ウンデシルイミダゾリル－（１’）］－エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２’－エチル－４’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジン、２，４－ジアミノ－６－［２’－メチルイミダゾリル－（１’）］－エチル－ｓ－トリアジンイソシアヌル酸付加物、２－フェニルイミダゾールイソシアヌル酸付加物、２－フェニル－４，５－ジヒドロキシメチルイミダゾール、及び２－フェニル－４－メチル－５－ヒドロキシメチルイミダゾール等が挙げられる。 Examples of imidazole-based curing accelerators 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'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct 2-phenyl-4,5-dihydroxymethylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole.
　本開示の接着剤組成物が硬化促進剤を含有する場合、前記硬化促進剤の含有量は、接着性、及び、耐熱性の観点から、エポキシ樹脂（Ｂ）１００質量部に対して、好ましくは１質量部～１０質量部、より好ましくは２質量部～５質量部である。 When the adhesive composition of the present disclosure contains a curing accelerator, 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.
　前記カップリング剤としては、例えば、シラン系カップリング剤、チタネート系カップリング剤、アルミネート系カップリング剤、及びジルコニウム系カップリング剤等が挙げられる。
　シラン系カップリング剤としては、例えば、ビニルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、ｐ－スチリルトリメトキシシラン、３－メタクリロキシプロピルメチルジメトキシシラン、３－アクリロキシプロピルトリメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトシキシラン、３－ウレイドプロピルトリエトキシシラン、３－メルカプトプロピルメチルジメトキシシラン、ビス（トリエトキシシリルプロピル）テトラスルフィド、３－イソシアネートプロピルトリエトキシシラン、イミダゾールシラン等が挙げられる。
　これらは、１種単独で用いてよいし、２種以上を組み合わせて用いてもよい。 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.
　前記熱老化防止剤としては、例えば、フェノ－ル系酸化防止剤、イオウ系酸化防止剤、及びリン系酸化防止剤等が挙げられる。
　フェノ－ル系酸化防止剤としては、例えば、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノ－ル、ｎ－オクタデシル－３－（３’，５’－ジ－ｔｅｒｔ－ブチル－４’－ヒドロキシフェニル）プロピオネ－ト、テトラキス〔メチレン－３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネ－ト〕メタン等が挙げられる。
　イオウ系酸化防止剤としては、例えば、ジラウリル－３，３’－チオジプロピオネ－ト、ジミリスチル－３，３’－ジチオプロピオネ－ト等が挙げられる。
　リン系酸化防止剤としては、例えば、トリスノニルフェニルホスファイト、トリス（２，４－ジ－ｔｅｒｔ－ブチルフェニル）ホスファイト等が挙げられる。
　これらは、１種単独で用いてよいし、２種以上を組み合わせて用いてもよい。 Examples of the heat aging inhibitor include phenolic antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants.
Examples of 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.
　本開示の接着剤組成物は、ポリエステルポリアミド樹脂（Ａ）、エポキシ樹脂（Ｂ）、及び、必要に応じ、その他成分を混合することにより調製することができる。
　本開示の接着剤組成物は、溶液又は分散液の状態で好ましく用いられることから、溶剤を含有することが好ましい。
　溶剤としては、例えば、アルコール類、ケトン類、芳香族炭化水素類、エステル類、及び脂肪族炭化水素類等が挙げられる。
　アルコール類としては、例えば、メタノール、エタノール、イソプロピルアルコール、ｎ－プロピルアルコール、イソブチルアルコール、ｎ－ブチルアルコール、ベンジルアルコール、エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、及びジアセトンアルコール等が挙げられる。
　ケトン類としては、例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン、メチルアミルケトン、シクロヘキサノン、及びイソホロン等が挙げられる。
　芳香族炭化水素類としては、例えば、トルエン、キシレン、エチルベンゼン、及びメシチレン等が挙げられる。
　エステル類としては、例えば、酢酸メチル、酢酸エチル、エチレングリコールモノメチルエーテルアセテ－ト、３－メトキシブチルアセテート等が挙げられる。
　脂肪族炭化水素類としては、例えば、ヘキサン、ヘプタン、シクロヘキサン、メチルシクロヘキサン等が挙げられる。
　ポリエステルポリアミド樹脂（Ａ）はプロトン性溶媒に溶解しやすく、これらの中でアルコール類を含む溶剤が好ましい。
　これらの溶剤は、１種単独で用いてよいし、２種以上を組み合わせて用いてもよい。本開示の接着剤組成物が溶剤を含む溶液又は分散液であると、被着体への塗工及び接着剤組成物層の形成を円滑に行うことができ、所望の厚さの接着剤組成物層を容易に得ることができる。 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.
Examples of the solvent include alcohols, ketones, aromatic hydrocarbons, esters, and aliphatic hydrocarbons.
Examples of 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.
Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, cyclohexanone, and isophorone.
Examples of aromatic hydrocarbons include toluene, xylene, ethylbenzene, and mesitylene.
Examples of esters include methyl acetate, ethyl acetate, ethylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate.
Examples of 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. When the adhesive composition of the present disclosure is a solution or dispersion containing a solvent, coating on an adherend and formation of an adhesive composition layer can be performed smoothly, and the adhesive composition can be formed into a desired thickness. A layer can be easily obtained.
　本開示の接着剤組成物が溶剤を含む場合、塗膜形成性を含む作業性等の観点から、溶剤の固形分濃度は、好ましくは３質量％～８０質量％、より好ましくは１０質量％～５０質量％である。 When the adhesive composition of the present disclosure contains a solvent, 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.
　本開示の接着剤組成物による好適な被着体の材質は、例えば、高分子材料、金属材料等が挙げられる。高分子材料としては、例えば、ポリイミド樹脂、ポリエーテルエーテルケトン樹脂、ポリフェニレンサルファイド樹脂、アラミド樹脂、及び液晶ポリマー等が挙げられる。金属材料としては、例えば、銅、アルミニウム、及びステンレス等が挙げられる。被着体の形状は、特に限定されない。被着体としての２つの部材同士を、本開示の接着剤組成物により接着させることで、一体化した複合化物を製造することができる。２つの部材の材質は、同一であってもよいし、異なっていてもよい。本開示の接着剤組成物を用いることで、接着性を有する接着剤組成物層を有する製品（例えば、カバーレイフィルム、ボンディングシート等）を製造することができる。 Suitable materials for the adherend using the adhesive composition of the present disclosure include, for example, polymer materials, metal materials, and the like. Examples of the polymeric material include polyimide resin, polyetheretherketone resin, polyphenylene sulfide resin, aramid resin, and liquid crystal polymer. Examples of 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. By using the adhesive composition of the present disclosure, products having an adhesive composition layer having adhesive properties (for example, a coverlay film, a bonding sheet, etc.) can be manufactured.
　本開示の接着剤組成物において、本開示の接着剤組成物を硬化させた硬化物を２３℃の水に２４時間浸漬させたときの吸水率は、はんだ耐熱性、接着性、及び、防湿性の観点から、４％以下であることが好ましく、３％以下であることがより好ましく、２．７％以下であることが特に好ましい。前記吸水率の下限値は、０％である。
　本開示における接着剤組成物の硬化物の吸水率は、下記のようにして算出される。シート、接着剤組成物層及びシートをこの順に重ね合わせて、重ね合わせ体を得る。重ね合わせ体を１５０℃、３ＭＰａの条件で５分間加熱圧着した後、１６０℃で２時間加熱硬化させ、厚さ１００μｍの接着剤組成物の硬化物を作製する。これにより、積層体を得る。積層体は、シート、接着剤組成物の硬化物及びシートがこの順に積層されてなる。ＪＩＳ　Ｋ　７１１４（２００１）に準拠して、積層体を２３℃の水に２４時間浸漬させたときの吸水率を、接着剤組成物の硬化物の吸水率とする。 In the adhesive composition of the present disclosure, 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. for 2 hours to produce a cured adhesive composition having a thickness of 100 μm. Thereby, a laminate is obtained. The laminate is formed by laminating a sheet, a cured adhesive composition, and a sheet in this order. In accordance with JIS K 7114 (2001), 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.
（接着剤組成物層付き積層体、及び、積層体）
　本開示の接着剤組成物層付き積層体は、本開示の接着剤組成物を用いた積層体である。本開示の接着剤組成物層付き積層体は、接着剤組成物層と、前記接着剤組成物層の少なくとも一方の面に接する基材フィルムとを備える。前記接着剤組成物層は、本開示の接着剤組成物の未硬化物からなる接着剤組成物層、前記接着剤組成物を一部硬化してなるＢステージ状の接着剤組成物層、又は、前記接着剤組成物を硬化してなる硬化層である。
　本開示において、「接着剤組成物の未硬化物」とは、接着剤組成物の未硬化状態を示す。
　本開示において、「接着剤組成物層がＢステージ状である」とは、接着剤組成物層の一部が硬化し始めた半硬化状態を示す。換言すると、Ｂステージ状は、加熱等により、接着剤組成物層の硬化が更に進行する状態である。
　本開示の接着剤組成物の未硬化物からなる前記接着剤組成物層は、溶剤を含む接着剤組成物を用いる場合、本開示の接着剤組成物から溶剤の少なくとも一部を除去した層であることが好ましい。 (Laminated body with adhesive composition layer and laminate)
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.
In the present disclosure, "uncured adhesive composition" refers to an uncured state of the adhesive composition.
In the present disclosure, "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. In other words, the B-stage state is a state in which the adhesive composition layer further progresses in curing due to heating or the like.
When using an adhesive composition containing a solvent, 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.
　本開示の接着剤組成物層付き積層体、及び、本開示の積層体は、基材を有することが好ましく、基材上に本開示の接着剤組成物からなる層を有することがより好ましい。
　基材としては、特に制限はなく、公知の基材を用いることができる。
　基材としては、フィルム状の基材（基材フィルム）であることが好ましい。
　基材フィルムとしては、樹脂フィルムであることが好ましく、ポリイミドフィルム又はアラミドフィルムであることがより好ましく、ポリイミドフィルムであることが特に好ましい。
　前記ポリイミドフィルム又はアラミドフィルムは、電気的絶縁性を有するものであれば、特に限定されず、ポリイミド樹脂又はアラミド樹脂のみからなるフィルム、ポリイミド樹脂又はアラミド樹脂と添加剤とを含むフィルム等が挙げられる。接着剤組成物層が形成される側には、表面処理が施されていてもよい。
　前記基材の厚さは、特に制限はないが、３μｍ～１２５μｍであることが好ましい。
　前記接着剤組成物層の厚さは、５μｍ～５０μｍであることが好ましく、１０μｍ～４０μｍであることがより好ましい。 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.
There are no particular limitations on the base material, and any known base material can be used.
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 μm to 125 μm.
The thickness of the adhesive composition layer is preferably 5 μm to 50 μm, more preferably 10 μm to 40 μm.
　本開示の接着剤組成物層付き積層体を製造する方法としては、例えば、溶剤を含む本開示の接着剤組成物を、基材フィルム（例えば、ポリイミドフィルム等）の表面に塗布して接着剤組成物層を形成した後、前記接着剤組成物層から前記溶剤の少なくとも一部を除去する方法（以下、「第１方法」ともいう）等が挙げられる。第１方法により、Ｂステージ状の接着剤組成物層を有する積層体を製造することができる。
　前記溶剤を除去するときの乾燥温度は、４０℃～２５０℃であることが好ましく、７０℃～１７０℃であることがより好ましい。
　乾燥は、接着剤組成物が塗布された積層体を、炉の中を通過させることにより行われる。炉では、熱風乾燥、遠赤外線加熱、及び高周波誘導加熱等がなされる。
　本開示の接着剤組成物層付き積層体は、必要に応じて、前記接着剤組成物層の表面に、保管等のため、離型性フィルムを更に有していてもよい。
　前記離型性フィルムとしては、ポリエチレンテレフタレートフィルム、ポリエチレンフィルム、ポリプロピレンフィルム、シリコーン離型処理紙、ポリオレフィン樹脂コート紙、ポリメチルペンテン（ＴＰＸ）フィルム、フッ素系樹脂フィルム等が挙げられる。離型性フィルムは、公知のものであってもよい。 As a method for manufacturing a laminate with an adhesive composition layer of the present disclosure, for example, 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. Examples include a method of removing at least a portion of the solvent from the adhesive composition layer after forming the composition layer (hereinafter also referred to as "first method"). By the first method, a laminate having a B-stage adhesive composition layer can be manufactured.
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. In the furnace, hot air drying, far infrared heating, high frequency induction heating, etc. are performed.
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.
Examples of 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.
　Ｂステージ状の接着剤組成物層の厚さは、５μｍ～１００μｍであることが好ましく、５μｍ～７０μｍであることがより好ましく、５μｍ～５０μｍであることが更に好ましく、１０μｍ～４０μｍであることが特に好ましい。
　前記基材フィルム及び接着剤組成物層の厚さは、用途により選択されるが、電気特性を向上させるために基材フィルムはより薄い厚さであってもよい。前記基材フィルムの好ましい厚さとしては、前述した前記基材の好ましい厚さと同様である。
　本開示の接着剤組成物層付き積層体においては、接着剤組成物層の厚さ（Ａ）と、基材フィルムの厚さ（Ｂ）との比（Ａ／Ｂ）は、１～１０であることが好ましく、１～５であることがより好ましい。更に、接着剤組成物層の厚さが、基材フィルムの厚さより厚いことが好ましい。 The thickness of the B-stage adhesive composition layer is preferably 5 μm to 100 μm, more preferably 5 μm to 70 μm, even more preferably 5 μm to 50 μm, and preferably 10 μm to 40 μm. 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.
In the laminate with an adhesive composition layer of the present disclosure, 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.
　本開示の積層体を製造する方法としては、例えば、基材フィルムの表面に、溶剤を含む本開示の接着剤組成物を塗工した後、本開示の接着剤組成物層付き積層体の場合と同様にして乾燥し、次いで、形成した接着剤組成物層の表面と被着体とを面接触させ、ラミネート（、例えば、８０℃～１５０℃で熱ラミネート）を行う。これにより、積層体（基材フィルム／接着剤組成物層／被着体）が得られる。積層体（基材フィルム／接着剤組成物層／被着体）は、基材フィルム、接着剤組成物層及び被着体がこの順に積層されてなる。次いで、この積層体（基材フィルム／接着剤組成物層／被着体）を加熱圧着し、更にアフターキュアにより接着剤組成物層を硬化し硬化層とする方法が好適に挙げられる。
　加熱圧着の条件は、圧着可能であれば、特に制限はないが、好ましくは、１５０℃～２００℃、及び、圧力１ＭＰａ～３ＭＰａの条件で１分間～６０分間とすることができる。アフターキュアの条件は、特に制限はないが、好ましくは１００℃～２００℃、３０分～４時間とすることができる。
　硬化層の厚さは、５μｍ～１００μｍであることが好ましく、５μｍ～７０μｍであることがより好ましく、５μｍ～５０μｍであることが更に好ましく、１０μｍ～４０μｍであることが特に好ましい。
　被着体は、特に制限はなく、前述したものが挙げられる。中でも、金属被着体が好ましく、銅箔、又は、めっきされた銅箔がより好ましく、金めっきされた銅箔が特に好ましい。
　被着体の形状及び大きさ等についても、特に制限はなく、公知のものを用いることができる。 As a method for manufacturing 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) is formed by laminating a base film, an adhesive composition layer, and an adherend in this order. Next, 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 μm to 100 μm, more preferably 5 μm to 70 μm, even more preferably 5 μm to 50 μm, and particularly preferably 10 μm to 40 μm.
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.
　本開示の積層体は、本開示の接着剤組成物を硬化してなる硬化層を備える。
　本開示の積層体の一実施態様としては、フレキシブル銅張積層板が挙げられる。
　すなわち、本開示のフレキシブル銅張積層板は、本開示の接着剤組成物からなる接着剤組成物を硬化してなる硬化層を有する。本開示のフレキシブル銅張積層板は、ポリイミドフィルム又はアラミドフィルムと、本開示の接着剤組成物を硬化してなる硬化層と、銅箔とを備える積層体であることが好ましい。
　本開示のフレキシブル銅張積層板において、前記硬化層及び前記銅箔は、ポリイミドフィルム又はアラミドフィルムの両面に形成されていてもよい。本開示の接着剤組成物は、銅を含む物品との接着性に優れる。そのため、本開示のフレキシブル銅張積層板は、一体化物として安定性に優れる。 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.
In the flexible copper-clad laminate of the present disclosure, 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.
　前記ポリイミドフィルム又はアラミドフィルムの構成は、前述した本開示のカバーレイフィルムにおけるポリイミドフィルム又はアラミドフィルムと同様である。
　前記硬化層の厚さは、５μｍ～５０μｍであることが好ましく、１０μｍ～４０μｍであることがより好ましい。
　前記銅箔としては、特に限定されず、電解銅箔、及び圧延銅箔等が挙げられる。
　前記銅箔は、公知の金属（例えば、金及び銀等）又は合金によりめっきされたものであってもよい。 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 μm to 50 μm, more preferably 10 μm to 40 μm.
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.
　本開示の接着剤組成物層付き積層体の一実施態様としては、後述するボンディングフィルム、電磁波シールドフィルム、及びカバーレイフィルム等が挙げられる。 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.
－ボンディングフィルム－
　本開示のボンディングフィルムは、本開示の接着剤組成物を用いたものである。本開示のボンディングフィルムは、本開示の接着剤組成物を一部硬化してなるＢステージ状の接着剤組成物層と、前記接着剤組成物層の少なくとも一方の面に接する離型フィルムとを備えることが好ましい。
　本開示のボンディングフィルムは、上述した本開示の接着剤組成物層付き積層体の一実施態様でもある。
　本開示のボンディングフィルムは、２枚の離型性フィルムの間に接着剤組成物層を備える態様であってもよい。
　前記離型性フィルムとしては、前述したような公知のものが用いられる。
　前記離型性フィルムの厚さは、２０μｍ～１００μｍであることが好ましい。
　前記接着剤組成物層の厚さは、５μｍ～１００μｍであることが好ましく、１０μｍ～６０μｍであることがより好ましい。 -Bonding film-
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 μm to 100 μm.
The thickness of the adhesive composition layer is preferably 5 μm to 100 μm, more preferably 10 μm to 60 μm.
　本開示のボンディングシートを製造する方法としては、例えば、離型性フィルムの表面に、溶剤を含む本開示の接着剤組成物を塗工した後、前述した本開示の接着剤組成物層付き積層体の場合と同様にして乾燥する方法が好ましく挙げられる。 As a method for manufacturing the bonding sheet of the present disclosure, for example, after coating the adhesive composition of the present disclosure containing a solvent on the surface of a releasable film, 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.
－電磁波シールドフィルム－
　本開示の電磁波シールドフィルムは、本開示の接着剤組成物を用いたものである。本開示の電磁波シールドフィルムは、接着剤組成物層を有することが好ましい。接着剤組成物層は、本開示の接着剤組成物の未硬化物からなる接着剤組成物層、前記接着剤組成物を一部硬化してなるＢステージ状の接着剤組成物層、又は、前記接着剤組成物を硬化してなる硬化層である。本開示の電磁波シールドフィルムは、前記接着剤組成物を硬化してなる硬化層を有することがより好ましい。
　本開示の電磁波シールドフィルムは、前記接着剤組成物層と、保護層とを有することが好ましい。
　保護層は、絶縁性接着剤組成物からなる層であれば特に限定されず、公知のものであればよい。保護層は、本開示の接着剤組成物に使用される樹脂成分を使用してもよい。保護層は、組成や硬度が異なる２以上の層から形成されていてもよい。
　保護層は、必要に応じて硬化促進剤、粘着性付与剤、酸化防止剤、顔料、染料、可塑剤、紫外線吸収剤、消泡剤、レベリング剤、充填剤、難燃剤、粘度調節剤、及びブロッキング防止剤等を含んでもよい。 -Electromagnetic shielding film-
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.
　本開示の電磁波シールドフィルムにおける接着剤組成物層の厚さは、特に制限はないが、導電性、及び、グランド回路との接続性の観点から、３μｍ～３０μｍであることが好ましい。 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 μm to 30 μm.
　次に本開示の電磁波シールドフィルムの製造方法の具体的態様について説明する。
　本開示の電磁波シールドフィルムの製造方法としては、例えば、はく離性フィルムの一方の面に保護層用接着剤組成物をコーティング及び乾燥し、保護層を形成し、前記保護層上に、本開示の接着剤組成物をコーティング及び乾燥し、接着剤組成物層を形成する方法等を挙げられる。
　例示したような製造方法により、接着剤組成物層、保護層及びはく離性フィルムがこの順に積層されてなる電磁波シールドフィルムを得ることができる。 Next, a specific embodiment of the method for manufacturing the electromagnetic shielding film of the present disclosure will be described.
As a method for producing the electromagnetic shielding film of the present disclosure, for example, 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.
By the manufacturing method as exemplified, it is possible to obtain an electromagnetic shielding film in which an adhesive composition layer, a protective layer, and a releasable film are laminated in this order.
　接着剤組成物層及び保護層を設ける方法は、公知のコーティング方法であればよい。接着剤組成物層及び保護層を設ける方法として、例えば、グラビアコート方式、キスコート方式、ダイコート方式、リップコート方式、コンマコート方式、ブレードコート方式、ロールコート方式、ナイフコート方式、スプレーコート方式、バーコート方式、スピンコート方式、ディップコート方式等が挙げられる。 The adhesive composition layer and the protective layer may be provided by any known coating method. Examples of 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.
　本開示の電磁波シールドフィルムは、例えば、熱プレスによってプリント配線板上に接着させることができる。前記接着剤組成物層は、加熱により軟かくなり、加圧により、プリント配線板上に設けられたグランド部に流れ込む。これによって、グランド回路と導電性接着剤とが電気的に接続される。その結果、シールド効果は向上する。 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.
　以下、実施例に基づいて本開示を具体的に説明する。本開示は、これらの実施例により限定されるものではない。以下において「部」及び「％」は、特に断らない限り、「質量部」及び「質量％」をそれぞれ意味する。 Hereinafter, the present disclosure will be specifically described based on Examples. The present disclosure is not limited by these examples. In the following, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.
＜＜使用した原料＞＞
１．ポリエステルポリアミド樹脂（Ａ）
＜ポリエステルポリアミド樹脂（ａ１）の作製＞
　撹拌機、還流脱水装置及び蒸留管を備えたフラスコに、ダイマー酸７質量部、アゼライン酸４０６質量部、イソホロンジアミン３６４質量部及び蒸留水１２０質量部を仕込んだ。温度を１２０℃に昇温して水を留出させた後に、２０℃／時間の割合で２４０℃まで昇温し、１時間保持した。この反応生成物にさらにアゼライン酸２００質量部、ネオペンチルグリコール１２５質量部、及びエステル化触媒としてテトラブトキシチタネート２．１質量部を添加したところ、温度が１５０℃まで低下した。再び２２０℃まで昇温してアミン価が７．６ｍｇＫＯＨ／ｇになるまで反応を継続し、ポリエステルポリアミド樹脂（ａ１）を得た。 <<Raw materials used>>
1. 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. When 200 parts by mass of azelaic acid, 125 parts by mass of neopentyl glycol, and 2.1 parts by mass of tetrabutoxy titanate as an esterification catalyst were further added to this reaction product, the temperature decreased to 150°C. The temperature was raised to 220° C. again and the reaction was continued until the amine value reached 7.6 mgKOH/g to obtain a polyester polyamide resin (a1).
＜ポリエステルポリアミド樹脂（ａ２）の作製＞
　アミン価が４．３ｍｇＫＯＨ／ｇになるまで反応を継続する以外は、ポリエステルポリアミド樹脂（ａ１）の作製と同様にして、ポリエステルポリアミド樹脂（ａ２）を得た。 <Preparation of polyester polyamide resin (a2)>
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.
２．ポリエステルを含まないポリアミド樹脂（Ａ’）
＜ポリエステルを含まないポリアミド樹脂（ａ３）の作製＞
　撹拌機、還流脱水装置及び蒸留管を備えたフラスコに、アゼライン酸６５質量部、ドデカン二酸１９０質量部、ピペラジン１００質量部及び蒸留水１２０質量部を仕込んだ。温度を１２０℃に昇温して水を留出させた後に、２０℃／時間の割合で２４０℃にまで昇温し、３時間反応を継続してポリアミド樹脂（ａ３）を得た。この樹脂のアミン価は４．５ｍｇＫＯＨ／ｇであった。 2. 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.
３．エポキシ樹脂（Ｂ）
　エポキシ樹脂（ｂ１）：三菱ケミカル（株）製トリスフェノールメタン型エポキシ樹脂「ｊＥＲ　１０３２Ｈ６０」（商品名）
　エポキシ樹脂（ｂ２）：ＤＩＣ（株）製ビスフェノールＡノボラック型エポキシ樹脂「ＥＰＩＣＬＯＮ　Ｎ－８６５」（商品名）
　エポキシ樹脂（ｂ３）：三菱ケミカル（株）製ビスフェノールＡ型エポキシ樹脂「ｊＥＲ　１０５５」（商品名） 3. 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
４．ポリウレタン樹脂（Ｃ）
＜ポリウレタン樹脂（ｃ１）の作製＞
　撹拌機、還流脱水装置及び蒸留管を備えたフラスコに、「ＰＥＳ－３６０ＨＶＸＭ３０」（東亞合成（株）製アロンメルト（登録商標）ＰＥＳ－３６０ＨＶＸＭ３０、数平均分子量：２０，０００、ガラス転移点：６５℃）を６００質量部、トルエン１００質量部及びネオペンチルグリコール２０質量部を仕込んだ。温度を１２０℃に昇温して水を含む溶媒を１００質量部留出させた後、温度を１０５℃に下げ、２，２－ジメチロールプロピオン酸０．４質量部を仕込み溶解させた。その後、ヘキサメチレンジイソシアネートを３４質量部添加し、３０分後にジラウリン酸ジブチル錫を０．２質量部加えた。６時間反応を継続した後、トルエン／２－プロパノールで希釈して固形分濃度を３０％に調整したポリエステルポリウレタン樹脂（ｃ１）の溶液を得た。ポリエステルポリウレタン樹脂（ｃ１）の数平均分子量は３６，０００であり、重量平均分子量は１４０，０００であり、酸価は２ｍｇＫＯＨ／ｇであった。 4. Polyurethane resin (C)
<Preparation of polyurethane resin (c1)>
In a flask equipped with a stirrer, a reflux dehydrator, and a distillation tube, "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. After raising the temperature to 120°C and distilling off 100 parts by mass of the solvent containing water, the temperature was lowered to 105°C, and 0.4 parts by mass of 2,2-dimethylolpropionic acid was charged and dissolved. Thereafter, 34 parts by mass of hexamethylene diisocyanate was added, and 30 minutes later, 0.2 parts by mass of dibutyltin dilaurate was added. After continuing the reaction for 6 hours, a solution of 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.
＜ポリウレタン樹脂（ｃ２）の作製＞
　撹拌機、還流脱水装置及び蒸留管を備えたフラスコに、「ＰＥＳ－３６０ＨＶＸＭ３０」　６００質量部、トルエン１００質量部、２－ブチル－２－エチル－１，３－プロパンジオール３０質量部を仕込んだ。温度を１２０℃に昇温して水を含む溶媒を１００質量部留出させた後に、温度を１０５℃に下げ、２，２－ビス（ヒドロキシメチル）プロピオン酸０．４質量部仕込み溶解させた。その後、ノルボルナンジイソシアネート（ＮＢＤＩ）を４２質量部添加し、３０分後にジラウリン酸ジブチルすずを０．２質量部加えた。所定の分子量に到達するまで反応を継続した後、トルエン／２－プロパノールで希釈して固形分濃度を３０％に調整したポリエステルポリウレタン樹脂（ｃ２）の溶液を得た。ポリエステルポリウレタン樹脂（ｃ２）の数平均分子量は３５，０００であり、重量平均分子量は１２０，０００であり、酸価は２ｍｇＫＯＨ／ｇであった。 <Preparation of polyurethane resin (c2)>
A flask equipped with a stirrer, a reflux dehydrator, and a distillation tube was charged with 600 parts by mass of "PES-360HVXM30", 100 parts by mass of toluene, and 30 parts by mass of 2-butyl-2-ethyl-1,3-propanediol. After raising the temperature to 120°C and distilling off 100 parts by mass of the solvent containing water, the temperature was lowered to 105°C, and 0.4 parts by mass of 2,2-bis(hydroxymethyl)propionic acid was charged and dissolved. . Thereafter, 42 parts by mass of norbornane diisocyanate (NBDI) was added, and 30 minutes later, 0.2 parts by mass of dibutyltin dilaurate was added. After the reaction was continued until a predetermined molecular weight was reached, a solution of 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.
５．導電性フィラー（Ｄ）
　福田金属箔粉工業（株）製銅粉「ＦＣＣ－１１５Ａ」（商品名） 5. Conductive filler (D)
Copper powder manufactured by Fukuda Metal Foil and Powder Co., Ltd. “FCC-115A” (product name)
６．イミダゾールシラン化合物（Ｅ）
　１－（２－ヒドロキシ－３－トリメトキシシリルプロポキシプロピル）イミダゾール 6. Imidazole silane compound (E)
1-(2-hydroxy-3-trimethoxysilylpropoxypropyl)imidazole
６．導電性を有しない無機フィラー（Ｆ）
　無機フィラー（ｆ１）：日本アエロジル（株）製「Ｒ９７２」（商品名；平均粒径１６ｎｍ、シリカ粒子）
　無機フィラー（ｆ２）：日本タルク（株）製タルク「ＳＧ－９５」（商品名；平均粒径２．５μｍ、タルク粒子） 6. Inorganic filler (F) without conductivity
Inorganic filler (f1): “R972” manufactured by Nippon Aerosil Co., Ltd. (trade name; average particle size 16 nm, silica particles)
Inorganic filler (f2): Talc “SG-95” manufactured by Nippon Talc Co., Ltd. (trade name; average particle size 2.5 μm, talc particles)
７．導電性を有しない有機フィラー（Ｇ）
　有機フィラー（ｇ１）：根上工業（株）製アクリルビーズ「Ｊ－４Ｐ」（商品名；平均粒径２．２μｍ、アクリル樹脂粒子）
　有機フィラー（ｇ２）：根上工業（株）製ウレタンビーズ「ＴＫ－８００Ｔ」（商品名；平均粒径８μｍ、ポリウレタン樹脂粒子） 7. 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 μm, acrylic resin particles)
Organic filler (g2): Urethane beads "TK-800T" manufactured by Negami Kogyo Co., Ltd. (trade name; average particle size 8 μm, polyurethane resin particles)
８．難燃剤
　クラリアント社製ホスフィン酸金属塩「Ｅｘｏｌｉｔ　ＯＰ９３５」（商品名） 8. Flame retardant Clariant phosphinate metal salt “Exolit OP935” (product name)
９．溶剤
　トルエン、メチルイソブチルケトン及び２－プロパノールからなる混合溶媒（質量比＝１００：２０：２０） 9. Solvent Mixed solvent consisting of toluene, methyl isobutyl ketone and 2-propanol (mass ratio = 100:20:20)
（実施例１～１６、及び、比較例１～４）
　撹拌装置付きフラスコに、上記の原料を表１に示す割合で添加し、６０℃加温下で６時間撹拌して、溶剤にポリエステルポリアミド樹脂（Ａ）又はポリエステルを含まないポリアミド樹脂（Ａ’）、エポキシ樹脂（Ｂ）、ポリウレタン樹脂（Ｃ）、イミダゾールシラン化合物（Ｅ）、及び、硬化促進剤を溶解させ、導電性フィラー（Ｄ）、無機フィラー（Ｆ）、有機フィラー（Ｇ）、及び、難燃剤を分散させることにより、液状接着剤組成物を製造した。その後、これらすべての液状接着剤組成物を用いて、カバーレイフィルム、ボンディングシート、並びに、接着試験片Ａ、及びＢを作製し、下記の（ｉ）～（ｘ）の評価を行った。評価結果を表１に示す。 (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.
（１）カバーレイフィルムの作製
　厚さ２５μｍのポリイミドフィルムの表面に、液状接着剤組成物を、乾燥後の厚さが１５μｍとなるようロ－ル塗布し、１２０℃で２分間乾燥させて、接着剤層を有するカバーレイフィルムを得た。 (1) Preparation of coverlay film A liquid adhesive composition was roll-coated on the surface of a polyimide film with a thickness of 25 μm so that the thickness after drying was 15 μm, and dried at 120° C. for 2 minutes. A coverlay film having an adhesive layer was obtained.
（２）接着試験片Ａの作製
　福田金属箔粉工業（株）製厚さ３５μｍの圧延処理銅箔を用意した。鏡面を上記カバーレイフィルムの接着剤層面に接触するように重ね合わせ、１５０℃、０．３ＭＰａ、１ｍ／分の条件でラミネートを行い、積層体（ポリイミドフィルム／接着剤層／銅箔）を得た。得られた積層体（ポリイミドフィルム／接着剤層／銅箔）は、ポリイミドフィルム、接着剤層及び銅箔がこの順に積層されてなる。得られた積層体（ポリイミドフィルム／接着剤層／銅箔）を、１５０℃、３ＭＰａの条件で５分間加熱して圧着した後、更に、オ－ブンにて１６０℃で２時間のアフターキュアを行った。これにより、接着試験片Ａを得た。 (2) Preparation of Adhesion Test Piece A A rolled copper foil with a thickness of 35 μm 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.
（３）ボンディングシートの作製
　厚さ３５μｍの離型性ＰＥＴフィルムを用意した。液状接着剤組成物と福田金属箔粉工業（株）製銅粉「ＦＣＣ－１１５Ａ」とを、固形分樹脂全体の１５質量％になるように配合した混合物を用意した。離型性ＰＥＴフィルムの表面に、上記混合物を、乾燥後の厚さが２５μｍとなるようロ－ル塗布し、１４０℃で２分間乾燥させて、接着剤層を有するボンディングシートを得た。 (3) Production of bonding sheet A releasable PET film with a thickness of 35 μm 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 μm, and dried at 140° C. for 2 minutes to obtain a bonding sheet having an adhesive layer.
（４）接着試験片Ｂの作製
　フレキシブルプリント配線板を用意した。フレキシブルプリント配線板は、ニッケルめっきされたＳＵＳ３０４板（厚さ：３００μｍ）と、ポリイミドフィルム（厚さ：２５μｍ）と、回路パターン（材質：銅）と、カバーレイフィルム（厚さ：３７．５μｍ）とを備える。ＳＵＳ３０４板、ポリイミドフィルム及び回路パターンは、この順に積層されてなる。カバーレイフィルムは、回路パターン上に積層されている。カバーレイフィルムは、直径１ｍｍのスルーホールを有する。
　初めに、ＳＵＳ３０４板のニッケルめっき処理面を上記ボンディングシートの接着剤層面に接触するように重ね合わせ、１５０℃、０．３ＭＰａ、１ｍ／分の条件でラミネートを行い、積層体（ＳＵＳ板／接着剤層／離型性ＰＥＴフィルム）を得た。積層体（ＳＵＳ板／接着剤層／離型性ＰＥＴフィルム）は、ＳＵＳ３０４板、接着剤層及び離型性ＰＥＴフィルムがこの順に積層されてなる。その後、積層体（ＳＵＳ板／接着剤層／離型性ＰＥＴフィルム）から離型性ＰＥＴフィルムを剥がして、露出した接着剤層の表面に、フレキシブルプリント配線板（厚み２５μｍのポリイミドフィルム上に銅箔回路が形成されており、その銅箔回路上に直径１ｍｍのスルーホールを有する厚み３７．５μｍのカバーレイフィルムが積層された配線板）に１５０℃、３ＭＰａの条件で５分間加熱圧着した後、更にオ－ブンにて１６０℃で２時間のアフターキュアを行った。これにより、接着試験片Ｂ（ＳＵＳ板／接着剤層／フレキシブルプリント配線板）を作製した。接着試験片Ｂは、ＳＵＳ板、接着剤層及びフレキシブルプリント配線板がこの順に積層されてなる。 (4) Preparation of adhesive test piece B A flexible printed wiring board was prepared. The flexible printed wiring board is made of a nickel-plated SUS304 board (thickness: 300 μm), a polyimide film (thickness: 25 μm), a circuit pattern (material: copper), and a coverlay film (thickness: 37.5 μm). 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.
First, 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. After that, 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 μm thick polyimide film) is applied to the surface of the exposed adhesive layer. After heat and pressure bonding for 5 minutes at 150°C and 3 MPa to a wiring board on which a 37.5 μm thick coverlay film with a 1 mm diameter through hole was laminated on the copper foil circuit on which a foil circuit was formed. Further, after-curing was performed in an oven at 160°C for 2 hours. Thereby, adhesive test piece B (SUS board/adhesive layer/flexible printed wiring board) was produced. Adhesion test piece B is made by laminating a SUS board, an adhesive layer, and a flexible printed wiring board in this order.
（ｉ）ポリエステルポリアミド樹脂（Ａ）等のアミン価
　ＪＩＳ　Ｋ　７２３７（１９９５）に準拠し、電位差滴定法により樹脂のアミン価を算出した。測定結果を表１に示す。 (i) Amine value of polyester polyamide resin (A) etc. The amine value of the resin was calculated by potentiometric titration according to JIS K 7237 (1995). The measurement results are shown in Table 1.
（ｉｉ）硬化物の吸水率
　ボンディングシートを重ね合わせて１５０℃、３ＭＰａの条件で５分間加熱圧着した後、１６０℃で２時間加熱硬化させ、厚さ１００μｍの接着剤硬化物を作製した。ＪＩＳ　Ｋ　７１１４（２００１）に準拠して、接着剤硬化物を２３℃の水に２４時間浸漬させたときの吸水率を算出した。測定結果を表１に示す。 (ii) Water absorption rate of cured product Bonding sheets were stacked and heat-pressed at 150° C. and 3 MPa for 5 minutes, and then heat-cured at 160° C. for 2 hours to produce a cured adhesive with a thickness of 100 μm. Based on JIS K 7114 (2001), the water absorption rate when the cured adhesive was immersed in water at 23° C. for 24 hours was calculated. The measurement results are shown in Table 1.
（ｉｉｉ）はく離接着強さ
　接着性を評価するために、ＪＩＳ　Ｃ　６４８１「プリント配線板用銅張積層板試験方法」に準拠し、温度２３℃及び引張速度５０ｍｍ／分の条件で、各接着試験片Ａの銅箔をポリイミドフィルムから剥がすときの１８０°はく離接着強さ（Ｎ／ｃｍ）を測定した。測定時の接着試験片の幅は１．０ｃｍとした。測定結果を表１に示す。
　表１中、「はく離接着強さ」の項目を、はく離接着強さの「初期」と表示した。はく離接着強さの測定値が５．０Ｎ／ｃｍ以上のものを「Ａ」と表示した。はく離接着強さの測定値が３．５Ｎ／ｃｍ以上５．０Ｎ／ｃｍ未満のものを「Ｂ」と表示した。はく離接着強さの測定値が、３．５Ｎ／ｃｍ未満のものを「Ｃ」と表示した。 (iii) Peel adhesion strength In order to evaluate the adhesion, each adhesion test was conducted at a temperature of 23°C and a tensile speed of 50 mm/min in accordance with JIS C 6481 "Test method for copper-clad laminates for printed wiring boards". The 180° peel adhesion strength (N/cm) when the copper foil of Piece A was peeled off from the polyimide film was measured. The width of the adhesive test piece during measurement was 1.0 cm. The measurement results are shown in Table 1.
In Table 1, the item "peel adhesive strength" is indicated as "initial" peel adhesive strength. Those with a measured value of peel adhesion strength of 5.0 N/cm or more were designated as "A". Those with a measured value of peel adhesion strength of 3.5 N/cm or more and less than 5.0 N/cm were designated as "B". Those with a measured value of peel adhesion strength of less than 3.5 N/cm were designated as "C".
（ｉｖ）長期湿熱試験後のはく離接着強さ（長期の耐湿熱性）
　各接着試験片Ａを８５℃、８５％ＲＨ、１，０００時間保管し、ＪＩＳ　Ｃ　６４８１「プリント配線板用銅張積層板試験方法」に準拠し、温度２３℃及び引張速度５０ｍｍ／分の条件で、保管後の各接着試験片Ａの銅箔をポリイミドフィルムから剥がすときの１８０°はく離接着強さ（Ｎ／ｍｍ）を測定した。測定時の接着試験片の幅は１．０ｃｍとした。測定結果を表１に示す。
　表１中、「長期湿熱試験後のはく離接着強さ（長期の耐湿熱性）」の項目を、はく離接着強さの「８５℃／８５％ＲＨ１０００ｈｒ試験後」と表示した。はく離接着強さの測定値が５．０Ｎ／ｃｍ以上のものを「Ａ」と表示した。はく離接着強さの測定値が３．５Ｎ／ｃｍ以上５．０Ｎ／ｃｍ未満のものを「Ｂ」と表示した。はく離接着強さの測定値が３．５Ｎ／ｃｍ未満のものを「Ｃ」と表示した。長期湿熱試験後のはく離接着強さ（長期の耐湿熱性）の許容可能な評価結果は、「Ａ」又は「Ｂ」である。 (iv) Peeling adhesive strength after long-term moist heat test (long-term moist heat resistance)
Each adhesive test piece A was stored at 85°C, 85% RH for 1,000 hours, and tested at a temperature of 23°C and a tensile speed of 50 mm/min in accordance with JIS C 6481 "Test method for copper-clad laminates for printed wiring boards." Then, the 180° peel adhesive strength (N/mm) when the copper foil of each adhesive test piece A was peeled off from the polyimide film after storage was measured. The width of the adhesive test piece during measurement was 1.0 cm. The measurement results are shown in Table 1.
In Table 1, the item "Peel adhesive strength after long-term moist heat test (long-term moist heat resistance)" is indicated as "After 85° C./85% RH 1000 hr test" of peel adhesive strength. Those with a measured value of peel adhesion strength of 5.0 N/cm or more were designated as "A". Those with a measured value of peel adhesion strength of 3.5 N/cm or more and less than 5.0 N/cm were designated as "B". Those with a measured value of peel adhesion strength of less than 3.5 N/cm were designated as "C". An acceptable evaluation result of peel adhesion strength (long-term moist heat resistance) after a long-term moist heat test is "A" or "B".
（ｖ）はんだ耐熱性（はんだ時の外観、はんだ処理後のはく離接着強さ）
　ＪＩＳ　Ｃ　６４８１（１９９６）に準拠し、下記の条件で試験を行った。
　絶乾はんだ試験：ＪＩＳ　Ｃ　６４８１（１９９６）に準拠、１０５±２℃で前処理を行った直後に、ポリイミドフィルムの面を上にして、２６０℃のはんだ浴に６０秒間浮かべた。
　常湿はんだ試験：ＪＩＳ　Ｃ　６４８１（１９９６）に準拠、１０５±２℃で前処理を行った後、常湿下（２３±２℃、５０～６０％ＲＨ）で２４時間放置してから、ポリイミドフィルムの面を上にして、２６０℃のはんだ浴に６０秒間浮かべた。
　各はんだ試験後の接着試験片Ａについて、接着剤層の膨れ、剥がれ等の外観異常の有無を目視によりそれぞれ評価した。評価結果を表１に示す。
　表１中、「はんだ時の外観」の項目を、外観の「常湿はんだ試験後」と表示した。マイクロボイドや膨れ及び剥がれ等の外観異常が確認されなかったものを「Ａ」と表示した。マイクロボイドがわずかに見られたものを「Ｂ」と表示した。膨れ及び剥がれ等の外観異常が確認されたものを「Ｃ」と表示した。 (v) Soldering heat resistance (appearance when soldering, peel adhesion strength after soldering)
The test was conducted under the following conditions in accordance with JIS C 6481 (1996).
Bone-dry solder test: According to JIS C 6481 (1996), immediately after pretreatment at 105±2°C, the polyimide film was floated in a solder bath at 260°C for 60 seconds with its side facing up.
Normal humidity soldering test: According to JIS C 6481 (1996), after pretreatment at 105±2℃, leave it at normal humidity (23±2℃, 50-60%RH) for 24 hours, and then solder the polyimide. The film was placed face up in a solder bath at 260° C. for 60 seconds.
After each solder test, 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.
In 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".
　更に、常湿はんだ試験後の接着試験片Ａについて、ＪＩＳ　Ｃ　６４８１に準拠し、２３℃において、ポリイミドフィルムを金めっきされた銅箔から剥がすときの１８０°はく離接着強さ（Ｎ／ｃｍ）を測定した。測定時の接着試験片の幅は１０ｍｍとし、引張速度は５０ｍｍ／分とした。測定時の接着試験片の幅は１０ｍｍとした。測定結果を表１に示す。
　表１中、「はんだ処理後のはく離接着強さ」の項目を、はく離接着強さの「常湿はんだ試験後」と表示した。はく離強度の測定値が５．０Ｎ／ｃｍ以上のものを「Ａ」と表示した。はく離強度の測定値が３．５Ｎ／ｃｍ以上５．０Ｎ／ｃｍ未満のものを「Ｂ」と表示した。はく離強度の測定値が３．５Ｎ／ｃｍ未満のものを「Ｃ」と表示した。はんだ処理後のはく離接着強さの許容可能な結果は、「Ａ」又は「Ｂ」である。 Furthermore, for the adhesive test piece A after the normal humidity soldering test, 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". Those with a measured value of peel strength of 3.5 N/cm or more and less than 5.0 N/cm were designated as "B". Those with a measured value of peel strength of less than 3.5 N/cm were designated as "C". Acceptable results for peel adhesion strength after soldering are "A" or "B".
（ｖｉ）導電性（初期、接続抵抗）
　上記接着試験片Ｂ（ＳＵＳ板／接着剤層／フレキシブルプリント配線板）のＳＵＳ板とフレキシブルプリント配線板の銅箔回路との間の接続抵抗値を抵抗値測定器で測定した。測定結果を表１に示す。
　表１中、「導電性（初期、接続抵抗）」の項目を、導電性の「初期」と表示した。接続抵抗値の測定値が０．３Ω未満のものを「Ａ」と表示した。接続抵抗値の測定値が０．３Ω以上１．０Ω未満のものを「Ｂ」と表示した。接続抵抗値の測定値が１．０Ω以上のものを「Ｃ」と表示した。 (vi) Conductivity (initial, connection resistance)
The connection resistance between the SUS board of the adhesive test piece B (SUS board/adhesive layer/flexible printed wiring board) and the copper foil circuit of the flexible printed wiring board was measured using a resistance value measuring device. The measurement results are shown in Table 1.
In Table 1, the item "conductivity (initial, connection resistance)" is indicated as "initial" of conductivity. Those with a measured connection resistance value of less than 0.3Ω were designated as “A”. Those with a measured connection resistance value of 0.3Ω or more and less than 1.0Ω were designated as “B”. Those with a measured connection resistance value of 1.0Ω or more were designated as “C”.
（ｖｉｉ）長期湿熱試験後の導電性
　上記接着試験片Ｂを８５℃、８５％ＲＨの恒温恒湿槽に１，０００時間放置した。その後、接着試験片ＢのＳＵＳ板とフレキシブルプリント配線板の銅箔回路との間の接続抵抗値を抵抗値測定器で測定した。測定結果を表１に示す。
　表１中、「長期湿熱試験後の導電性」の項目を、導電性の「８５℃／８５％ＲＨ１０００ｈｒ試験後」と表示した。接続抵抗値の測定値が０．３Ω未満のものを「Ａ」と表示した。接続抵抗値の測定値が０．３Ω以上１．０Ω未満のものを「Ｂ」と表示した。接続抵抗値の測定値が１．０Ω以上のものを「Ｃ」と表示した。 (vii) Conductivity after long-term heat and humidity test The adhesive test piece B was left in a constant temperature and humidity chamber at 85° C. and 85% RH for 1,000 hours. Thereafter, the connection resistance value between the SUS board of adhesive test piece B and the copper foil circuit of the flexible printed wiring board was measured using a resistance value measuring device. The measurement results are shown in Table 1.
In Table 1, the item "Electroconductivity after long-term moist heat test" is indicated as "After 85° C./85% RH 1000 hr test" for conductivity. Those with a measured connection resistance value of less than 0.3Ω were designated as “A”. Those with a measured connection resistance value of 0.3Ω or more and less than 1.0Ω were designated as “B”. Those with a measured connection resistance value of 1.0Ω or more were designated as “C”.
（ｖｉｉｉ）はんだ処理後の導電性（はんだ後導電性、接続抵抗）
　上記接着試験片Ｂを２６０℃のはんだ浴に６０秒間浮かべた。その後、はんだ浴から取出した接着試験片ＢのＳＵＳ板とフレキシブルプリント配線板の銅箔回路との間の接続抵抗値を抵抗値測定器で測定した。測定結果を表１に示す。
　表１中、「はんだ処理後の導電性（はんだ後導電性、接続抵抗）」の項目を、導電性の「常湿はんだ試験後」と表示した。接続抵抗値の測定値が０．３Ω未満のものを「Ａ」として表示した。接続抵抗値の測定値が０．３Ω以上１．０Ω未満のものを「Ｂ」として表示した。接続抵抗値の測定値が１．０Ω以上のものを「Ｃ」として表示した。 (viii) Conductivity after soldering (conductivity after soldering, connection resistance)
The adhesive test piece B was floated in a solder bath at 260° C. for 60 seconds. Thereafter, the connection resistance value between the SUS board of the adhesive test piece B taken out from the solder bath and the copper foil circuit of the flexible printed wiring board was measured using a resistance value measuring device. The measurement results are shown in Table 1.
In Table 1, the item "Conductivity after soldering (conductivity after soldering, connection resistance)" is indicated as "After normal humidity soldering test" for conductivity. Those with a measured connection resistance value of less than 0.3Ω were designated as “A”. Those with a measured connection resistance value of 0.3Ω or more and less than 1.0Ω were indicated as “B”. Those with a measured connection resistance value of 1.0Ω or more were designated as “C”.
（ｉｘ）難燃性
　前記カバーレイフィルムを１６０℃で２時間加熱硬化させ、ＵＬ－９４に準拠して難燃性の評価を行った。評価結果を表１に示す。
　「ＶＴＭ－０」の判定基準を満たすもの（ＶＴＭ－０クラス）を「Ａ」として表示した。「ＶＴＭ－０」の判定基準を満たさないもの（ＶＴＭ－１クラス又はＶＴＭ－２クラス）を「Ｆ」として表示した。 (ix) Flame retardancy The coverlay film was cured by heating at 160° C. for 2 hours, and flame retardancy was evaluated in accordance with UL-94. The evaluation results are shown in Table 1.
Those that meet the criteria for "VTM-0" (VTM-0 class) are indicated as "A". Those that did not meet the criteria for "VTM-0" (VTM-1 class or VTM-2 class) were indicated as "F".
（ｘ）接着剤組成物の貯蔵安定性
　表１に記載の組成を有する実施例１～１６及び比較例１～４の接着剤組成物（接着剤組成物）を、それぞれガラス瓶に入れ密封し、５℃で所定時間保管し組成物の結晶性を観察した。所定時間保管後、接着剤組成物のゲル化又は液分離が確認されたものを貯蔵安定性不良と見なし、下記の評価基準で接着剤組成物の貯蔵安定性の評価を行った。評価結果を表１に示す。
＜評価基準＞
　Ａ：１週間以上ゲル化又は液分離が確認されなかった。
　Ｆ：１週間未満でゲル化又は液分離が生じた。 (x) Storage stability of adhesive composition The adhesive compositions (adhesive compositions) of Examples 1 to 16 and Comparative Examples 1 to 4 having the compositions shown in Table 1 were placed in glass bottles and sealed, The composition was stored at 5° C. for a predetermined period of time, and the crystallinity of the composition was observed. After storage for a predetermined time, adhesive compositions in which gelation or liquid separation was confirmed were considered to have poor storage stability, and the storage stability of the adhesive compositions was evaluated using the following evaluation criteria. The evaluation results are shown in Table 1.
<Evaluation criteria>
A: No gelation or liquid separation was observed for more than one week.
F: Gelation or liquid separation occurred in less than one week.
　表１に記載の接着剤組成物組成における各成分欄の数値の単位は、質量部である。 The units of numerical values in each component column in the adhesive composition composition listed in Table 1 are parts by mass.
　前記表１に示す結果から明らかなように、実施例１～１６の接着剤組成物は、比較例１～４の接着剤組成物に比べ、得られる硬化物が、常湿環境下においてもはんだ耐熱性に優れ、かつ長期の耐湿熱性にも優れる接着剤組成物であった。
　実施例３～１６の接着剤組成物、導電性フィラー（Ｄ）及び難燃剤を含んでおり、得られる硬化物が、難燃性及び導電性に優れるものであった。実施例２～６ではエポキシ樹脂（Ｂ）の添加量を変化させているが、ポリエステルポリアミド樹脂（Ａ）１００質量部に対してエポキシ樹脂（Ｂ）３５質量部以上を添加した実施例４～６において常湿はんだ試験後におけるはく離接着強さが高かった。特にイミダゾール系化合物（Ｅ）を添加した実施例５では、得られた接着剤組成物は常湿はんだ試験後の導電性にも優れていた。実施例１１においては無機フィラー（Ｆ）を接着剤組成物に添加し、常湿はんだ試験後におけるはく離接着強さが改善されていた。実施例１２においては無機フィラー（Ｆ）及び有機フィラー（Ｇ）を接着剤組成物に添加し、常湿はんだ試験後におけるはく離接着強さ及び導電性が改善されていた。 As is clear from the results shown in Table 1, 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. In Examples 2 to 6, 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. In particular, in Example 5 in which the imidazole compound (E) was added, the resulting adhesive composition also had excellent conductivity after the normal humidity soldering test. In 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. In 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.
　２０２２年７月６日に出願された日本国特許出願２０２２－１０９１８８の開示は、その全体が参照により本明細書に取り込まれる。
　本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。 The disclosure of Japanese Patent Application No. 2022-109188 filed on July 6, 2022 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards mentioned herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference. Incorporated herein by reference.

Claims (14)

  1. 　ポリエステル部分とポリアミド部分を有するポリエステルポリアミド樹脂（Ａ）と、
    　エポキシ樹脂（Ｂ）と
    を含み、
    　前記ポリエステルポリアミド樹脂（Ａ）１００質量部に対し、前記エポキシ樹脂（Ｂ）の量が１質量部～６０質量部である
    　接着剤組成物。     A polyester polyamide resin (A) having a polyester part and a polyamide part,
    Including epoxy resin (B),
    An adhesive composition in which 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).
  2. 　前記ポリエステルポリアミド樹脂（Ａ）のアミン価が、１．０ｍｇＫＯＨ／ｇ～１２．０ｍｇＫＯＨ／ｇである請求項１に記載の接着剤組成物。 The adhesive composition according to claim 1, wherein the polyester polyamide resin (A) has an amine value of 1.0 mgKOH/g to 12.0 mgKOH/g.
  3. 　前記ポリエステルポリアミド樹脂（Ａ）の前記ポリエステル部分が、炭素数６～２２の脂肪族ジカルボン酸、炭素数６～２２の芳香族ジカルボン酸及び／又は炭素数６～２２の脂環式ジカルボン酸と、炭素数２～５４の脂肪族ジオール、炭素数２～５４の芳香族ジオール又は炭素数２～５４の脂環式ジオールとの重縮合物であり、
    　前記ポリエステルポリアミド樹脂（Ａ）の前記ポリアミド部分が、炭素数６～２２の脂肪族ジカルボン酸、炭素数６～２２の芳香族ジカルボン酸及び／若しくは炭素数６～２２の脂環式ジカルボン酸並びに／又は炭素数２０～４８の二量化脂肪族二酸を含むジカルボン酸と、炭素数６～４４の芳香族及び／又は炭素数６～４４の脂環式骨格を有するジアミンとの重縮合物である請求項１に記載の接着剤組成物。     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. Or 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 claim 1.
  4. 　ポリウレタン樹脂（Ｃ）を更に含む請求項１に記載の接着剤組成物。 The adhesive composition according to claim 1, further comprising a polyurethane resin (C).
  5. 　硬化物を２３℃の水に２４時間浸漬させたときの吸水率が、３％以下である請求項１に記載の接着剤組成物。 The adhesive composition according to claim 1, which has a water absorption rate of 3% or less when the cured product is immersed in water at 23°C for 24 hours.
  6. 　導電性フィラー（Ｄ）を更に含む請求項１に記載の接着剤組成物。 The adhesive composition according to claim 1, further comprising a conductive filler (D).
  7. 　前記導電性フィラー（Ｄ）の含有量が、前記接着剤組成物における前記ポリエステルポリアミド樹脂（Ａ）、前記エポキシ樹脂（Ｂ）及び任意成分として含有してもよいポリエステルウレタン樹脂（Ｃ）の合計量１００質量部に対して、１０質量部～３５０質量部である請求項６に記載の接着剤組成物。 The content of the conductive filler (D) is the total amount of the polyester polyamide resin (A), the epoxy resin (B), and the optional polyester urethane resin (C) in the adhesive composition. The adhesive composition according to claim 6, which is 10 parts by mass to 350 parts by mass based on 100 parts by mass.
  8. 　アルコキシシリル基を有するイミダゾール系化合物（Ｅ）を更に含む請求項１に記載の接着剤組成物。 The adhesive composition according to claim 1, further comprising an imidazole compound (E) having an alkoxysilyl group.
  9. 　導電性を有しない無機フィラー（Ｆ）を更に含む請求項１に記載の接着剤組成物。 The adhesive composition according to claim 1, further comprising an inorganic filler (F) having no conductivity.
  10. 　導電性を有しない有機フィラー（Ｇ）を更に含む請求項１に記載の接着剤組成物。 The adhesive composition according to claim 1, further comprising an organic filler (G) having no conductivity.
  11. 　請求項１～請求項１０のいずれか１項に記載の接着剤組成物を一部硬化してなるＢステージ状の接着剤組成物層と、前記接着剤組成物層の少なくとも一方の面に接する離型フィルムとを備えるボンディングフィルム。 A B-stage adhesive composition layer formed by partially curing the adhesive composition according to any one of claims 1 to 10, and in contact with at least one surface of the adhesive composition layer. A bonding film comprising a release film.
  12. 　接着剤組成物層と、前記接着剤組成物層の少なくとも一方の面に接する基材フィルムとを備え、
    　前記接着剤組成物層が、請求項１～請求項１０のいずれか１項に記載の接着剤組成物の未硬化物からなる接着剤組成物層、前記接着剤組成物の一部が硬化してなるＢステージ状の接着剤組成物層、又は前記接着剤組成物が硬化してなる硬化層である、接着剤組成物層付き積層体。     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 an adhesive composition layer consisting of an uncured adhesive composition according to any one of claims 1 to 10, wherein a part of the adhesive composition is cured. A laminate with an adhesive composition layer, which is a B-stage adhesive composition layer or a cured layer obtained by curing the adhesive composition.
  13. 　請求項１～請求項１０のいずれか１項に記載の接着剤組成物を硬化してなる硬化層を備える積層体。 A laminate comprising a cured layer obtained by curing the adhesive composition according to any one of claims 1 to 10.
  14. 　請求項１～請求項１０のいずれか１項に記載の接着剤組成物を硬化してなる硬化層を備える電磁波シールドフィルム。 An electromagnetic shielding film comprising a cured layer obtained by curing the adhesive composition according to any one of claims 1 to 10.
PCT/JP2023/024689 2022-07-06 2023-07-03 Adhesive composition, bonding film, laminate with adhesive composition layer, laminate, and electromagnetic wave shield film WO2024009969A1 (en)

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JP2022109188 2022-07-06
JP2022-109188 2022-07-06

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JPH10338807A (en) * 1997-04-07 1998-12-22 Hitachi Ltd Resin composition and adhesive film
JP2001354938A (en) * 2000-06-12 2001-12-25 Toray Ind Inc Adhesive composition for semiconductor device, and adhesive sheet prepared by using the composition, semiconductor-connecting substrate, and semiconductor device prepared by using the composition
JP2009001793A (en) * 2008-06-06 2009-01-08 Kaneka Corp Adhesive
WO2012011265A1 (en) * 2010-07-23 2012-01-26 タツタ電線株式会社 Adhesive agent composition and adhesive film
CN103923585A (en) * 2014-04-03 2014-07-16 新纶科技（常州）有限公司 Conductive adhesive composition and conductive adhesive membrane
JP2015228457A (en) * 2014-06-02 2015-12-17 デクセリアルズ株式会社 Conductive adhesive for solar cell, solar cell module, and manufacturing method of solar cell module
WO2016001949A1 (en) * 2014-07-02 2016-01-07 東洋インキＳｃホールディングス株式会社 Heat-curable resin composition, polyamide, adhesive sheet, cured article, and printed wiring board
WO2022085563A1 (en) * 2020-10-23 2022-04-28 東亞合成株式会社 Resin composition, bonding film, laminate with resin composition layer, laminate, and electromagnetic wave shield film

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10338807A (en) * 1997-04-07 1998-12-22 Hitachi Ltd Resin composition and adhesive film
JP2001354938A (en) * 2000-06-12 2001-12-25 Toray Ind Inc Adhesive composition for semiconductor device, and adhesive sheet prepared by using the composition, semiconductor-connecting substrate, and semiconductor device prepared by using the composition
JP2009001793A (en) * 2008-06-06 2009-01-08 Kaneka Corp Adhesive
WO2012011265A1 (en) * 2010-07-23 2012-01-26 タツタ電線株式会社 Adhesive agent composition and adhesive film
CN103923585A (en) * 2014-04-03 2014-07-16 新纶科技（常州）有限公司 Conductive adhesive composition and conductive adhesive membrane
JP2015228457A (en) * 2014-06-02 2015-12-17 デクセリアルズ株式会社 Conductive adhesive for solar cell, solar cell module, and manufacturing method of solar cell module
WO2016001949A1 (en) * 2014-07-02 2016-01-07 東洋インキＳｃホールディングス株式会社 Heat-curable resin composition, polyamide, adhesive sheet, cured article, and printed wiring board
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