TW202413584A - Adhesive composition - Google Patents

Abstract

An object of the present invention is to provide an adhesive composition which has low dielectric properties and excellent adhesiveness between resin and metal.

As a result of intensive studies, the inventors of the present invention have found that an adhesive composition which contains (A) an acid-modified styrene elastomer, and (B) an alicyclic epoxy resin containing a structure in which the unsaturated bond of the cyclic olefin structure is epoxidized, and does not contain (C) a tertiary amine, a tertiary amine salt, an imidazole and a cationic polymerization initiator, has low dielectric properties and excellent adhesion between resin and metal.

Description

Adhesive composition

The present invention relates to an adhesive composition having excellent low dielectric properties (low dielectric constant, low dielectric dissipation factor) and adhesiveness, and is suitable for the manufacture of electronic components, especially flexible printed circuit boards (hereinafter referred to as FPC) and related components.

In recent years, with the development of wireless communication technology such as smartphones and mobile computers, there is a demand for high-speed processing of large amounts of information and the development of high-frequency transmission signals. With the high frequency, FPC and its related components, which are one of the components of wireless communication devices, are also required to have low dielectric properties (low dielectric constant, low dielectric loss factor) in high-frequency bands (for example, International Publication No. 2016/017473 (Patent Document 1)).

In addition, regarding the above-mentioned related components, for example, in order to protect the wiring part when manufacturing FPC, a laminate with an adhesive layer called a "coverlay film" is used, and the adhesive layer is also required to have strong adhesion to the wiring part and the base film.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] International Publication No. 2016/017473

In view of such a situation, the present invention aims to provide an adhesive composition having excellent low dielectric properties and adhesion between resin and metal.

As a result of intensive research to solve the above-mentioned problems, the inventors of the present invention have found that the above-mentioned problems can be solved by using an adhesive composition containing (A) an acid-modified styrene-based elastomer and (B) an aliphatic epoxy resin having an unsaturated bond containing a cyclic olefin structure through epoxidation, and not containing (C) tertiary amines, tertiary amine salts, imidazoles and cationic polymerization initiators. Specifically, the present invention includes the following inventions.

[1]

An adhesive composition comprising the following (A) and (B), and not containing the following (C),

(A) Acid-modified styrene elastomers,

(B) A cyclic epoxy resin having an unsaturated bond containing a cyclic olefin structure formed by epoxidation,

(C) Tertiary amines, tertiary amine salts, imidazoles and cationic polymerization initiators.

[2]

The adhesive composition as described in [1], wherein the adhesive composition contains 0.1 to 50 parts by weight of (B) relative to 100 parts by weight of (A).

[3]

The adhesive composition as described in [1] or [2], wherein (A) is a styrene-based elastomer selected from the group consisting of styrene-ethylene butylene-styrene block copolymers and styrene-ethylene propylene block copolymers, modified by at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides.

[4]

The adhesive composition as described in any one of [1] to [3], wherein (B) is at least one cyclohexyl epoxy resin selected from the group consisting of compounds represented by the following formulas (1) to (4).

In the above formula (1), X represents a single bond or a divalent alkyl group, carbonyl group, ether group, thioether group, ester group, carbonate group, amide group, siloxane bond or a group formed by bonding multiple such groups.

[5]

The adhesive composition as described in any one of [1] to [4] further contains (D) an organic solvent.

[6]

A bonding film formed using the bonding agent composition described in any one of [1] to [5].

The adhesive composition of the present invention has excellent low dielectric properties and adhesion between resin and metal. Therefore, the adhesive composition of the present invention is suitable for use in applications such as laminates with adhesive layers (covering films, bonding sheets), copper foils with resins, flexible copper clad laminates, and flexible flat cables.

The present invention is described in detail below. In addition, the present invention is not limited to the following implementation forms, and can be implemented in various ways within the scope of its main purpose.

<Adhesive composition of the present invention>

The adhesive composition of the present invention contains (A) an acid-modified styrene-based elastomer and (B) an epoxy resin having a structure in which the unsaturated bonds of a cyclic olefin structure are epoxidized. The above formulas (A) and (B) will be described in detail below.

[(A) Acid-modified styrene elastomer]

In the adhesive composition of the present invention, as the main component, a styrene-based elastomer (acid-modified styrene-based elastomer) modified with at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides is used. The method of modifying the styrene-based elastomer includes, for example, a method of subjecting the styrene-based elastomer and at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides to a grafting reaction.

Specific examples of styrene-based elastic materials include styrene-butadiene block copolymer, styrene-ethylene propylene block copolymer, styrene-butadiene-styrene block copolymer (SBS), styrene isoprene-styrene block copolymer (SIS), styrene-ethylene butylene-styrene block copolymer (SEBS), styrene-ethylene propylene-styrene block copolymer (SEPS), etc. Among these styrene-based elastic materials, styrene-ethylene butylene-styrene block copolymer (SEBS) and styrene-ethylene propylene-styrene block copolymer (SEPS) are preferred from the perspective of adhesion and low dielectric properties.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, succinic acid, itaconic acid, fumaric acid, etc. Examples of unsaturated carboxylic anhydrides include succinic anhydride, itaconic anhydride, fumaric anhydride, etc. Among these unsaturated carboxylic acids and unsaturated carboxylic anhydrides, succinic acid, fumaric acid, succinic anhydride are preferred, and succinic anhydride is more preferred. The amount of modification caused by at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides is generally about 0.1 to 10% by mass of the total acid-modified styrene-based elastomer. In addition, the acid-modified styrene-based elastomer is preferably an acid anhydride in which at least a portion of the total acidic groups in the acid-modified elastomer are acid anhydrides.

The acid value of the acid-modified styrene elastomer is not particularly limited. For example, the lower limit is 0.1 mgCH ₃ ONa/g or more, preferably 0.5 mgCH ₃ ONa/g or more, more preferably 1.0 mgCH ₃ ONa/g or more; the upper limit is 20 mgCH ₃ ONa/g or less, preferably 18 mgCH ₃ ONa/g or less, more preferably 15 mgCH ₃ ONa/g or less.

The molecular weight of the acid-modified styrene-based elastomer is, for example, a weight average molecular weight of 10,000 or more, preferably 30,000 or more, more preferably 50,000 or more, and, for example, 500,000 or less, preferably 300,000 or less, and more preferably 200,000 or less. In addition, the weight average molecular weight in the present invention is a molecular weight converted to polystyrene measured by gel permeation chromatography (GPC).

Commercially available acid-modified styrene-based elastomers include, for example, the Tuftec M series manufactured by Asahi Kasei Corporation and the Kraton FG series manufactured by Kraton Polymer Japan.

In the present invention, the above-mentioned acid-modified styrene-based elastomer can be used alone or in combination of two or more.

[(B) An epoxide resin having an unsaturated bond containing a cyclic olefin structure obtained by epoxidation]

Alicyclic epoxy resins are epoxy resins containing alicyclic structures. The structure formed by epoxidation of unsaturated bonds of a cyclic olefin structure contains a cycloalkane structure corresponding to the cyclic olefin structure, and an epoxide group formed by two adjacent carbon atoms and oxygen atoms constituting the aforementioned cycloalkane structure. The cyclic olefin structure may be monocyclic or polycyclic. The cyclic olefin structure may also have a substituent such as an alkyl group. Alicyclic epoxy resins containing a structure formed by epoxidation of unsaturated bonds of a cyclic olefin structure include, for example, compounds represented by the following formulas (1) to (4).

(在上述式(1)中，X表示單鍵或2價的烴基、羰基、醚基、硫醚基、酯基、碳酸酯基、醯胺基、矽氧烷鍵或由複數個此等基鍵結而成之基)

(In the above formula (1), X represents a single bond or a divalent alkyl group, carbonyl group, ether group, thioether group, ester group, carbonate group, amide group, siloxane bond or a group formed by bonding a plurality of these groups)

Examples of the compound represented by the above formula (1) include 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4,4'-bis(1,2-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, and the compound represented by the following formula (1-1).

Among the alicyclic epoxy resins having a structure in which the unsaturated bonds of the cyclic olefin structure are epoxidized, preferred are 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 4,4'-bis(1,2-epoxycyclohexane), the compound represented by the above formula (1-1), the compound represented by the above formula (2), the compound represented by the above formula (3), and the compound represented by the above formula (4).

Furthermore, commercially available products of epoxide resins containing unsaturated bonds of cyclic olefin structures formed by epoxidation include, for example, CELLOXIDE 2021P, CELLOXIDE 8010P, CELLOXIDE 2081, and EPOLEAD GT401 from DAICEL; THI-DE, DE-102, and DE-103 from ENEOS; and X-40-2669 and KR-470 from Shin-Etsu Silicone.

In the present invention, the above-mentioned cycloolefin-containing unsaturated bonds formed by epoxidation can be used alone or in combination of two or more.

The amount of (B) contained in the adhesive composition of the present invention is generally 0.1 to 50 parts by weight, preferably 0.4 to 30 parts by weight, more preferably 0.4 to 20 parts by weight, and even more preferably 0.4 to 4 parts by weight, relative to 100 parts by weight of (A).

[Other ingredients]

In addition to the above formulas (A) and (B), the adhesive composition of the present invention may also contain other thermoplastic resins other than (A) acid-modified styrene elastomers, tackifiers, flame retardants, coupling agents, antioxidants, fillers and (D) organic solvents, etc.

Examples of the above-mentioned other thermoplastic resins include: styrene-based elastomers that do not contain anhydride groups, phenoxy resins, polyamide resins, polyester resins, polycarbonate resins, polyphenylene ether resins, polyurethane resins, polyacetal resins, polyethylene resins, polypropylene resins, and polyethylene resins. These thermoplastic resins can be used alone or in combination of two or more.

Examples of the above-mentioned thickeners include coumarone-indene resin, terpene resin, terpene-phenol resin, rosin resin, tert-butylphenol-acetylene resin, phenol-formaldehyde resin, xylene-formaldehyde resin, petroleum hydrocarbon resin, hydrogenated hydrocarbon resin, turpentine resin, etc. These thickeners can be used alone or in combination of two or more.

系化合物；及三聚氰酸化合物、異三聚氰酸化合物、三唑系化合物、四唑系化合物、重氮化合物、尿素等氮系阻燃劑；矽氧化合物、矽烷化合物等矽系阻燃劑。再者，無機阻燃劑可舉例如：氫氧化鋁、 氫氧化鎂、氫氧化鋯、氫氧化鋇、氫氧化鈣等金屬氫氧化物；氧化錫、氧化鋁、氧化鎂、氧化鋯、氧化鋅、氧化鉬、氧化鎳等金屬氧化物；碳酸鋅、碳酸鎂、碳酸鋇、硼酸鋅、水合玻璃等。此等阻燃劑可以單獨使用，亦可以併用2種以上。 The flame retardant mentioned above may include, for example, organic flame retardants, inorganic flame retardants, and the like. Examples of organic flame retardants include: melamine phosphate, melamine polyphosphate, guanidine phosphate, guanidine polyphosphate, ammonium phosphate, ammonium polyphosphate, ammonium amide phosphate, ammonium amide polyphosphate, phosphate amide formate, polyphosphate amide formate, tris(diethyl hypophosphite) aluminum, tris(methylethyl hypophosphite) aluminum, tris(diphenyl hypophosphite) aluminum, bis(diethyl hypophosphite) zinc, bis(methylethyl hypophosphite) zinc, bis(diphenyl hypophosphite) zinc, bis(diethyl hypophosphite) titanium oxide, tetrakis(diethyl hypophosphite) titanium, bis(methylethyl hypophosphite) titanium oxide, tetrakis(methylethyl hypophosphite) titanium, bis(diphenyl hypophosphite) titanium oxide, tetrakis(diphenyl hypophosphite) titanium and the like phosphorus-based flame retardants; melamine, melam, melamine cyanurate (Melamine cyanurate); cyanurate) etc.

and nitrogen-based flame retardants such as cyanuric acid compounds, isocyanuric acid compounds, triazole compounds, tetrazole compounds, diazo compounds, and urea; and silicon-based flame retardants such as silicon oxide compounds and silane compounds. In addition, inorganic flame retardants include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, and calcium hydroxide; metal oxides such as tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, and nickel oxide; zinc carbonate, magnesium carbonate, barium carbonate, zinc borate, and hydrated glass. These flame retardants can be used alone or in combination of two or more.

Examples of the coupling agent include silane-based coupling agents such as vinyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-phenylenetrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltriethoxysilane, 3-butylpropylmethyldimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxysilane, and imidazole silane; titanium ester-based coupling agents; aluminum ester-based coupling agents; zirconium-based coupling agents, and the like. These coupling agents can be used alone or in combination of two or more.

Examples of the antioxidant include phenolic antioxidants such as 2,6-di-tert-butyl-4-cresol, n-octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate]methane, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], and triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate]; sulfur-based antioxidants such as dilauryl 3,3'-thiodipropionate and myristyl 3,3'-thiodipropionate; and phosphorus-based antioxidants such as tris(nonylphenyl)phosphite and tris(2,4-di-tert-butylphenyl)phosphite. These antioxidants can be used alone or in combination of two or more.

The fillers include, for example, polyacrylate powder, epoxy resin powder, polyamide powder, polyurethane powder, polysiloxane powder, etc., as well as polymer fillers such as core-shell layers of multilayer structures using polysilicone, acrylic acid, styrene butadiene rubber, butadiene rubber, etc.; silica, mica, talc, kaolin, clay, hydrotalcite, wollastonite, hard silica, silicon nitride, nitrogen Boron, aluminum nitride, calcium hydrogen phosphate, calcium phosphate, glass flakes, hydrated glass, calcium titanate, sepiolite, magnesium sulfate, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, barium hydroxide, calcium hydroxide, titanium oxide, tin oxide, aluminum oxide, magnesium oxide, zirconium oxide, zinc oxide, molybdenum oxide, antimony oxide, nickel oxide, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, zinc borate, aluminum borate and other inorganic fillers. These fillers can be used alone or in combination of two or more. Furthermore, the shapes can be, for example, spherical, powdery, fibrous, needle-like, scaly, etc.

烷、環戊基甲醚、二氯甲烷、氯仿、1,2-二氯乙烷、γ-丁內酯、賽路蘇、丁賽路蘇、卡必醇、丁基卡必醇等。此等有機溶劑可以單獨使用，亦可以併用2種以上。 Examples of the organic solvent (D) include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, cyclohexane, methylcyclohexane, toluene, xylene, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, ethylene glycol monomethyl ether acetate, propylene glycol dimethyl ether acetate, dimethicone ...

alkane, cyclopentyl methyl ether, dichloromethane, chloroform, 1,2-dichloroethane, γ-butyrolactone, celulose, butylcelulose, carbitol, butyl carbitol, etc. These organic solvents may be used alone or in combination of two or more.

Furthermore, in addition to the above-mentioned other components, the adhesive composition of the present invention may also contain stabilizers such as light stabilizers, weather stabilizers, and heat stabilizers; leveling agents, defoaming agents, and other anionic, cationic, and non-ionic surfactants; dyes, pigments, plasticizers, etc., to the extent that the functions of the adhesive composition are not affected.

In addition, the adhesive composition of the present invention does not contain (C) tertiary amines, tertiary amine salts, imidazoles and cationic polymerization initiators (so-called curing accelerators). For example, it is also obvious from the comparison with the various embodiments and comparative examples of Patent Document 1 that (C) is usually used for the purpose of promoting the reaction between elastic materials and epoxy resins. By not including these, as shown in the items of the embodiments described below, excellent adhesion is shown.

、三乙二胺、1,8-二吖雙環[5.4.0]十一烯等。三級胺鹽類之例可舉例如：1,8-二吖雙環[5.4.0]十 一烯的甲酸酯、己酸乙酯、辛酸鹽、對甲苯磺酸酯、鄰酞酸酯、苯酚鹽或酚醛清漆樹脂鹽；及1,5-二吖雙環[4.3.0]壬烯的甲酸酯、己酸乙酯、辛酸鹽、對甲苯磺酸酯、鄰酞酯鹽、苯酚鹽或酚醛樹脂清漆鹽等。咪唑類之例可舉例如：2-甲基咪唑、2-十一基咪唑、2-十七基咪唑、1,2-二甲基咪唑、2-甲基-4-乙基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、2,4-二胺基-6-[2-甲基咪唑基-(1)]乙基-s-三

、2,4-二胺基-6-[2-十一基咪唑基-(1)]乙基-s-三

、2,4-二胺基-6-[2-乙基-4-甲基咪唑基-(1)]乙基-s-三

、2,4-二胺基-6-[2-甲基咪唑基-(1)]乙基-s-三

異三聚氰酸加成物、2-苯基咪唑異三聚氰酸加成物、2-苯基-4,5-二羥甲基咪唑、2-苯基-4-甲基-5-羥甲基咪唑等。陽離子聚合起始劑之例可舉例如：芳香族碘鹽、芳香族鋶鹽等。 Examples of tertiary amines include benzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol, tetramethylguanidine, triethanolamine, N,N-dimethylpiperidin

, triethylenediamine, 1,8-diazabicyclo[5.4.0]undecene, etc. Examples of tertiary amine salts include formate, ethyl hexanoate, octanoate, p-toluenesulfonate, o-phthalate, phenol salt, or novolac salt of 1,8-diazabicyclo[5.4.0]undecene; and formate, ethyl hexanoate, octanoate, p-toluenesulfonate, o-phthalate, phenol salt, or novolac salt of 1,5-diazabicyclo[4.3.0]nonene. Examples of imidazoles include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 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-triazole,

, 2,4-diamino-6-[2-undecylimidazolyl-(1)]ethyl-s-tri

, 2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1)]ethyl-s-tri

, 2,4-diamino-6-[2-methylimidazolyl-(1)]ethyl-s-tri

isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. Examples of the cationic polymerization initiator include aromatic iodine salts, aromatic cobalt salts, etc.

The adhesive composition of the present invention can be produced by mixing (A) an acid-modified styrene-based elastomer, (B) an epoxy resin having an unsaturated bond containing a cyclic olefin structure by epoxidation, and other required components. The mixing method is not particularly limited as long as the adhesive composition can be made uniform. Since the adhesive composition is preferably used in a solution state (hereinafter referred to as a liquid adhesive composition), the above-mentioned (D) organic solvent is also usually used. By making the adhesive composition into a liquid, coating on the base film and forming the adhesive layer can be carried out more smoothly when manufacturing FPC-related components, and an adhesive layer with a desired thickness can be obtained more easily.

When the adhesive composition is in liquid form, the solid content concentration is, for example, 3 to 80% by weight, preferably 10 to 50% by weight, and more preferably 20 to 35% by weight, from the perspective of processability including the formation of the adhesive layer.

<Purpose>

The adhesive composition of the present invention is suitable as an adhesive (such as an adhesive film) for manufacturing FPC-related components due to its low dielectric properties and excellent adhesion between resin and metal. The FPC-related components in the present invention include, for example, covering films, adhesive sheets, copper foil with resin, flexible copper-clad laminates, flexible flat cables, etc.

[Implementation example]

The present invention is described in more detail with the following examples, but the present invention is not limited thereto. In addition, in the following examples, the adhesive layer is in the B-stage state, which means that a part of the adhesive composition begins to harden in a semi-hardened state, and the adhesive composition is further hardened by heating, etc.

(Examples 1 to 7, Comparative Examples 1 to 6)

Each component was added to a 1000 ml flask with a stirrer in the proportion (weight parts) shown in Table 1 or Table 2, and the adhesive composition was prepared by stirring at room temperature for 6 hours to disperse it. The obtained adhesive composition was used to measure various physical properties by the following method. The results are shown in Table 1 or Table 2.

(1) Dielectric coefficient, dielectric loss factor (also known as dielectric loss factor)

Prepare a release-treated glass plate, apply the adhesive composition prepared as above so that the thickness after drying becomes 100μm. Then, place the coated glass plate in an oven and dry it at 100℃ for 10 minutes to form a B-stage adhesive composition (thickness 100μm), and then place the adhesive layer in an oven and heat-harden it at 160℃ for 60 minutes to make a test piece. For this test piece, use the dielectric constant measuring device made by AET to obtain the dielectric constant (Dk) and dielectric loss factor (Df) at a measuring temperature of 25℃ and a measuring frequency of 10GHz by the cavity resonator method.

(2) Peel-off strength

A polyimide film ("Kapton 100EN" manufactured by DU PONT-TORAY) with a thickness of 25 μm was prepared, and the adhesive composition prepared as described above was applied to one surface thereof. Then, the film with the coating was placed in an oven and dried at 100°C for 5 minutes to form a B-stage adhesive layer (thickness of about 15 μm), and a covering film (laminated body with adhesive layer) was obtained. Then, the rolled copper foil with a thickness of 20 μm was superimposed in surface contact with the surface of the adhesive layer of the covering film (polyimide film/adhesive layer/copper foil), and heated and pressed for 60 minutes at a temperature of 160°C and a pressure of 4.5 MPa to obtain a flexible copper-clad laminate. The flexible copper-clad laminate was cut into 10 mm wide × 100 mm long, and the peel strength was measured in the 90° direction (the direction perpendicular to the surface direction of the laminate) using the Autograph AGS-500 manufactured by Shimadzu Corporation under the following measurement conditions. The measurement conditions were to set the test speed to 50 mm/min.

In addition, the components in Table 1 and Table 2 are as follows.

[(A): Acid-modified styrene elastomer]

(A-1): Tuftec M1911 (maleic anhydride-modified styrene-ethylene butylene-styrene block copolymer, acid value: 2 mgCH ₃ ONa/g, weight average molecular weight: 150,000, manufactured by Asahi Kasei Chemicals Co., Ltd.)

[(B): An epoxide resin containing an unsaturated bond of a cyclic olefin structure that is epoxidized]

(B-1): CELLOXIDE 2021P (3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, manufactured by DAICEL)

(B-2): CELLOXIDE 8010P (4,4'-bis(1,2-epoxycyclohexane), manufactured by DAICEL)

(B-3): DE-103 (the compound represented by the above formula (4), manufactured by ENEOS)

(B-4): X-40-2669 (the compound represented by the above formula (1-1), manufactured by Shin-Etsu Silicone Co., Ltd.)

[other]

(C-1): U-CAT SA102 (manufactured by San-Apro, tertiary amine salt, 2-ethylhexanoate of DBU)

(C-2): SAN AID 100L (manufactured by Sanshin Chemical Co., Ltd., cationic polymerization initiator, aromatic cobalt salt)

(C-3): 2E4MZ (2-ethyl-4-methylimidazole, manufactured by Wako Pure Chemical Industries, Ltd.)

(D): Toluene

(E): HP-7200L (epoxypropyl ether type epoxy resin, manufactured by DIC Corporation)

(F): Tuftec H1041 (acid unmodified styrene elastomer, manufactured by Asahi Kasei Chemicals Co., Ltd.)

[Table 1]

[Table 2]

Claims (6)

An adhesive composition comprising the following (A) and (B), and not comprising the following (C), (A) Acid-modified styrene elastomers, (B) An epoxy resin containing an unsaturated bond of a cyclic olefin structure formed by epoxidation, (C) Tertiary amines, tertiary amine salts, imidazoles and cationic polymerization initiators. The adhesive composition as described in claim 1, wherein the adhesive composition contains 0.1 to 50 parts by weight of (B) relative to 100 parts by weight of (A). The adhesive composition as described in claim 1 or 2, wherein (A) is obtained by modifying at least one styrene-based elastomer selected from the group consisting of styrene-ethylene butylene-styrene block copolymers and styrene-ethylene propylene block copolymers by at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. The adhesive composition as described in any one of claims 1 to 3, wherein (B) is at least one epoxide resin selected from the group consisting of compounds represented by the following formulas (1) to (4),

In the above formula (1), X represents a single bond or a divalent alkyl group, carbonyl group, ether group, thioether group, ester group, carbonate group, amide group, siloxane bond or a group formed by bonding multiple such groups;

The adhesive composition as described in any one of claims 1 to 4 further contains (D) an organic solvent. An adhesive film formed using the adhesive composition described in any one of claims 1 to 5.