KR20240019757A - Heat resistant adhesive film - Google Patents

Abstract

In an adhesive film used in a high-temperature heat treatment process, a heat-resistant adhesive film is provided that can be peeled off without adhesive remaining on the adherend even when the adhesive strength to the adherend increases through a high-temperature environment. An adhesive film in which a substrate, an easily adhesive layer, and a silicone-based adhesive layer are laminated on at least one side of the substrate in this order, wherein the easily adhesive layer includes a cycloalkene oxide-type alicyclic epoxy compound (A-i) and a glycidylamine-type epoxy. An adhesive film characterized in that it is a cured product obtained by heat curing a composition containing an epoxy compound (A), an acid anhydride (B), and a polyol compound (C) selected from the group consisting of compound (A-ii).

Description

Heat resistant adhesive film

The present invention relates to a heat-resistant adhesive film used in a high-temperature heat treatment process.

Conventionally, as a heat-resistant adhesive film, a silicone-based adhesive film with excellent heat resistance is used to laminate a plastic film such as a polyester film or a polyimide film, or a metal foil such as a copper foil or an aluminum foil.

These heat-resistant adhesive films are appropriately used for protecting and fixing electronic components even in manufacturing processes involving high-temperature environments related to semiconductor devices.

For example, Patent Document 1 discloses a heat-resistant adhesive film used during the manufacturing process of a QFN (QuadFlat Non-leaded package) package, which is a type of semiconductor package. The heat-resistant adhesive film used in the semiconductor package manufacturing process is an adhesive film used to adhere to a lead frame when resin sealing a semiconductor chip, and is used in terms of adhesion to the lead frame and reworkability at room temperature. It is considered desirable for the adhesive strength to increase in a high-temperature environment to prevent resin leakage in the high-temperature resin sealing process of 175 to 200°C with low adhesive strength.

Typically, the silicone-based adhesive layer has poor adhesion to a base material such as a plastic film or metal foil, so it is common to form a primer layer (easy-adhesion layer) to increase adhesion between the base material and the silicone-based adhesive layer (Patent Document 2) reference).

However, when exposed to a high-temperature environment after adhesion to an adherend, or when a silicone-based adhesive layer whose adhesive strength increases in a high-temperature environment is used, a phenomenon occurs in which the adhesive layer adheres to the adherend when the adhesive film is peeled off after cooling. There were many cases where “adhesive residue” occurred.

In Patent Document 3 and Patent Document 4, an easily adhesive layer made of a specific material is formed between the substrate and the silicone-based adhesive layer, so that when the protective sheet is peeled from the adherend even after exposure to a high temperature environment, the adhesive remains on the adherend. A heat-resistant adhesive sheet using a removable protective sheet is disclosed. However, when a silicone-based adhesive layer whose adhesive strength increases in a high temperature environment is used, adhesive residue may occur depending on the high temperature processing conditions or the adherend, so further improvement is necessary.

Patent Document 1: Japanese Patent Publication No. 2012-151360 Patent Document 2: Japanese Patent Publication No. 2002-338890 Patent Document 3: Japanese Patent Publication No. 2014-213545 Patent Document 4: Japanese Patent Publication No. 2014-221877

The present invention relates to a heat-resistant adhesive film used in a heat treatment process in a high-temperature environment such as a semiconductor device manufacturing process, and even if it is a silicone adhesive layer that increases the adhesive force to the adherend in a high-temperature environment, the adhesive film is used in a heat treatment process in a high-temperature environment such as a semiconductor device manufacturing process. The purpose is to provide a heat-resistant adhesive film with excellent adhesive residue suppression effect.

As a result of intensive studies to achieve the above object, the present inventors have found that, on one side of the substrate, a cycloalkene oxide-type alicyclic epoxy compound (A-i) and a glycidylamine-type epoxy compound (A-ii) are selected from the group consisting of An easily adhesive layer is formed containing a cured product obtained by heat curing a composition containing an epoxy compound (A), an acid anhydride (B), and a polyol compound (C), and a silicone-based adhesive composition is laminated and coated thereon, followed by thermal crosslinking. By forming a silicone-based pressure-sensitive adhesive layer, unreacted hydroxyl groups excessively contained in the easily adhesive layer react with reactive functional groups in the silicone-based pressure-sensitive adhesive composition, so that the substrate and the silicone-based pressure-sensitive adhesive layer adhere very strongly. It was discovered that the cured product of the easily adhesive layer has high heat resistance and can maintain adhesion even when exposed to a high temperature environment, leading to completion of the present invention.

The first invention is an adhesive film in which a substrate, an easily-adhesive layer, and a silicone-based adhesive layer are laminated on at least one side of the substrate in this order, wherein the easily-adhesive layer is a cycloalkene oxide-type alicyclic epoxy Curing by thermosetting a composition containing an epoxy compound (A), an acid anhydride (B), and a polyol compound (C) selected from the group consisting of compound (A-i) and glycidylamine-type epoxy compound (A-ii). It is an adhesive film characterized by being water.

The second invention is the adhesive film according to the first invention, wherein the polyol compound (C) is a silicate hydrolyzate.

The third invention is the adhesive film according to the first invention, wherein the polyol compound (C) is acrylic polyol.

The fourth invention is an epoxy compound (A) selected from the group consisting of cycloalkene oxide type alicyclic epoxy compound (A-i) and glycidylamine type epoxy compound (A-ii), which forms the easily adhesive layer, and an acid anhydride ( B) and a polyol compound (C), wherein the mass ratio of the total mass of the epoxy compound (A) and the acid anhydride (B) and the mass of the polyol compound (C) {[(A) + (B) ]:(C)} is the adhesive film according to any one of the first to third inventions, wherein the ratio is 10:90 to 90:10.

The fifth invention is an epoxy compound (A) selected from the group consisting of cycloalkene oxide type alicyclic epoxy compound (A-i) and glycidylamine type epoxy compound (A-ii), which forms the easily adhesive layer, and an acid anhydride ( In the composition containing B) and the polyol compound (C), the molar ratio of the epoxy group of the epoxy compound (A) and the acid group of the acid anhydride (B) {[epoxy group of (A)]:[acid group of (B)] } is an adhesive film according to any one of the first to fourth inventions, wherein the ratio is 20:80 to 80:20.

The sixth invention is the adhesive film according to any one of the first to fifth inventions, wherein the easily adhesive layer has a film thickness of 0.05 to 3.00 μm.

According to the present invention, on one side of the substrate, an epoxy compound (A) selected from the group consisting of a cycloalkene oxide type alicyclic epoxy compound (A-i) and a glycidylamine type epoxy compound (A-ii), an acid anhydride ( B) and a polyol compound (C) are formed by forming an easily adhesive layer containing a cured product obtained by heat curing the composition, laminating and coating a silicone-based adhesive composition thereon, and forming a silicone-based adhesive layer by thermal crosslinking, Since unreacted hydroxyl groups excessively contained in the easily adhesive layer react with reactive functional groups in the silicone-based adhesive composition, the substrate and the silicone-based adhesive layer adhere very strongly, and the cured product of the easily adhesive layer has high heat resistance, Because it can maintain adhesion even when exposed to a high-temperature environment, a heat-resistant adhesive film has an excellent effect of suppressing adhesive residue on the adherend when peeled from the adherend even when the adhesion to the adherend increases in a high-temperature environment. It has become possible to provide

1 is a cross-sectional schematic diagram showing one embodiment of the heat-resistant adhesive film of the present invention.

Below, embodiments of the present invention will be described.

The heat-resistant adhesive film of the present invention is configured by laminating an easily adhesive layer and a silicone-based adhesive layer in this order on at least one side of a substrate, and the easily adhesive layer includes a cycloalkene oxide type alicyclic epoxy compound (A-i) and glycidyl It is an adhesive film containing a cured product obtained by thermosetting a composition containing an epoxy compound (A), an acid anhydride (B), and a polyol compound (C) selected from the group consisting of amine-type epoxy compounds (A-ii).

(base material)

As a base material constituting the heat-resistant adhesive film of the present invention, a plastic film or metal foil that can withstand high temperature heating can be used, but it is preferable to use a plastic film from the viewpoint of ease of handling and flexibility as an adhesive film.

When using a plastic film as a base material, a heat-resistant synthetic resin with a melting point of 250°C or higher is preferable, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), Examples include polyetherimide (PEI), polysulfone (PSF), polyethersulfone (PES), polyphenylene sulfide (PPS), and polyetheretherketone (PEEK). Among these heat-resistant synthetic resin films, it is more preferable to use polyimide film, which has excellent dimensional stability at high temperatures.

The thickness of the base material is preferably in the range of 5 to 250 μm, more preferably 10 to 150 μm, and still more preferably 20 to 100 μm from the viewpoint of processability and handling of the adhesive film. When the thickness of the substrate is 5 μm or more, preferably 10 μm or more, and more preferably 20 μm or more, the substrate is provided with elasticity, the coatability of the adhesive layer is improved, and the handleability when attaching the adhesive film is also improved. On the other hand, when the thickness of the substrate is 250 μm or less, preferably 150 μm or less, and more preferably 100 μm or less, the peelability is improved due to the appropriate flexibility of the substrate during rework, and the adherend is protected during peeling. As performance increases, equipment costs are also suppressed.

The surface of the base material on which the easily adhesive layer and the adhesive layer are formed may be subjected to corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, etc. as needed.

(Easily adhesive layer)

The easily adhesive layer constituting the heat-resistant adhesive film of the present invention is an epoxy compound (A) selected from the group consisting of a cycloalkene oxide type alicyclic epoxy compound (A-i) and a glycidylamine type epoxy compound (A-ii), an acid It is a cured product obtained by thermosetting a composition containing an anhydride (B) and a polyol compound (C).

The easily adhesive layer composition containing the above (A), (B), and (C) is mixed with a solvent and the like to form a coating solution, and is uniformly applied onto a substrate, solvent dried, and heat cured to form an easily adhesive layer. In the easily adhesive layer, the epoxy compound (A) and the acid anhydride (B), and the acid anhydride (B) and the polyol compound (C) react respectively to form a cured product through thermal curing.

Since the easily adhesive layer contains an epoxy cured product with high adhesiveness to synthetic resins or metals, it adheres firmly to substrates such as plastic films and metal foils.

Next, a silicone-based adhesive composition is laminated and coated on the heat-cured easily adhesive layer, and a silicone-based adhesive layer is formed by thermal crosslinking. However, in the heat crosslinking process of the silicone-based adhesive layer, the polyol compound in the easily adhesive layer is excessively contained. The unreacted hydroxyl group reacts with the reactive functional group (silanol (SiOH) group, hydrosilyl (SiH) group, etc.) of the main agent or crosslinking agent component in the silicone-based adhesive composition, so that the easily adhesive layer and the silicone-based adhesive layer adhere tightly. do. Therefore, the adhesion between the substrate and the silicone-based adhesive layer becomes stronger.

In addition, since the easily adhesive layer contains a cured product of a highly heat-resistant cycloalkene oxide-type alicyclic epoxy compound and/or a glycidylamine-type epoxy compound and an acid anhydride, it can adhere to the substrate and the silicone-based adhesive layer even when exposed to a high-temperature environment. Adhesion can be maintained.

From the viewpoint of actual roll-to-roll productivity, the easily adhesive layer of the present invention needs to be cured in a short time and have a tack-free surface. Since the composition of the easily adhesive layer uses a cycloalkene oxide-type alicyclic epoxy compound and/or a glycidylamine-type epoxy compound, which are more reactive than the widely used non-glycidylamine-type bisphenol-type epoxy resin, it can be used at low temperatures. It has curability and can easily form a tack-free, easily adhesive layer on the surface.

Among the epoxy compounds (A) used in the easily adhesive layer composition, the cycloalkene oxide type alicyclic epoxy compound (A-i) is an epoxy compound in which an epoxy group is formed between two adjacent carbon atoms constituting an alicyclic (aliphatic hydrocarbon ring). , which has one or more epoxy groups in one molecule. Specific examples of the cycloalkene oxide type alicyclic epoxy compound (A-i) include, for example, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 3,4-epoxy-6-methylcyclo. Hexylmethyl-3',4'-epoxy-6'-methylcyclohexylcarboxylate, 2,3-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, 4-(3,4-epoxy- 5-methylcyclohexyl)butyl-3',4'-epoxycyclohexylcarboxylate, 3,4-epoxycyclohexylethylene oxide, cyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, 3,4-epoxy- 6-methylcyclohexylmethyl-6'-methylsiloxylcarboxylate, bis-epoxydicyclopentadienyl ether, bis-epoxycyclohexyl adipate, 3,4-dimethyl-1,2-epoxycyclohexane, 3, 5-dimethyl-1,2-epoxycyclohexane, 3-methyl-5-t-butyl-1,2-epoxycyclohexane, octadecyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, N -Butyl-2,2-dimethyl-3,4-epoxycyclohexylcarboxylate, cyclohexyl-2-methyl-3,4-epoxycyclohexylcarboxylate, N-butyl-2-isopropyl-3,4-epoxy -5-methylcyclohexylcarboxylate, octadecyl-3,4-epoxycyclohexylcarboxylate, 2-ethylhexyl-3',4'-epoxycyclohexylcarboxylate, 4,6-dimethyl-2,3-epoxy Cyclohexyl-3',4'-epoxycyclohexylcarboxylate, diethyl-4,5-epoxy-cis-1,2-cyclohexyldicarboxylate, di-n-butyl-3-t-butyl-4, 5-epoxy-cis-1,2-cyclohexyldicarboxylate, a polycyclic saturated hydrocarbon having an epoxy group (the polycyclic saturated hydrocarbon skeleton preferably has cyclic saturated hydrocarbons bonded to each other through two or more atoms, such Examples of the polycyclic saturated hydrocarbon skeleton include hydroindan, dicyclonorbornane, etc. The polycyclic saturated hydrocarbon having an epoxy group has an epoxy group bonded to the polycyclic saturated hydrocarbon skeleton, and a particularly preferable example is tetrahydroyne. (examples include diepoxide, etc.), silane coupling agents having an epoxy group (examples include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.), etc. there is. Among these, it is more preferable to use a cycloalkene oxide type alicyclic epoxy compound having two or more epoxy groups in one molecule. In addition, the cycloalkene oxide type alicyclic epoxy compound (A-i) can be used alone or in combination of two or more types.

The epoxy equivalent weight of the cycloalkene oxide type alicyclic epoxy compound (A-i) is preferably 80 to 500 g/eq, more preferably 100 to 400 g/eq, and still more preferably 120 to 500 g/eq from the viewpoint of curability with the curing agent. 300 g/eq, more preferably 120 to 250 g/eq.

Among the epoxy compounds (A) used in the easily adhesive layer composition, the glycidylamine type epoxy compound (A-ii) is an epoxy compound having a glycidyl group bonded to a nitrogen atom, and contains two or more epoxy groups in one molecule, It has one or more tertiary nitrogen atoms. The glycidylamine type epoxy compound (A-ii) may be an aromatic epoxy compound or an alicyclic epoxy compound. Specific examples of the glycidylamine type epoxy compound (A-ii) include, for example, N,N-diglycidylaniline, N,N-diglycidyl-2-methylbenzenamine, and N,N-di. Glycidyl-4-(glycidyloxy)aniline, N,N,N',N'-tetraglycidyl-1,3-benzenedi(methanamine), 4,4'-methylenebis(N, N-diglycidylaniline), 4,4'-[1,4-phenylenebis(dimethylmethylene)]bis(N,N-diglycidylaniline), 4,4'-[(1,4 -Phenylene)bisoxy]bis(N,N-diglycidylaniline), 4,4'-methylenebis(N,N-diglycidyl-2-methylaniline), 4,4'-methylenebis (N,N-diglycidyl-3-methylaniline), 4,4'-[1,4-phenylenebis(dimethylmethylene)]bis(N,N-bisglycidyl-2,6-dimethyl aniline), 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, etc. Among these, it is more preferable to use a glycidylamine-type epoxy compound having three or more epoxy groups in one molecule. In addition, the glycidylamine type epoxy compound (A-ii) can be used individually or in combination of two or more types.

The epoxy equivalent weight of the glycidylamine type epoxy compound (A-ii) is preferably 80 to 500 g/eq, more preferably 85 to 400 g/eq, and still more preferably 90 g/eq from the viewpoint of curability with the curing agent. ~ 300 g/eq, more preferably 95 ~ 150 g/eq.

As the acid anhydride (B) used in the easily adhesive layer composition, a known acid anhydride used as various epoxy curing agents can be preferably used.

Examples of the acid anhydride (B) include phthalic anhydride, succinic anhydride, HET acid anhydride, hymic acid anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydraphthalic anhydride, tetrabromophthalic anhydride, Tetrachlorophthalic anhydride, trimellitic anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, cyclohexane-1,2-dicarboxylic anhydride, 4-methylcyclo Hexane-1,2-dicarboxylic acid anhydride, 5-(2,5-oxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, silane coupling agent having an acid anhydride group and an alkoxysilane group (Examples include 3-trimethoxysilylpropylsuccinic anhydride, etc.).

The acid anhydride (B) can be used individually or in combination of two or more of the above acid anhydrides.

The mixing ratio of the acid anhydride (B) to the total amount of the epoxy compound (A) is the molar ratio of the epoxy group of the epoxy compound (A) and the acid group of the acid anhydride (B) from the viewpoint of improving the tack-free property of the easily adhesive layer. [Epoxy group of (A)]:[Acid group of (B)]} is preferably in the range of 20:80 to 80:20.

The polyol compound (C) used in the easily adhesive layer composition is a compound having two or more hydroxyl groups in one molecule. The hydroxyl group of the polyol compound (C) reacts with the acid anhydride (B) of the easily adhesive layer composition and reactive functional groups such as silanol group (SiOH group) and hydrosilyl group (SiH group) of the components of the silicone adhesive composition, respectively. Thus, it contributes to firmly adhering the easily adhesive layer and the silicone-based adhesive layer.

The polyol compound (C) is preferably a polymer (oligomer or polymer), and examples of organic polymers include acrylic polyol, polyester polyol, and polyether polyol. As the organic polymer-based polyol compound (C), acrylic polyol is more preferable from the viewpoint of further improving the effect of suppressing adhesive residue. Additionally, examples of the inorganic polyol compound (C) include silicate hydrolysates.

Examples of the acrylic polyol include a copolymer obtained by copolymerizing a polymerizable monomer having one or more hydroxyl groups in the molecule and another monomer copolymerizable therewith, and examples of the polymerizable monomer having a hydroxyl group include, for example, 2- Hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2,2-dihydroxymethylbutyl (meth)acrylate, polyhydroxyalkyl maleate, poly Hydroxyalkyl fumarate, etc. can be mentioned. In addition, monomers that can be copolymerized with these include, for example, (meth)acrylic acid, alkyl (meth)acrylate (C1 to C12), maleic acid, alkyl maleate, fumaric acid, alkyl fumarate, itaconic acid, alkyl itaconic acid, styrene, α. -Methyl styrene, vinyl acetate, (meth)acrylonitrile, 3-(2-isocyanate-2-propyl)-α-methyl styrene, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate etc. can be mentioned. Then, acrylic polyol can be obtained by copolymerizing these monomers in the presence of an appropriate solvent and polymerization initiator.

Examples of the polyester polyol include polyester polyol obtained by condensation polymerization of a polyol and polycarboxylic acid (polybasic acid), and polyester polyol obtained by ring-opening polymerization of lactones.

Polyols used in condensation polymerization to obtain the polyester polyol include, for example, ethylene glycol, diethylene glycol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,3 ,5-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 2,6-hexane Diol, 1,8-octanediol, 1,4-cyclohexanedimethanol, 1,2-dimethylolcyclohexane, 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane, 1,12-dode Candiol, polybutadienediol, neopentyl glycol, tetramethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, 1,3-dihydroxyacetone, hexylene glycol, 1,2,6-hexanetriol , ditrimethylolpropane, mannitol, sorbitol, and pentaerythritol.

Examples of polycarboxylic acids used in condensation polymerization to obtain the polyester polyol include oxalic acid, adipic acid, sebacic acid, fumaric acid, malonic acid, succinic acid, glutaric acid, azelaic acid, citric acid, and 2,6-naphthalenedi. Carboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, citraconic acid, 1,10-decanedicarboxylic acid, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride and trihydrocytic acid. Examples include mellitic acid.

Examples of lactones used in ring-opening polymerization to obtain the polyester polyol include ε-caprolactone, δ-valerolactone, and γ-butyrolactone.

Examples of the polyether polyol include polyether polyol obtained by addition reaction of a cyclic ether compound to polyols, and polyether polyol obtained by ring-opening polymerization of alkylene oxide.

More specifically, the polyether polyol includes, for example, ethylene glycol, diethylene glycol, 1,2-propanediol (propylene glycol), 2-methyl-1,3-propanediol, 1,3-propanediol, 1,4-butanediol (tetramethylene glycol), 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentane Diol, 2,3,5-trimethyl-1,5-pentanediol, 1,6-hexanediol, 2-ethyl-1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 2,6-hexanediol, 1,8-octanediol, 1,4-cyclohexanedimethanol, 1,2-dimethylolcyclohexane, 1,3-dimethylolcyclohexane, 1,4-dimethylolcyclohexane, 1,12-Dodecanediol, polybutadienediol, neopentyl glycol, dipropylene glycol, glycerin, trimethylolpropane, 1,3-dihydroxyacetone, hexylene glycol, 1,2,6-hexanetriol, di Polyol polymers such as trimethylolpropane, mannitol, sorbitol, and pentaerythritol; Addition of the above polyols and alkylene oxides such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, and epichlorohydrin. water; and ring-opening polymers of cyclic ethers such as tetrahydrofurans (for example, polytetramethylene glycol).

The number average molecular weight of the polyol compound (C) is not particularly limited, but for example, it is preferably within the range of 200 to 100,000, more preferably within the range of 500 to 50,000, and preferably within the range of 1,000 to 10,000. More preferably, it is further preferably within the range of 2,000 to 7,000. When the number average molecular weight is 200 or more, preferably 500 or more, more preferably 1,000 or more, and even more preferably 2,000 or more, the flexibility of the easily adhesive layer is improved, and the crack resistance of the easily adhesive layer during processing is improved. . On the other hand, when the number average molecular weight is 100,000 or less, preferably 50,000 or less, more preferably 10,000 or less, and even more preferably 7,000 or less, the effect of suppressing precipitation of the polyol compound in the easily adhesive layer composition and other components of the polyol compound are reduced. Solubility is improved. In addition, the number average molecular weight of the polyol compound (C) means the number average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).

The weight average molecular weight of the polyol compound (C) is not particularly limited, but for example, it is preferably within the range of 200 to 300,000, more preferably within the range of 1,000 to 100,000, and preferably within the range of 10,000 to 40,000. It is more desirable. When the weight average molecular weight is 200 or more, preferably 1,000 or more, and more preferably 10,000 or more, the flexibility of the easily adhesive layer improves and the crack resistance of the easily adhesive layer during processing improves. On the other hand, when the weight average molecular weight is 300,000 or less, preferably 100,000 or less, and more preferably 40,000 or less, the effect of suppressing precipitation of the polyol compound in the easily adhesive layer composition and the solubility of the polyol compound in other components are improved. In addition, the weight average molecular weight of the polyol compound (C) means the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).

The polyol compound (C) preferably has a hydroxyl value in the range of 10 to 200 KOH mg/g, more preferably in the range of 15 to 100 KOH mg/g, and even more preferably in the range of 35 to 85 KOH mg/g. , it is more preferable to be within the range of 50 to 70KOHmg/g. The hydroxyl value is 10KOHmg/g or more, preferably 15KOHmg/g or more, more preferably 35KOHmg/g or more, and even more preferably 50KOHmg/g or more, so that the hydroxyl value remains even after reaction with the acid anhydride (B) in the easily adhesive layer composition. Because it remains, hydroxyl groups that contribute to adhesion to the silicone-based adhesive layer can be effectively secured, and the adhesion between the easily adhesive layer and the silicone-based adhesive layer can be improved. On the other hand, the hydroxyl value is 200KOHmg/g or less, preferably 100KOHmg/g or less, more preferably 85KOHmg/g or less, and even more preferably 70KOHmg/g or less, so that the reactive functional group and polyol that contribute to crosslinking of the silicone adhesive layer By appropriately reacting with the hydroxyl group of the compound, the crosslinking property of the silicone adhesive layer can be improved. As a result, by sufficiently crosslinking the silicone adhesive layer, cohesion can be improved and the effect of suppressing adhesive residue can be improved. there is.

As the polyol compound (C), an inorganic silicate hydrolyzate can be used. The silicate hydrolyzate has a large number of hydroxyl groups (silanol groups) and alkoxy groups, and the silanol groups undergo a curing reaction with the acid anhydride (B) when forming an easily adhesive layer coating film. In addition, most of the alkoxy groups of the silicate hydrolyzate are dealcoholized to become hydroxyl groups (silanol groups) when forming an easily adhesive layer coating film, and then self-condensate to form a silicate polymer structure, so heat resistance can be further improved. In addition, the hydroxyl group (silanol group) on the surface of the silicate polymer structure of the silicate hydrolyzate also reacts with reactive functional groups such as silanol groups and hydrosilyl groups contained in the components of the silicone adhesive, reducing the adhesion between the easily adhesive layer and the silicone adhesive layer. contributes to.

The silicate hydrolyzate can be obtained by hydrolyzing and condensing an alkyl silicate in an organic solvent such as an alcohol solvent in the presence of a specific amount of water and a condensation catalyst (acid or base). As a raw material for forming the silicate hydrolyzate, for example, methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, etc. can be used. Additionally, silicate oligomers such as tetramer of tetramethoxysilane and pentamer of tetraethoxysilane can also be used.

As the silicate hydrolyzate, a silicate hydrolyzate liquid containing a commercially available silicate hydrolyzate may be appropriately used.

The compounding amount of the polyol compound (C) in the easily adhesive layer composition is the total mass of the epoxy compound (A) and the acid anhydride (B) and the polyol compound (C) from the viewpoint of ensuring adhesion between the substrate and the silicone adhesive. The mass ratio {[(A)+(B)]:(C)} is preferably in the range of 10:90 to 90:10, more preferably in the range of 30:70 to 90:10, and 40:60. It is more preferable that it is in the range of - 90:10, and it is still more preferable that it is in the range of 45:55 - 90:10. By setting the total mixing amount of the epoxy compound (A) and the acid anhydride (B) to 10:90 or more, preferably 30:70 or more, more preferably 40:60 or more, and even more preferably 45:55 or more, the base material The adhesion of the easily adhesive layer is improved, and by setting the total mixing amount of the epoxy compound (A) and the acid anhydride (B) to 90:10 or less, the mixing amount of the polyol compound (C) is effectively secured, thereby forming the easily adhesive layer and the silicone adhesive layer. Adhesion is improved, and the effect of suppressing adhesive residue on the adherend after a high-temperature heat treatment process is improved. In addition, when using a silicate hydrolyzate as the component (C), a silicate polymer structure (SiO ₂ ) is formed at the time of forming the easily adhesive layer, so the mass ratio is obtained by using the amount of SiO ₂ in the silicate hydrolyzate as the mass of the polyol compound (C). Let's do it.

Various additives such as antioxidants, antistatic agents, leveling agents, and antifoaming agents can be blended into the easily adhesive layer of the present invention as long as the effects of the present invention are obtained. The types and amounts of these additives can be appropriately selected within the range that achieves the effects of the present invention.

The film thickness of the easily adhesive layer of the present invention is preferably in the range of 0.05 to 3.00 μm, more preferably in the range of 0.1 to 3.00 μm, and 0.15 to 3.00 from the viewpoint of adhesion to the substrate and silicone adhesive and flexibility of the easily adhesive layer film. The range of ㎛ is more preferable. By setting the film thickness of the easily adhesive layer to 0.05 μm or more, preferably 0.1 μm or more, and more preferably 0.15 μm or more, adhesion is improved, and the effect of suppressing adhesive residue on the adherend after a high temperature heat treatment process is improved. On the other hand, when the film thickness of the easily adhesive layer is 3.00 μm or less, the cured film of the easily adhesive layer is provided with desirable flexibility, the film bending followability is improved, and the crack suppression of the easily adhesive layer is improved, so that the adherend after the high temperature heat treatment process is improved. The effect of suppressing adhesive residue is improved.

(Adhesive layer)

The adhesive layer constituting the heat-resistant adhesive film of the present invention is particularly made of a silicone-based adhesive because it has excellent heat resistance. Silicone-based adhesives mainly include silicone rubber (a long-chain polymer of polydimethylsiloxane with a structure consisting of D units [(CH ₃ ) ₂ SiO _2/2 ]) and MQ resin (M units [R ₃ SiO _1/2 : R is Examples include adhesives containing a monovalent organic group such as a methyl group or a phenyl group) and a polymer of a three-dimensional silicone resin having a structure composed of Q units [SiO _4/2 ]. The adhesive containing such silicone rubber and MQ resin has superior adhesiveness compared to silicone rubber monolith. In addition, basic adhesive properties such as adhesive strength, holding power, and tack can be controlled by changing the molecular weight of silicone rubber, crosslinking density, and ratio of MQ resin in the adhesive.

Silicone-based adhesives include addition curing type silicone adhesives, peroxide curing type silicone adhesives, and condensation reaction curing type silicone adhesives, depending on their curing mechanism. However, they can be crosslinked by curing at a relatively low temperature, and the production of by-products can be suppressed during curing. In this regard, an addition curing type silicone adhesive is preferable.

As the above addition curing type silicone adhesive, for example, one obtained by curing by addition reaction a silicone composition containing diorganopolysiloxane having two or more alkenyl groups in one molecule and organohydrogenpolysiloxane as a crosslinking agent is suitably used. . An adhesive layer can preferably be obtained by uniformly coating the silicone composition, heat curing the silicone composition, and crosslinking the silicone composition.

Examples of the diorganopolysiloxane having two or more alkenyl groups in one molecule of the silicone composition include, for example, linear polydiorganosiloxane having vinyl groups only at both terminals, linear polyorganosiloxane having vinyl groups at both terminals and side chains, Examples include branched polyorganosiloxanes having vinyl groups only at the terminals, and branched polyorganosiloxanes having vinyl groups at the terminals and side chains.

The weight average molecular weight of the diorganopolysiloxane having two or more alkenyl groups in one molecule of the silicone composition is preferably in the range of 20,000 to 700,000, more preferably in the range of 50,000 to 400,000, and in the range of 70,000 to 100,000. It is more desirable. When the weight average molecular weight of the diorganopolysiloxane is 20,000 or more, preferably 50,000 or more, and more preferably 70,000 or more, curability is improved and adhesion to the adherend is improved because the crosslinking density is preferable. In addition, when the weight average molecular weight of the diorganopolysiloxane is 700,000 or less, preferably 400,000 or less, and more preferably 100,000 or less, the viscosity of the silicone composition is desirable, and thus manufacturability is improved. In addition, the weight average molecular weight means the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).

A known crosslinking agent for the silicone composition may be used. The organohydrogenpolysiloxane used as the crosslinking agent has at least three hydrogen atoms bonded to silicon atoms in one molecule, and linear, branched, or cyclic shapes can be used as the molecule. The hydrosilyl (SiH) group contained in the organohydrogenpolysiloxane reacts with the alkenyl group of the diorganopolysiloxane having an alkenyl group of the silicone composition, and also reacts with the hydroxyl group contained in the easily adhesive layer of the present invention. Strong adhesion between the adhesive layer and the silicone-based adhesive layer is obtained.

The range of the molar ratio (SiH group/alkenyl group) of the SiH group in the organohydrogenpolysiloxane to the alkenyl group in the diorganopolysiloxane having an alkenyl group of the silicone composition (SiH group/alkenyl group) is, for example, 0.5 to 3.0, more preferably 1.0. ~ 2.0, more preferably 1.0 ~ 1.5, even more preferably 1.1 ~ 1.4. When the molar ratio (SiH group/alkenyl group) is 0.5 or more, preferably 1.0 or more, and more preferably 1.1 or more, the crosslinking density of the silicone composition is improved, the cohesion is increased, the adhesive residual suppression effect is improved, and the easily adhesive layer of the easily adhesive layer is improved. Adhesion is improved due to the reaction between hydroxyl groups and SiH groups. On the other hand, the molar ratio (SiH group/alkenyl group) is 3.0 or less, preferably 2.0 or less, more preferably 1.5 or less, and even more preferably 1.4 or less to suppress the remaining unreacted hydrosilyl group in the cured product, Inhibition against changes in physical properties over time and deterioration of heat resistance of the cured product is improved, and inhibition of foaming due to dehydrogenation reaction in the cured product is also improved.

In the silicone composition, from the viewpoint of improving adhesion, M unit (R ₃ SiO _1/2 : R is a monovalent organic group such as methyl group or phenyl group), D unit (R ₂ SiO _2/2 ), T unit (RSiO _{3/ 2} ), a silicone resin containing a unit selected from the group consisting of Q units (SiO _4/2 ) can be used, but in that the effect of improving the adhesive strength of the adhesive layer is large, a conventionally known silicone resin consisting of M units and Q units is used. It is preferable to contain MQ resin. The mixing amount of MQ resin is appropriately mixed according to the required adhesive strength.

The platinum-based catalyst used in the crosslinking reaction of the silicone composition may be any known catalyst, and examples thereof include chloroplatinic acids such as chloroplatinic acid and diplatinic acid, alcohol compounds of chloroplatinic acid, aldehyde compounds, or chloroplatinic acid and various olefins. Examples include striae.

Additives may be appropriately added to the silicone composition of the silicone-based adhesive layer of the present invention for the purpose of improving other properties. Additives include organic/inorganic particles, colorants, silicone oil, silicone resin, silane coupling agents, antioxidants, etc.

The film thickness of the silicone-based adhesive layer of the present invention is preferably at least 5 μm or more, and usually 10 to 100 μm, in order to ensure adhesion and holding power to the adherend. When the film thickness of the adhesive layer is 5 μm or more, the holding power in the shear direction becomes good with respect to the adhesive force to the adherend, and the adhesion to the adherend improves. Additionally, when the film thickness of the adhesive layer is 100 μm or less, the amount of silicone composition used in the adhesive layer can be suppressed, thereby suppressing manufacturing costs.

As a method for forming a silicone-based adhesive layer of the present invention, the silicone composition is used as is or a coating liquid whose viscosity is adjusted with a solvent or the like, and the coating liquid is applied to the easily adhesive layer of the present invention formed on a substrate to a predetermined thickness. A silicone-based adhesive layer can be formed by uniformly coating, solvent drying, and further heating to crosslink the silicone composition.

Examples of the coating method of the coating liquid for the easily adhesive layer and the silicone-based adhesive layer of the present invention include a gravure coater, bar coater, comma knife coater, die coater, and reverse coater.

(separator)

In the present invention, for the purpose of preventing contamination or adhesion of foreign substances to the surface of the silicone-based adhesive layer, or improving handling of the adhesive film, it is suitable to use a separator made of a plastic film by bonding it to the surface of the silicone-based adhesive layer. The separator is made of a plastic film with high peelability, and if desired, a release agent formed on the surface of the plastic film can be used as appropriate.

Example

The heat-resistant adhesive film of the present invention will be described in detail below by showing examples and comparative examples, but the present invention is not limited to these examples.

<Preparation of easily adhesive layer coating solution>

Examples 1-1 to 1-19, Comparative Example 1-, using the following cycloalkene oxide type alicyclic epoxy compound (A-i), acid anhydride (B), and polyol compound (C) as the easily adhesive layer coating solution material. Each easily adhesive layer coating liquid of 1 to 1-3, Examples 2-1 to 2-19, and Comparative Examples 2-1 to 2-3 was produced. The materials used and compounding amounts of each easily adhesive layer coating liquid are shown in Tables 1 to 8. The easily adhesive layer coating liquid material and solvent were mixed according to the mixing ratio shown in Tables 1 to 8 to obtain an easily adhesive layer coating liquid.

[Epoxy compound (A)]

[Cycloalkene oxide type alicyclic epoxy compound (A-i)]

A-i-1: Celoxide 2021P (3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexylcarboxylate, non-volatile matter 100%, epoxy equivalent 130.5 g/eq), manufactured by Daicel Co., Ltd., A-i-2 : Epokaric THI-DE manufactured by Eneos Co., Ltd. (diepoxide of tetrahydroindene, non-volatile matter 100%, epoxy equivalent weight 80g/eq), A-i-3: KBM manufactured by Shin-Etsu Chemical Co., Ltd. -303 (2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, non-volatile matter 100%, epoxy equivalent weight 246.4 g/eq)

[Glycidylamine type epoxy compound (A-ii)]

A-ii-1: TETRAD-C manufactured by Mitsubishi Chemical Corporation (1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, non-volatile matter 100%, epoxy equivalent weight 102.5 g/eq), A -ⅱ-2: jER630 manufactured by Mitsubishi Chemical Corporation (N,N-diglycidyl-4-(glycidyloxy)aniline, non-volatile component 100%, epoxy equivalent weight 98 g/eq), A-ii-3 : GAN manufactured by Nippon Kayaku Co., Ltd. (N,N-diglycidylaniline, non-volatile component 100%, epoxy equivalent weight 125g/eq)

[Epoxy compound for comparative example]

A-4: As a comparative example, jER828 manufactured by Mitsubishi Chemical Corporation, a bisphenol-type epoxy compound that is neither a cycloalkene oxide-type alicyclic epoxy compound nor a glycidylamine-type epoxy compound (non-volatile matter 100%, epoxy equivalent weight 189 g/eq) )

[Acid anhydride (B)]

B-1: Shin Nihon Chemical Co., Ltd. Rikacid MH-700 (mixture containing cyclohexane-1,2-dicarboxylic acid anhydride and 4-methylcyclohexane-1,2-dicarboxylic acid anhydride, non-volatile content 100 %, acid anhydride equivalent 163.5g/eq), B-2: /eq)

[Polyol compound (C)]

C-1: HAS-1 manufactured by Corcoat Co., Ltd. (SiO ₂ concentration 21%, ethyl silicate hydrolyzate), C-2: Acridic A-817 manufactured by DC Co., Ltd. (non-volatile matter 50%, acrylic polyol) , styrene-acrylic copolymer, hydroxyl value: 60 mg KOH/g, glass transition temperature: 95° C., weight average molecular weight: 20,000), C-3: Byron GK-810 manufactured by Toyobo Corporation (100% non-volatile matter, polyester polyol) , hydroxyl value is 19㎎KOH/g, glass transition temperature is 46℃, number average molecular weight is 4,600)

<Mass ratio of easily adhesive layer components>

Epoxy compound (A) in the easily adhesive layer component of Examples 1-1 to 1-19, Comparative Examples 1-1 to 1-3, Examples 2-1 to 2-19, and Comparative Examples 2-1 to 2-3, and The total mass of the acid anhydride (B) [(A) + (B)] and the mass of the polyol compound (C) are converted to the following calculation formulas 1 and 2, and the mass ratio {[(A) + (B)]: (C )} are shown in Tables 1 to 8, respectively.

(Calculation Formula 1) {Total mass of epoxy compound (A) and acid anhydride (B) [(A) + (B)]} = [mass part of (A) + mass part of (B)] ÷ [(A) Mass part of + mass part of (B) + mass part of (C) (non-volatile matter)] × 100

(Calculation Formula 2) [Mass of polyol compound (C)] = [Mass part of (C) (non-volatile matter)] ÷ [Mass part of (A) + Mass part of (B) + Mass part of (C) (non-volatile matter) Volatile matter)]×100

<Molar ratio of easily adhesive layer components>

Of the epoxy compound (A) in the easily adhesive layer component of Examples 1-1 to 1-19, Comparative Examples 1-1 to 1-3, Examples 2-1 to 2-19, and Comparative Examples 2-1 to 2-3 The moles of the epoxy group and the acid group of the acid anhydride (B) are converted into the following calculation formulas 3 and 4, and the molar ratio {[epoxy group of (A)]:[acid group of (B)]} is shown in Tables 1 to 4, respectively. .

(Calculation Formula 3) [Number of moles of epoxy group of epoxy compound (A)] = [Part by mass of (A) ÷ Epoxy equivalent of (A)] ÷ [Part by mass of (A) ÷ Epoxy equivalent of (A) + (B) Part by mass ÷ Acid anhydride equivalent of (B)] × 100

(Calculation formula 4) [Number of moles of acid group of acid anhydride (B)] = [Mass part of (B) ÷ Acid anhydride equivalent of (B)] ÷ [Mass part of (A) ÷ Epoxy equivalent of (A) + (B) ) mass part ÷ acid anhydride equivalent of (B)] × 100

<Production of easily adhesive layer coated substrate>

The coating solutions of Examples 1-1 to 1-19, Comparative Examples 1-1 to 1-3, Examples 2-1 to 2-19, and Comparative Examples 2-1 to 2-3 are shown in Tables 1 to 8. On each base film described in , the easily adhesive layer thickness after solvent drying was respectively applied with Meyer bar so that it became the thickness shown in Tables 1 to 4. The substrate to which each easily adhesive layer coating liquid was applied was immediately heated in a gear oven at 120°C for 1 minute, solvent dried, and heat cured to obtain an easily adhesive layer coated substrate.

<Evaluation of hardenability of easily adhesive layer>

Surface of each easily adhesive layer coating substrate of Examples 1-1 to 1-19, Comparative Examples 1-1 to 1-3, Examples 2-1 to 2-19, and Comparative Examples 2-1 to 2-3 When the surface was rubbed with a finger five times, the surface condition and the transfer of easily adhesive layer components to the finger were visually confirmed and evaluated according to the following criteria. The evaluation results are shown in Tables 1 to 8, respectively.

○: No change in the surface of the coating film and no transitional components on the surface of the finger.

△: There is some whitening on the surface of the coating film, but there is no transitional component on the surface of the finger.

×: The surface of the coating film is whitened, and transitional components are also present on the surface of the finger.

In Comparative Example 1-3 and Comparative Example 2-3, the sclerosis evaluation of the easily adhesive layer was "×", and subsequent evaluation could not be performed.

<Evaluation of adhesion between substrate and easily adhesive layer>

Surface of the easily adhesive layer of each easily adhesive layer coating substrate of Examples 1-1 to 1-19, Comparative Examples 1-1, 1-2, Examples 2-1 to 2-19, and Comparative Examples 2-1 and 2-2 was rubbed with a finger, the adhesion between the base material and the easily adhesive layer was observed with the naked eye, and evaluated according to the following standards. The evaluation results are shown in Tables 1 to 8, respectively.

◎: No peeling from the substrate after 50 finger rubs.

○: Falling off from substrate after finger rubbing more than 10 times and less than 50 times

×: Falling off from the substrate occurs after finger rubbing less than 10 times.

<Production of adhesive film>

As the adhesive layer coating liquid, each material was mixed in the mixing ratio shown in Table 9 to produce adhesive layer coating liquids 1 to 3. Examples 1-1 to 1-19, Comparative Examples 1-1, 1-2, Examples 2-1 to 2-19, and Comparative Examples 2-1 and 2-2. Forming an easily adhesive layer on the coated substrate. The adhesive layer coating liquid shown in Tables 1 to 8 was applied to one side using an applicator so that the adhesive layer thickness after solvent drying was 10 μm. The substrate onto which each adhesive layer coating liquid was laminated was immediately heated in a gear oven at 150°C for 1 minute, solvent-dried, and heat-cured to prepare each adhesive film.

<Evaluation of adhesion between easily adhesive layer and adhesive layer>

From each of the adhesive films produced above in Examples 1-1 to 1-19, Comparative Examples 1-1 and 1-2, Examples 2-1 to 2-19, and Comparative Examples 2-1 and 2-2, horizontal and vertical A 50 mm sample was cut out, the cut cross section of the adhesive layer of the cut sample was rubbed with a finger, the adhesion between the easily adhesive layer and the adhesive layer was observed with the naked eye, and evaluated according to the following criteria. The evaluation results are shown in Tables 1 to 8, respectively.

◎: No peeling from the substrate after 15 finger rubs.

○: Finger rubbing occurs 5 times or more, but falls off from the substrate after 15 times or less.

×: There is separation from the substrate after finger rubbing less than 5 times.

<Production of rolled copper foil adhesive samples>

From each of the adhesive films produced above in Examples 1-1 to 1-19, Comparative Examples 1-1 and 1-2, Examples 2-1 to 2-19, and Comparative Examples 2-1 and 2-2, a width of 25 A sample of size 120 mm in length was cut, the adhesive layer side of the cut sample was attached to a rolled copper foil with a width of 50 mm, a length of 150 mm, and a thickness of 50 μm, and left at room temperature for 20 to 40 minutes for evaluation. was used as a sample with rolled copper foil attached. A total of 6 adhesive samples, 1 for flexibility evaluation and 5 for heat resistance adhesive residual evaluation, were produced from each adhesive film.

<Flexibility evaluation>

Adhesion of the rolled copper foil-attached samples of Examples 1-1 to 1-19, Comparative Examples 1-1 and 1-2, Examples 2-1 to 2-19, and Comparative Examples 2-1 and 2-2 produced above. When the film was peeled from the rolled copper foil at a speed of 300 mm/min in the 180 degree direction at room temperature, the occurrence of cracks in the easily adhesive layer of each adhesive film was visually confirmed and evaluated based on the following criteria. The evaluation results are shown in Tables 1 to 8, respectively.

○: No cracks occurred in the easily adhesive layer during peeling, and the layer could be easily peeled off.

△: Partial cracks occurred in the easily adhesive layer during peeling.

×: Cracks occurred on the entire surface of the easily adhesive layer during peeling.

<Evaluation of heat resistance and adhesive residue>

Five rolled copper foil-coated samples of Examples 1-1 to 1-19, Comparative Examples 1-1 and 1-2, Examples 2-1 to 2-19, and Comparative Examples 2-1 and 2-2 produced above. was placed in a gear oven at 175°C and subjected to heat treatment. For each of the five rolled copper foil-coated samples, one sheet was taken out after 2, 4, 6, 8, and 10 minutes, and left at room temperature for 5 minutes or more to cool. When the adhesive film of each heat-treated and cooled rolled copper foil-attached sample was peeled from the rolled copper foil at a speed of 300 mm/min in a direction of 180 degrees at room temperature, the presence or absence of adhesive residue on the rolled copper foil surface after peeling the adhesive film was visually observed. It was confirmed and evaluated based on the following criteria. The evaluation results are shown in Tables 1 to 8, respectively.

◎: No adhesive residue occurred at heat treatment at 175°C x 10 minutes.

○: Adhesive residue occurred after heat treatment at 175°C for 4 to 10 minutes.

×: Adhesive residue occurred after heat treatment at 175°C x 2 minutes.

<Confirmation of adhesion before and after heat treatment>

From the adhesive films of Examples 1-1 to 1-3 and Examples 2-1 to 2-3 (representative samples of adhesive layer coating solutions 1 to 3) produced above, a sample with a width of 25 mm and a length of 250 mm was obtained. was cut out, and the adhesive layer side of the cut sample was attached to a rolled copper foil with a width of 50 mm, a length of 120 mm, and a thickness of 50 μm, and was pressed from thereon with a 2 kg roller to produce an attached sample. Two of each of the above-mentioned attachment samples were produced, one side was left at 23°C and 50%RH for 30 minutes (before heat treatment), the other side was left at 23°C and 50%RH for 30 minutes, and then the gear was placed at 175°C. Heat treatment was performed by placing in an oven for 10 minutes, and additionally left at 23°C and 50%RH for 5 minutes (after heat treatment) were used as samples for measuring adhesion.

For the sample for measuring adhesion, in accordance with JIS Z0237: 2009, an adhesive film was prepared from rolled copper foil using a tensile tester in an environment of 23°C and 50%RH, at a peeling angle of 180 degrees and a peeling speed of 300 mm/min. The force at the time of peeling was measured, and this was taken as adhesive force (N/25 mm). The measurement results are shown in Tables 1 and 5.

1: Adhesive film
2: Description
3: Easily adhesive layer
4: Silicone-based adhesive layer
5: Separator

Claims (6)

An adhesive film in which a substrate, an easily adhesive layer, and a silicone-based adhesive layer are laminated on at least one side of the substrate in this order, wherein the easily adhesive layer includes a cycloalkene oxide-type alicyclic epoxy compound (A-i) and a glycidylamine-type epoxy. An adhesive film, characterized in that it is a cured product obtained by thermosetting a composition containing an epoxy compound (A), an acid anhydride (B), and a polyol compound (C) selected from the group consisting of compound (A-ii). According to claim 1,
An adhesive film, characterized in that the polyol compound (C) is a silicate hydrolyzate. According to claim 1,
An adhesive film, characterized in that the polyol compound (C) is acrylic polyol. According to claim 1,
An epoxy compound (A), an acid anhydride (B), and a polyol selected from the group consisting of cycloalkene oxide type alicyclic epoxy compound (Ai) and glycidylamine type epoxy compound (A-ii) forming the easily adhesive layer. In the composition containing compound (C), the mass ratio of the total mass of the epoxy compound (A) and the acid anhydride (B) and the mass of the polyol compound (C) {[(A) + (B)]: (C) An adhesive film characterized in that } is 10:90 to 90:10. According to claim 1,
An epoxy compound (A), an acid anhydride (B), and a polyol selected from the group consisting of cycloalkene oxide type alicyclic epoxy compound (Ai) and glycidylamine type epoxy compound (A-ii) forming the easily adhesive layer. In the composition containing compound (C), the molar ratio between the epoxy group of epoxy compound (A) and the acid group of acid anhydride (B) {[epoxy group of (A)]:[acidic group of (B)]} is 20: An adhesive film characterized in that the ratio is 80 to 80:20. According to claim 1,
An adhesive film, characterized in that the film thickness of the easily adhesive layer is 0.05 to 3.00 μm.