TW201235430A - Heat-curing resin composition, heat-curing adhesive sheet, and method for producing heat-curing adhesive sheet - Google Patents

Abstract

Provided is a heat-curing resin composition capable of removing bubbles in a short time from between a circuit and the joining surface of an adhesive sheet during hot-pressing. The heat-curing resin composition is characterized by having a tensile modulus of 105-106Pa during hot-pressing at between 150 and 180 DEG C. In addition, the heat-curing resin composition contains: an acrylic copolymer containing a vinyl monomer that contains an epoxy group; an epoxy resin; a curing agent for the epoxy resin; and an organic acid dihydrazide as the curing agent.

Description

201235430 VI. OBJECT OF THE INVENTION: TECHNICAL FIELD The present invention relates to a sturdy hardenability τ 曰 and a j... hardening modified resin composition containing a hardener for an acrylic copolymer epoxy resin, and a thermosetting connection : A method for producing a sheet and a thermosetting adhesive sheet. The present application claims priority on the basis of a Japanese patent application filed on November 29, the Japanese patent application, the disclosure of which is hereby incorporated by reference. In order to obtain good results: the human base polymer contains a buffer group and an epoxy group, and the acrylic group is a combination of a dithiol-containing acrylic polymer and an epoxy group-containing acrylic acid. :: The material contains a soluble (tetra) type bismuth resin and an epoxy resin as a hardening component. The manufacturer proposes a good adhesion force by using the special acrylic polymer, the soluble phenol-dust phenol resin and the epoxy resin, which can be low and low, and the pressure curing (hardening) of the dish and the time is good.荽 y , A + enemies (refer to Patent Document 1 and the patents described in Patent Field 1 and Patent Document 2, the composition of the film contains a large number of groups, an epoxy group, and a soluble (tetra) θ 4 Forming a three-dimensional network structure, the hardening anti-depositive storage at room temperature is gradually subjected to a moderate anti-cracking hardening reaction, and the storage property at room temperature is poor. The relationship between the circuit and the bonding surface of the bonding sheet is completely excluded in Patent Document 1 and Patent Document 2 In the subsequent composition, the bubble is removed between the faces of the 201235430 surface, and it takes a long time to press. [Patent Document 1] Japanese Patent Laid-Open No. 2007_9057 [Patent Document 2] 曰本特开 2〇〇7_9〇58号 SUMMARY OF THE INVENTION The present invention has been proposed in the above-mentioned prior art, and its object is to provide a short-term heat-pressable press. A method of producing a thermosetting resin composition, a thermosetting adhesive sheet, and a thermosetting adhesive sheet of a bubble between the bonding surface of the bonding film and the bonding sheet. The thermosetting resin composition of the present invention is 150 to 180. In the thermosetting adhesive sheet of the present invention, a thermosetting adhesive layer composed of the above-mentioned thermosetting resin or a composition is formed on the base film. The method for producing a thermosetting adhesive sheet of the invention has the following steps: a preparation step, a front epoxy group (IV), and a (4) from the organic I crucible, the hardener for the % oxygen resin is dissolved in an organic solvent, By using the enamel plant to further form a coating for forming an underlayer, the organic solvent containing an acrylic copolymer containing an epoxy group-containing monomer dissolved in an organic ridge agent; In the step of applying the coating for forming a thermosetting adhesive layer onto a substrate crucible and drying it, the tensile modulus of elasticity is 1 () 5 〜 i () when pressed at 15 Torr. 6 h of thermosetting adhesive layer. The heat of the invention When the resin composition is added at 150 to 180 ° C, the tensile modulus is 1 g 5 to iq 6 h, and the bubble between the circuit and the bonding surface of the bonding sheet can be removed during the time of adding (4). 201235430 [ [Embodiment] Hereinafter, an example of a specific embodiment of a thermosetting resin composition, a thermosetting adhesive sheet, and a method for producing a thermosetting adhesive sheet according to the present invention will be described with reference to the following drawings. Thermosetting resin composition 1-1. Acrylic copolymer 1-2. Epoxy resin 1 - 3 . Hardener 1 - 4 · Amine-based curing agent 2 · Method for producing thermosetting resin composition 3 · Heat Curing adhesive sheet 4: Method for producing thermosetting adhesive sheet 5. Other embodiment 6 · Example < 1 · Thermosetting resin composition> The thermosetting resin composition of the present embodiment is 150 to 180 < The tensile modulus of the t-heated temple is 1〇5~1〇6 Pa. Therefore, the bubble between the circuit and the bonding surface of the bonding sheet can be removed in a short time during the pressing to suppress the tensile elastic modulus of y, which is based on the test method of dynamic mechanical properties of jisk7244_4 plastic. The value measured by Nai (stretching vibration). When the tensile elasticity of the thermosetting resin composition is less than 1 〇 5 Pa, the viscous stalk of the composition of the thermosetting tree is reduced after the heating and pressing, and the air is easily connected from the circuit. It enters between the mouths of the mouth, so it takes a long time to completely eliminate the bubbles. The tensile modulus of the composition of the curable resin composition is large. When %, the viscosity of the thermosetting resin composition of 201235430 becomes high, and it takes a long time to completely eliminate the bubbles existing between the circuit and the bonding surface of the bonding sheet. The thermosetting tree a composition includes, for example, an acrylic copolymer containing an epoxy group-containing ethylenic monomer, an epoxy resin, and an organic acid diterpene which is a curing agent for an epoxy resin. <1 -1. Acrylic copolymer> The acrylic copolymer is used to impart film formability when the film is formed, and to impart flexibility and toughness to the cured product. The acrylic copolymer is, for example, obtained by copolymerizing an epoxy group-containing vinyl monomer, an acrylonitrile monomer, or an epoxy group-free monomer. <Epoxy group-containing vinyl monomer> The epoxy group-containing vinyl single system is used for reacting with an epoxy resin hardener to form a three-dimensional crosslink in a hardened thermosetting resin composition. structure. When the three-dimensional crosslinked structure is formed, the moisture resistance and heat resistance of the cured product can be improved. For example, even a reinforced flexible printed wiring board composed of a reinforced resin sheet which is cured with a thermosetting resin composition and then fixed to a flexible printed wiring board is subjected to a soldering process (for example, reflow soldering). When it is treated, it is also prevented from swelling due to moisture absorption in the subsequent fixing portion. As such an epoxy group-containing vinyl monomer, it can be self-applied to the prior acrylic thermosetting property in the field of electronic parts. The user of the agent is appropriately selected and used, and examples thereof include glycidyl acrylate (GA), glycidyl methacrylate (hereinafter referred to as "GMA (giycidy! methacrylate)"), methyl glycidyl acrylate, and olefin. Propyl glycidol 201235430, etc. Among these epoxy group-containing vinyl monomers, GMA is preferably used from the viewpoint of safety and easy availability on the market. Further, it contains an epoxy group. The monomers may be used singly or in combination of two or more. If the amount of the vinyl monomer containing the epoxy resin in the total monomer used in the preparation of the acrylic copolymer is too small, If the amount is too small, the peel strength tends to decrease, and it is preferably 1 to 1% by mass. <Acrylonitrile monomer> The acrylonitrile single system is used for improving heat resistance. For example, as a propylene guess The acrylonitrile monomer and the acrylonitrile monomer may be used singly or in combination of two or more kinds. The amount of propylene monomer in the total monomer used in the preparation of the acrylic copolymer is exemplified. If the amount is too small, the heat resistance is lowered. If the amount is too large, it is difficult to dissolve in the solvent. Therefore, it is preferably 20 to 35 mass%, more preferably 25 to 3 parts by mass, and no epoxy group. (Acrylate) Monomer> As an epoxy group-free (fluorenyl) acrylate monomer, it can be appropriately selected from users of previous acrylic heat-curing adhesives used in the field of electronic parts. Further, as the epoxy group-free (meth) acrylate monomer, for example, decyl acrylate (MA ), ethyl acrylate (EA), n-propyl acrylate, n-butyl acrylate, and butyl acrylate may be mentioned. Ester, n-hexyl acrylate, n-octyl acrylate, isooctyl acrylate Acrylic acid 2_B, W witch C* 0, isodecyl acrolein, stearyl acrylate, decyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, N-hexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, 2·ethylhexyl methacrylate, isodecyl methacrylate, methyl acrylate is 201235430 dialkyl vinegar, 曱Isodecyl methacrylate, stearyl methacrylate. Among these epoxy group-free (meth) acrylate monomers, butyl acrylate is preferably used. The ester or the ethyl acrylate may be used alone or in combination of two or more. When the amount of the monomer of the epoxy tree is too small, the basic characteristics are lowered. If the amount is too large, the heat resistance tends to decrease, so that it is preferably 6 〇 to 7.5 mass%. <Weight average molecular weight> When the weight average molecular weight of the acrylic copolymer is too small, the peel strength and the heat resistance are lowered. When the weight is too large, the solution viscosity is increased and the coatability tends to be deteriorated. Therefore, the weight average molecular weight of the acrylic copolymer is preferably from 500,000 to 700,000. <Glass Transfer Temperature> The thermosetting resin composition can adjust the tensile elastic mold 35 by the glass transition temperature (Tg) of the acrylic acid copolymer. For example, the glass transition temperature of the acrylic copolymer is preferably -4.5. (: 〜2 (the range of rC. < 1 - 2. Epoxy resin) The epoxy resin constituting the thermosetting resin composition is used to form a three-dimensional network structure, and the adhesion is good. The resin and T are appropriately selected and used from the liquid ring or the solid epoxy tree used in the resin-based thermosetting adhesive used in the shell of the electronic component. For example, bisphenol a Type epoxy resin, phenol F type epoxy resin, bisphenol AD type epoxy resin, hydrogenated bisphenol a type epoxy tree, benzene (four) varnish type epoxy resin, A ray varnish type ring

S 8 201235430 Oxygen resin, polyalkylene polyol (neopentylene glycol, etc.) polyglycidyl ether, tetraglycidyldiamine diphenyl fluorene, triglycidyl-amino benzene, diglycidyl Base-m-aminoamine, tetraglycidyl-m-diphenylene diamine, diglycidyl phthalate, hexa-argon phthalate diglycolic acid, tetrahydrophthalic acid diglycidyl Series, vinyl cycl〇hexene dioxide, 3,4-epoxycyclohexane decanoic acid 3,4_epoxycyclohexyl decyl ester, adipic acid bis (3,4-epoxy _ 6_decylhexyl decyl) ester and the like. These epoxy resins may be used alone or in combination of two or more. When the amount of the epoxy resin used is too small, the heat resistance is lowered. If the amount of the epoxy resin is too large, the adhesiveness tends to decrease. Therefore, it is preferably 5 to 30 parts by mass, more preferably 1 part by mass, based on 1 part by mass of the acrylic copolymer. 1〇~2〇 parts by mass. < 1 - 3. Curing agent> The thermosetting resin composition contains an organic acid diterpene as a curing agent for an epoxy resin. By using the organic acid diterpene as a curing agent, the room temperature storage property of the thermosetting resin composition which is solid at normal temperature can be improved. It is preferred that the organic acid diterpene has an average particle diameter of 〇 5 to 15 μm ' and is uniformly dispersed. When the average particle diameter of the organic acid diterpene is less than 55/im, there is a possibility that the organic acid diterpene particles are dissolved when the organic solvent for coating the thermosetting resin composition is used. , the storage at room temperature is reduced. If the average particle diameter of the organic acid diterpenoid is more than 15" m, the coating property of the thermosetting resin composition is lowered, and it is impossible to melt with the C' dilute acid polymer or the epoxy resin due to the large particle size. Fully mixed. The organic acid dihydrazine can be appropriately selected from the organic dicesium which has been previously used as a hardener for epoxy resins. For example, bismuth oxalate, two 201235430 diterpene diacetate, diterpene succinate, diimine diacetate, diammonium adipate, diammonium pimelate, xin Bismuth diacid, diterpene sebacate, didecane dihydrazide, dodecane dihydrazide, diammonium hexadecandioate, diammonium maleate , antimonic acid diterpene, diglycolic acid diterpene, divalent tartrate, diterpene malate, diammonium isophthalate, diterpene terephthalate, 2,6_ Diterpene naphthoate, 4,4'-bisphenylhydrazine, iota, 4-naphthoic acid dioxime, Amicure VDH, Amicure UDH (trade name, manufactured by Ajinomoto Co., Ltd.), triterpene citrate, 7,11 - octadecadiene _ 1,1 8-bicarbon oxime, and the like. The organic acid diterpenoid may be used singly or in combination of two or more. Among these organic acid diterpenes, from the viewpoint of relatively low melting point, excellent balance of hardenability, and easy availability, it is preferred to use diammonium adipate or 7,11-octadecadiene. _ 1,1 8 _ two carbon 醯肼. When the amount of the curing agent used is too small, the unreacted epoxy group remains and the crosslinking is insufficient, so that heat resistance and adhesion are lowered. Further, when the amount of the curing agent used is too large, an excessive amount of the curing agent remains unreacted, and the heat resistance and the adhesion tend to be lowered. Therefore, the amount of the hardener to be used is preferably 2 parts to 2 parts by mass based on the total mass of the acrylic copolymer and the epoxy resin. < 1-4. Amine curing agent> In the sexually resistant composition, the epoxy group of the acrylic copolymer is partially crosslinked by an amine hardener. By partially crosslinking the decyloxy group of the acrylic copolymer in the thermosetting resin composition by the amine-based curing agent, the tensile elastic modulus can be adjusted to 1 〇 5 to 1 〇 6 as described above. 10 201235430

Pa. The amine-based hardener is preferably liquid in view of the fact that the epoxy resin is hardened at room temperature. The amine-based curing agent may, for example, be a liquid polyamine or a polyamine amine, and specifically may be a chain aliphatic aliphatic amine or a cyclic aliphatic polyamine which is an aliphatic polyamine. Examples of the chain aliphatic polyamine include diethylenetriamine, triamethylenediamine, tetraethylenepentamine, triethylenetetramine, dipropylenediamine, and diethylaminopropylamine. Examples of the cyclic aliphatic polyamine include menthane diamine and isophorone diamine. In the case where the epoxy group partially crosslinked in the acrylic copolymer is small, the tensile elastic modulus becomes poor. Further, in the case where a large number of epoxy groups are crosslinked in the acrylic copolymer, there is no problem in the tensile modulus of elasticity, but the storage property at room temperature is deteriorated. The ratio of the cross-linking of the epoxy group can be confirmed, for example, by observing the peak of heat generation in DSC (Differen Uai Scanning Cal〇rimetry) measurement. As described above, the thermosetting resin composition of the present embodiment is to be 150 to 180. (: The tensile elastic modulus at the time of heating pressing is set to 1〇5 to 1〇6 Pa', and the air bubbles between the circuit and the bonding surface of the bonding sheet can be eliminated in a short time during the heating pressing. Thereby, the step time can be shortened In addition, the thermosetting resin composition of the present embodiment contains an organic acid diterpene as a curing agent, and therefore has excellent storage stability at room temperature, and requires no equipment such as a freezer, and the operation such as transportation and storage is extremely Further, since the thermosetting resin composition of the present embodiment has excellent adhesive strength, it can maintain high adhesion to the polyimide film and the metal sheet. Further, the thermosetting resin composition of the present embodiment Since the moisture-absorbing soldering 201235430 is excellent in heat resistance, it is possible to make the good-time reflow property good at the time of wearing it even under high humidity such as summer. 2. 2. Method for producing thermosetting resin composition> The thermosetting resin composition of the form can be prepared by mixing an acrylic copolymer, an epoxy resin, a curing agent, and an amine curing agent by a usual method. The mixer mixes the acrylic copolymer and the amine-based curing agent dissolved in the organic solvent, and after mixing, a predetermined amount of the epoxy resin and the curing agent are added to the organic solvent to prepare the thermosetting property. In the form of a thermosetting resin composition, a paste, a film, a dispersion liquid, etc. may be mentioned. <3> Thermosetting adhesive sheet> A thermosetting adhesive sheet is, for example, a base. A thermosetting adhesive layer composed of the above-mentioned thermosetting resin composition is formed on the material film (release base material). The base film can be exemplified by a polystyrene film. Polyimine film, etc. The thermosetting adhesive sheet has a thickness of 1 〇A m from the thermosetting resin composition, and the S-curable adhesive layer composed of the thermosetting resin composition, in terms of storage property and handling property at the time of use. The film is formed on a base film obtained by peeling off a polyethylene terephthalate film or a polyimide film, such as polyoxazine, etc. as needed. 4. A method for producing a thermosetting adhesive sheet &gt; Chemical ΓΓΓ ΓΓΓ 片The method for producing a thermosetting coating 2 comprises the steps of preparing a layer for forming a thermosetting adhesive layer and the thermosetting property for forming a thermosetting adhesive layer. Next, in the preparation step, ;1丨$ I + into the heat hardening (4) 4 machine (four) minus the way to cast: 3, 'and do not' and disperse the hardener in the organic solvent, so that = '= material and epoxy resin dissolved in the organic solvent, thereby Preparation: coating for layer formation. For example, methyl ethyl ketone, toluene or the like can be used as the organic solvent. In the preparation step, it is preferred that the total organic acid diterpene particles are dissolved in solid particles at room temperature. The formation of the thermosetting adhesive layer can improve the room temperature storage property of the curable adhesive sheet. In the thermosetting adhesive layer forming step, a bar coater, a pro-: cloth machine, or the like is used in the preparation step. The prepared thermosetting adhesive layer-forming coating material is applied onto a base film so as to have a dry thickness of 10 to 5 Mm, and dried by a usual method to form a thermosetting adhesive layer. Thereby, a thermosetting adhesive layer sheet can be obtained. The above thermosetting resin composition and thermosetting property sheet can be preferably used, for example, in the field of electronic parts. In particular, the 'thermosetting adhesive sheet can be preferably used to fix the terminal portion of the flexible printed wiring board, and the like, and the polyethylene terephthalate, polyimide, and epoxy glass used as the lining thereof. , stainless steel, and other reinforcing resin sheets with a thickness of 50/zm to 2 mm. In this way, the terminal portion of the flexible printed wiring board and the reinforcing resin sheet are bonded together by the heat-curable adhesive layer of the thermosetting adhesive layer of the substrate which is removed by the curable adhesive layer t of the present embodiment. The flexible printed wiring board is reinforced. &lt;5. Other Embodiments&gt; In the above description, a part of the epoxy group in the acrylic copolymer is crosslinked by an amine-based curing agent, and will be 15〇~i8〇&lt;&gt;c Heating 13 201235430 The tensile elastic modulus at the time of pressing is set to 105 to 106 Pa, but is not limited to this example. For example, the glass transition temperature of the acrylic copolymer or the weight average molecular weight of the acrylic copolymer may be adjusted without using an amine-based hardener, and the tensile elastic modulus obtained when heated at 150 to 1801 may be 1 05 to 1 06 Pa thermosetting resin composition. [Examples] Hereinafter, specific examples of the invention will be described. Further, the scope of the present invention is not limited to the following embodiments. (Material) • Acrylic copolymer butyl acrylate (BA), ethyl acrylate (EA), acrylonitrile (AN), GMA, acrylic acid (AA), 2-hydroxyethyl methacrylate (HEMA) • epoxy resin JER806, JER1031S (all manufactured by Mitsubishi Chemical Corporation) • Hardener 7,11-octadecadiene-1,18-dicarbenium (1^11) • Amine-based hardener for pre-crosslinking Mixture of ethylenetetramine and its modified material (preparation of coating for thermosetting adhesive layer formation) In Examples 1 to 4, Example 6 and Comparative Example 4, the solution was dissolved in an organic solvent in such a manner as to achieve the composition of Table 1. The mixture of the acrylic copolymer and the triamethylenetetramine and the modified product thereof as an amine-based curing agent was mixed by a stirrer (DISS〇LVER, manufactured by Asada Iron Works Co., Ltd.) for 2 hours. After the mixing, a predetermined amount of the epoxy resin 14 201235430 is used as an adhesive solution (thermosetting grease or curing agent to prepare an apparent resin composition). Further, in Table 1, the unit of the addition amount of each compound is the unit of mass in parts by mass.

Follow the solution.

In Comparative Example 2, an adhesive solution having the composition shown in Table 1 was produced in the same manner as in Comparative Example 5 and Comparative Example 3, except that 2-hydroxyethyl methacrylate was used instead of the acrylic acid as the acrylic copolymer. (Production of thermosetting adhesive sheet) The obtained coating material for forming a thermosetting adhesive layer is applied onto a polyethylene terephthalate film subjected to a release treatment in a drying oven of 50 to 130 lt. The thermosetting adhesive sheet of the known examples 1 to 5 and the comparative examples 1 to 4 was produced by drying to form a thermosetting adhesive layer having a thickness of 35 mm. 15 201235430 •ss ·- 0.9Ζ ·0 91 0- 0. Bu 0- οτ 0800 ττ - 03 OK Ρ09ζ - 91 03 02 Ρ092 〇 roi

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(Umbrella reward) VW3H (φί 驷) 908^3⁄43⁄4 rate ^ϊί (甶驷1) Sls53f-Walk ^fi (ετζ)^4Ηαη I Intercept and 哿(IN)^ (§/M) Target error - (2 (3. 0-) 鹚趄 鹚趄 幸 4 201235430 (About tensile elastic modulus) The tensile elastic modulus of each of the thermosetting adhesive sheets was measured under i 7 。. The results are shown in Table 1. (Repression test) In the press S test, Vacuum Star (manufactured by Mikad 〇 Technos Co., Ltd.) was used as a vacuum press. The pressing conditions were set to the pressing temperature: 丨7〇(&gt;c, pressing pressure.1·8 MPa, pressing time: vacuum holding time 丨〇s. As shown in Fig. 1A, the heat according to the composition of the watch was blended. The sclerosing adhesive layer 2 was laminated on the polyimine film 1 as a reinforcing plate at 100 C, 1 m/min, and 5 kg/cm to obtain a laminated sample 3. Next, as shown in Fig. 及β and Fig. 1C As shown, the laminated sample 3 is stamped into an evaluation Fpc (

The film for evaluation (reinforcing plate/thermosetting sheet sample) 4 was prepared in the same size as the reinforcing portion of the Printed Circuits 'flexible printed wiring board. As shown in Fig. 1D, the stamped evaluation film 4 was attached to a single-sided FPC 5 as an evaluation FPC. As shown in FIG. 1D and FIG. 2, the single-sided FPC 5 is a single-sided CCL (copper clad laminate) having a thickness of 56 m and a thickness of 45 am provided on one side of the single-sided CCL 8. A cover layer (cover film) 7 is formed. The single-sided CCL 8 is formed by laminating a copper foil 6 having a thickness of 18"111 and a polyimide film 9 having a thickness of 25# through a thickness of the bonding layer U of the thickness i3. As shown in Fig. 1E, an optical microscope 10 is used. The subsequent portions of the reinforcing plate after pressing under the above conditions were confirmed to confirm the presence or absence of air bubbles. The shortest time from the start of pressing to the complete disappearance of the bubbles was taken as "pressing time (bubble exclusion)" in Table 1, and in Table 1, The pressing time is "〇17 201235430, which means that the pressing time is 45 seconds or less, and the pressing time is Γχ", which means that the pressing time exceeds 45 seconds. (Evaluation of Peel Strength) The evaluation of the peel strength was carried out as follows. The heat-hardened material that has just been obtained is cut into short strips of the specified size (5 cm χ 1 〇 〇 claw). The usage is set to 80. (The iaminator is a thermosetting adhesive layer in which a thermosetting adhesive sheet cut into a short strip is temporarily attached to a 175 μm polyimine film (175AH, manufactured by Kaneka Co., Ltd.) The base film is removed to expose the thermosetting adhesive layer. The exposed thermosetting adhesive layer is formed by superposing a 5 〇v claw thick polyimine film (200H, which is the same size as the thermosetting adhesive sheet from above). DUPONT company), after heating and pressurizing for 6 sec at a pressure of 2 〇 MPa for 6 sec, and keeping it in a 14 〇t: oven for 6 。 minutes. Also 'will be cut into short strips (5 cmX.10 cm) The thermosetting layer of the thermosetting adhesive sheet is temporarily adhered to a SUS3〇4 plate of 〇5 mm or a glass epoxy board having a thickness of 1 mm, and then the base film is removed to form a thermosetting adhesive layer. Exposed. For the exposed thermosetting adhesive layer, a short strip of 50 μm thick polyimine film (5 cmxi〇cm) was superposed on top, and heated at a pressure of 2_0 MPa for 60 seconds at 17 〇&lt;t. After that, it was kept at 140. (: oven for 60 minutes. Thereafter) at a peeling speed of 50 mm/min for the polyimide film. The 9-degree peel test was performed to determine the force required for peeling. The results obtained are shown in Table i. The peel strength is expected to be 1 〇N/cm in practical applications. (Hygroscopic back-weld heat resistance test) 201235430 The reflow soldering heat resistance test was carried out in the following manner. The thermosetting adhesive layer of the thermosetting adhesive sheet cut into short strips (2 cm x 2 cm) was temporarily attached to the crucible 7 by a bonding machine set at 80 °C. After a 5 μm-thick polyimide film (Apical 175AH, manufactured by Kaneka Co., Ltd.), the peeling base material was removed to expose the thermosetting adhesive layer. The exposed thermosetting adhesive layer was superposed on the same size from above. Polyimide film with a thickness of m thick (Kapton 2, manufactured by Dup〇NT Co., Ltd.) was heated and pressurized at i7〇〇c for 2 seconds, and kept at 6 于 in an oven of 140°. After that, the heat-hardened test piece was placed in a humidified oven of 9 〇RH for 96 hours. The test piece after the heat treatment was just set to the maximum temperature of 26 (the rc mesh furnace was visually observed). The subsequent test pieces have: an abnormal view, and the results are shown in Table 1. Table: moisture absorption back welding::: 260C Pass" indicates that the appearance is completely absent. The heat resistance of the weld is ^. c Ne" is expressed in the test piece "brother and;; the swelling caused by the bubble. From the hair (related to the storage temperature), the pipe was tested for the following properties. In Table 1, the normal temperature--: 丄 refers to the initial peel strength of each thermosetting film: In the comparison of the three rides, the rate of decrease in peel strength is not 30%. Brother: Although the rate of decrease in peel strength is not..., the heat resistance of the joint is evaluated as good (the above "26〇 The heat-resistance of the moisture absorption and heat-receiving of the moisture absorption and back-to-back after the normal temperature and the month after the storage of the mouth and the wet storage for 3 months (the above "26〇19 201235430 t NG") The sheet was evaluated as "△" because it was markedly changed in the room temperature. EXAMPLES The thermosetting sheet obtained in Example 6 had a tensile modulus of elasticity of ～35 χΐ〇 5 h at 15 when heated under HC heating. ~ The tensile modulus of elasticity when heated to waste is ι〇5~2=condition. Therefore, the pressing time of the thermosetting adhesive sheet obtained in the 'Example 丨 to the fifth embodiment at the time of heat pressing is 2 G to 4 G seconds, and can be between the joint surface of the heat-dissipating film and the thermosetting adhesive sheet in a short time. Bubbles... In fact: Example! In the thermosetting adhesive sheet obtained in Example 5, the evaluation of the film at room temperature storage, the peel strength, and the moisture absorption back welding heat test were also good. The thermosetting adhesive sheet obtained in Comparative Example 1 was subjected to i7 〇 (&gt;c, the tensile elastic modulus at the time of pressing and pressing was 7.0 χ...Pa', so that the circuit and the heat hardening were eliminated in a short time when the heating was not performed. Further, the thermosetting adhesive sheet obtained by the above-mentioned sheet has a poor hyalurability at room temperature. The thermosetting sheet obtained in Comparative Example 2 is heated at i7〇t. When the pressing elastic modulus at the time of pressing was 6.5 x 1 G &gt; a, the bubbles between the joint surface of the circuit and the thermosetting adhesive sheet were not removed in a short time during the heating press. Further, the heat obtained in Comparative Example 2 Since the curable adhesive sheet contains gma, it has poor storage stability at room temperature. The thermosetting adhesive sheet obtained in Comparative Example 3 is i 7 〇. The tensile elastic modulus at the time of heating and pressing is 7_〇xl 04 pa, so The bubble between the circuit and the joint surface of the thermosetting adhesive sheet can be removed in a short time during the heating press. The thermosetting adhesive sheet obtained in Comparative Example 4 is on ι 7 (Γ: heating press

20 201235430 The tensile modulus of elasticity is 6_〇xl o4 Pa, so that bubbles between the circuit and the joint surface of the thermosetting adhesive sheet are not removed in a short time during the heating press. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1A to Fig. 1E are diagrams showing the steps of a method of pressing test. Figure 2 is a schematic cross-sectional view showing a sample used in a compression test. [Main component symbol description] 1 Polyimine film 2 Thermosetting adhesive layer 3 Laminated sample 4 Evaluation film

5 single-sided FPC 6 copper foil 7 cover layer (cover film)

8 single-sided CCL 9 polyimide film 10 optical microscope 11 subsequent layer 21

Claims (1)

201235430 VII. Patent application scope: 1. A thermosetting resin composition, 150~180. (The tensile elastic modulus at the time of heat pressing is 1〇5 to 106 Pa. 2. The thermosetting resin composition of the first aspect of the patent application contains: an acrylic acid containing an epoxy group-containing vinyl monomer a copolymer, an epoxy resin, and a hardener for the epoxy resin, wherein the hardener contains an organic acid diterpene. 3. The thermosetting resin composition of claim 2, wherein 'relative to 1 part by mass of the acrylic copolymer contains: 60 to 75 parts by mass of the epoxy group-free acrylate monomer, 20 to 35 parts by mass of the acrylonitrile monomer, and the epoxy group-containing vinyl monomer 1 to The heat-curable resin composition of the second or third aspect of the patent application, wherein 'the mass of the epoxy resin is blended with 1 to 20 masses per 1 part by mass of the acrylic copolymer. 5. The thermosetting resin composition according to claim 2 or 3, wherein 'the mass of the organic acid is 1 〇 2 〇 2 相对 with respect to 1 〇〇 by mass of the acrylic copolymer 6. If the thermostable tree of claim 2 or 3 is applied for. a composition, wherein 'the organic acid diterpene has an average particle diameter of 0.5 to 5 μm and is uniformly dispersed. 7 · The thermosetting resin composition of the second or third aspect of the patent application, 22 201235430 wherein 'the acrylic acid The epoxy group in the copolymer is partially crosslinked by an amine hardener. 8. The thermosetting adhesive sheet is formed on the substrate film by any one of the claims ii 7 A thermosetting resin composition having a hardenable adhesive layer. ' 9. A method for producing a thermosetting adhesive sheet, comprising the steps of: preparing a step: making a ring f [fu + 匕 ^ β ^ The cerium and the hardener for the epoxy resin containing at least one selected from the group consisting of diterpenoids of the organic acid are dissolved therein to prepare a thermosetting layer, and the coating material for forming the erbium is prepared. The organic solvent contains a combination of @ „ an acrylic copolymer of the early base of the clothing base; and a step of forming the adhesive layer: the thermosetting layer is formed on the substrate film and dried, thereby forming At 15.~ Town heating suppression Tensile modulus w~iq6 23