JP2010171296A - Coverlay film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coverlay film which is intended for a tape carrier for a semiconductor device in which a wiring layer having a predetermined pattern is formed on a surface of a resin tape and a semiconductor chip mounting part is formed at a predetermined position and which has excellent flame retardancy and superior workability, and small curl variation due to a processing environment. <P>SOLUTION: The coverlay film is characterized that it includes an adhesive layer, containing a polyamide resin including a dimer acid residue and an organophosphorus compound, on a halogenated alamid film having a moisture absorption expansion coefficient of ≤20 ppm/%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a coverlay film. More specifically, a tape automated bonding (TAB) pattern processing tape used for mounting a semiconductor integrated circuit (IC), a substrate for connecting a semiconductor device such as an interposer for a ball grid array (BGA) package, copper The present invention relates to a coverlay film for electronic parts suitable for producing a tension laminate and the like.

  A flexible printed wiring board is a circuit forming substrate with excellent flexibility composed of a support film, an adhesive, a conductor layer for circuit formation, etc., and a cover composed of a solder resist of liquid resin or an adhesive and a support film After the formed conductor circuit layer is protected by the ray film, the wiring board is widely used as an interposer for various wiring routings and IC mounting of electronic devices.

  Now that various electronic parts are being developed along with the spread of electronic devices, flexible printed wiring boards and coverlay films are also required to satisfy a number of high requirements and safety improvements according to the application site. It has been. In particular, the coverlay film used for interposers for IC mounting is not only flame retardant required for general circuit boards, but also durability against exposure to various heat histories and process chemicals in the manufacturing process, and processing Suppressing the curl amount, which has a large effect on accuracy, is a major issue.

  A resin composition containing a brominated phenoxy resin, an epoxy resin, a curing agent, a curing accelerator, and a silane coupling agent has been proposed as a resin composition for a coverlay film having excellent flame retardancy (for example, Patent Document 1). reference). In addition, in response to recent demands for reducing environmental impact and improving safety, a composition containing a phosphoric ester amide flame retardant, a non-halogen thermosetting epoxy resin, a non-halogen elastomer and a non-halogen inorganic filler is used as an adhesive. A coverlay film to be used has been proposed (see, for example, Patent Document 2). However, the coverlay films using these conventionally known adhesives are insufficient in chemical resistance in use forms that are continuously exposed to acids, alkalis, etc. during the product lifetime, and are laminated on the circuit. In doing so, there was a problem in workability, such as the need for reduced-pressure pressing.

  In addition, in a tape carrier for a semiconductor device in which a wiring layer having a predetermined pattern is formed on the surface of the resin tape and a semiconductor chip mounting portion is formed at a predetermined position, it is proposed to attach a film-like cover material. An aramid resin is disclosed as a material (see, for example, Patent Document 3). Moreover, as an ultra-thin coverlay film having good bending characteristics and bending characteristics, a coverlay having an adhesive layer containing a filler having an average particle size of 10 μm or less on one surface of an aramid resin film having a thickness of 3 to 10 μm. A film has been proposed (see, for example, Patent Document 4). In addition, in order to improve the bending resistance of the flexible printed wiring board, a flexible printed wiring board is proposed in which the elastic modulus of the outer resin film of the first outer insulating layer that becomes the outer side when bent is 6 GPa or more. An aromatic polyamide resin is disclosed as a material for the above (for example, see Patent Document 5). However, these conventionally known coverlay films have a problem that the processing accuracy is significantly affected by the processing environment, such as a large amount of dimensional change with respect to humidity and a significant change in the amount of substrate curl.

JP 2001-098243 A JP 2005-015595 A JP 2002-198401 A JP 2005-235948 A JP 2006-310443 A

  An object of the present invention is to provide a coverlay film which is excellent in flame retardancy and processability and has little change in curl amount depending on the processing environment.

  In order to solve the above problems, the cover lay film of the present invention is characterized by having an adhesive layer containing a polyamide resin having a dimer acid residue on a halogenated aramid film.

  According to the present invention, it is possible to obtain a coverlay film that is excellent in flame retardancy and workability and has little change in curl amount due to the processing environment. The electronic component using the cover lay film of the present invention can achieve both workability and processing accuracy.

  Hereinafter, the present invention will be described in detail.

  The coverlay film of the present invention has an adhesive layer containing a polyamide resin having a dimer acid residue on a halogenated aramid film.

  The coverlay film of the present invention is characterized in that the adhesive layer contains (A) a polyamide resin having a dimer acid residue. Dimer acid is industrially a dibasic acid in the highest molecular weight region, and has a bulky hydrocarbon group and thus has a high hydrophobicity. Therefore, the dimer acid polyamide resin derived from dimer acid is tough and flexible due to its low crystallinity, and is an organic solvent necessary for realizing the coverlay film of the present invention while maintaining low water absorption. It has the solubility of. Furthermore, it has hydrolysis resistance and flame retardancy derived from the strong binding force of the amide bond. Therefore, by using a polyamide resin having a dimer acid residue, the flame retardancy and chemical resistance required for a coverlay film can be improved, and the absolute value of the curl amount can be reduced. A polyamide resin having a dicarboxylic acid residue having 36 carbon atoms is preferable in terms of toughness, film-forming property and processability. If it is a polyamide resin which has a dimer acid residue, a well-known various thing can be used and you may use 2 or more types.

  A polyamide resin having a dimer acid residue can be obtained by polycondensation of dimer acid and diamine by a conventional method. At this time, dicarboxylic acid other than dimer acid, azelaic acid and sebacic acid are used as copolymerization components. You may contain. As diamine, well-known things, such as ethylenediamine, hexamethylenediamine, and piperazine, can be used, and two or more kinds may be used.

  In the present invention, the amine value of the polyamide resin having a dimer acid residue is preferably 0.5 or more and 10 or less. The amine value here means the mg quantity of potassium hydroxide equivalent to hydrochloric acid required for titrating 1 g of polyamide resin. When two or more kinds of polyamide resins are contained, the amine value indicated by the mg quantity of potassium hydroxide equivalent to hydrochloric acid required for titrating 1 g of a resin mixture in which each polyamide resin is mixed at a content ratio in the adhesive layer. Point to. If the amine value is 0.5 or more, the crosslinking density of the adhesive layer is increased, and the chemical resistance of the obtained coverlay film to the alkali solution or organic acid mixture is further improved. If the amine value is 10 or less, it becomes possible to reduce the absolute value of the curl amount of the wiring board obtained after processing.

  (A) The polyamide resin having a dimer acid residue preferably has a melt viscosity at 190 ° C. of 10 Pa · s or more. If the melt viscosity at 190 ° C. is 10 Pa · s or higher, the excellent processability of the resulting coverlay film will be further improved, and not only will it be possible to process in a shorter time, but also the margin for processing conditions will be improved. , More stable processing becomes possible. Further, the melt viscosity at 190 ° C. is preferably 190 Pa · s or less. If the melt viscosity at 190 ° C. is 190 Pa · s or less, it is not necessary to perform processing at a high temperature during processing, so that it is possible to minimize the thermal deterioration of the conductor circuit. Here, the melt viscosity at 190 ° C. can be measured by an apparent viscosity measurement described in JIS K7210-1999, Annex C. When two or more kinds of polyamide resins are contained, the measurement is performed using a resin mixture in which each polyamide resin is mixed at a content ratio in the adhesive layer.

  The (A) polyamide resin having a dimer acid residue preferably includes a polyetheramide resin. The polyetheramide resin is highly flexible even when the molecular weight is increased, and the absolute value of the curl amount of the wiring board obtained after processing can be reduced.

  The adhesive layer of the present invention preferably contains (B) an organophosphorus compound. The cover lay film according to the present invention includes (B) an organophosphorus compound, whereby not only the flame retardancy required for the wiring board to which the cover lay film is applied can be improved, but also (A) dimer Since it has a plasticizing action on the polyamide resin containing acid residues, it is possible to optimize the melting characteristics of the adhesive layer required when processing the coverlay film.

  (B) The organic phosphorus compound is not particularly limited as long as it does not contain a halogen and has one or more phosphorus atoms in the unit molecule, but a phosphate ester compound or a phosphazene compound is preferably used. In particular, the phosphazene compound is preferably used because it contains a phosphorus atom and a nitrogen atom in the molecule, and thus has a higher effect of imparting flame retardancy to the obtained coverlay film, and is excellent in water resistance and chemical resistance. It is done.

  In addition, (B) the organophosphorus compound has at least one reaction selected from the group consisting of a hydroxyl group, a glycidyl group, a vinyl group, an acrylonitrile group, an amino group and a carboxyl group in order to achieve both plasticity and flame retardancy at a higher level. It preferably has a functional group. Two or more types of (B) organophosphorus compounds having different reactive groups may be contained, or (B) organophosphorus compounds having reactive groups and (B) organophosphorus compounds having no reactive groups are combined. Also good. In particular, a hydroxyl group is preferable because it has an excellent balance between plasticity and flame retardancy, and can obtain higher chemical resistance while maintaining high workability due to the plastic effect.

The phosphoric acid ester compound is esterified using an additive type phosphate ester such as triphenyl phosphate or cresyl diphenyl phosphate, or a polyhydric phenol such as resorcin, and a monohydric phenol such as phenol or cresol. Among them, there can be mentioned a reactive phosphate ester in which at least one hydroxyl group remains as a reactive free radical, and a condensed phosphate ester obtained by esterifying a free hydroxyl group in the reactive phosphate ester. The phosphazene compound is a chain or cyclic compound represented by the formula: —P (R ₂ ) ═N— [wherein R is a substituted or unsubstituted aryl group], and has heat resistance, moisture resistance, In view of flame retardancy and chemical resistance, a cyclophosphazene derivative is particularly preferably used. Examples of the phosphazene compound having a reactive group include phenoxyphosphazene, cyanophenoxyphosphazene, hydroxyphenoxyphosphazene, aminophenoxyphosphazene and the like.

  In the adhesive layer, the content of (B) the organophosphorus compound is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, based on 100 parts by weight of the (A) polyamide resin having a dimer acid residue, and 30 weights. Part or more is more preferable. Moreover, 150 weight part or less is preferable, 120 weight part or less is more preferable, and 100 weight part or less is further more preferable.

  In the present invention, the adhesive layer may contain (C) an epoxy resin. As the epoxy resin, those having two or more epoxy groups are preferable, diglycidyl ethers such as bisphenol A, bisphenol F, bisphenol S, resorcinol, dihydroxynaphthalene, dicyclopentadiene diphenol, dicyclopentadiene dixylenol, and phenol novolacs. , Cresol novolak, trisphenylol methane, epoxidized tetraphenylol ethane, epoxidized metaxylene diamine, cyclohexene oxide, bicycloheptene oxide, cyclopentene oxide and the like are preferable. Moreover, what has a total of 3 or more chemical reaction sites chosen from the group which consists of an allyl group, a methallyl group, an amino group, a hydroxyl group, and a carboxyl group other than an epoxy group is also preferable. When two or more different chemical reaction sites are included, it is sufficient that the total number of all types of chemical reaction sites in the unit molecule is three or more. The position of the chemical reaction site is not particularly limited, but preferably has a chemical reaction site at least in the side chain. Two or more of the above epoxy resins may be used.

  In the present invention, the adhesive layer may contain (D) a curing agent for epoxy resin. (D) Curing agent for epoxy resin is not particularly limited as long as it reacts with epoxy resin, but known amine compounds, phenol resins, acid anhydrides, melamine resins, xylene resins, furan resins, cyanate ester resins, etc. Are illustrated. Among these, phenol resin is particularly preferable from the viewpoint of insulation. The phenol resin is not particularly limited as long as it contains two or more phenolic hydroxyl groups in one molecule, and any known phenol resin such as novolac type phenol resin and resol type phenol resin can be used. Specifically, for example, alkyl-substituted phenols such as phenol, cresol, pt-butylphenol, nonylphenol, and p-phenylphenol, cyclic alkyl-modified phenols such as terpene and dicyclopentadiene, nitro groups, halogen groups, cyano groups, Examples thereof include those having a functional group containing a hetero atom such as an amino group, those having a skeleton such as naphthalene and anthracene, and resins made of polyfunctional phenols such as bisphenol F, bisphenol A, bisphenol S, resorcinol, and pyrogallol. Moreover, you may use 2 or more types of the said hardening | curing agent for epoxy resins. From the viewpoint of insulation reliability, it is preferable to use a resol type phenol resin.

  In the present invention, the adhesive layer may contain (E) a curing accelerator. For example, known ones such as aromatic polyamines, imidazole derivatives such as 2-alkyl-4-methylimidazole and 2-phenyl-4-alkylimidazole, dicyandiamide, triphenylphosphine and diazabicycloundecene can be exemplified. Two or more of these may be used.

  The coverlay film of the present invention is composed of an aramid film in which the base film is halogenated. Aramid film is characterized by excellent heat resistance and chemical resistance. However, because of its high moisture absorption and desorption rate and large dimensional change, it is difficult to ensure processing dimensional accuracy and to process circuit boards. Yes. However, the cover lay film of the present invention uses a halogenated aramid film to improve the flame retardancy of the aramid film and reduce the hygroscopic expansion coefficient while ensuring the necessary heat resistance and chemical resistance. It becomes possible to make it. For this reason, it is possible to obtain a stable machining accuracy by reducing a change in curl amount due to the machining environment. Examples of halogen include chlorine and fluorine, with chlorine being particularly preferred. The halogen element content is preferably 10 to 30% by weight based on the total weight of the base film.

The hygroscopic expansion coefficient of the halogenated aramid film is preferably 20 ppm /% or less at 23 ° C. If it is 20 ppm /% or less, it is possible to suppress hygroscopic expansion / dehumidification shrinkage of the film that occurs during process retention, heat treatment, and the like, and to suppress dimensional changes due to changes in the processing environment. Here, the hygroscopic expansion coefficient in the present invention refers to a value measured by the following method. Humidified aramid film cut to about 100 mm x 100 mm is conditioned at 23 ° C / 55% RH for 24 hours, and the actual dimensions are measured with a universal projector (Nikon V-16E). Then, after performing absolute dry humidity control for 24 hours in a desiccator adjusted to 0% relative humidity, the actual dimensions are measured again. The hygroscopic expansion coefficient is calculated from the measured actual dimension value according to the following equation.
Hygroscopic expansion coefficient (ppm /%) = ((actual dimension after humidity control−actual dimension after absolute drying) / (actual dimension after absolute drying × 55)) × 10 ⁶ .

  The thickness of the halogenated aramid film is preferably 2 μm or more and 25 μm or less, and more preferably 15 μm or less from the viewpoint of film strength, workability, and product bending repulsion. Moreover, you may perform surface treatments, such as a hydrolysis, a corona discharge, a low temperature plasma, a physical roughening, an easily bonding coating process, as needed.

  The coverlay film of the present invention may have a protective film that can be peeled off from the adhesive layer. For example, a three-layer structure of halogenated aramid film / adhesive layer / protective film corresponds to this.

  The protective film is not particularly limited as long as it can be peeled without impairing the form and function of the adhesive layer. For example, polyester, polyolefin, polyphenylene sulfide, polyvinyl chloride, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, polyvinyl butyral , Plastic films such as polyvinyl acetate, polyvinyl alcohol, polycarbonate, polyamide, polyimide, polymethyl methacrylate, films coated with a release agent such as silicone or fluorine compound, and papers laminated with these films, release films Examples thereof include paper impregnated or coated with a moldable resin.

  Next, the method for producing the cover lay film of the present invention will be described with examples.

  (A) The resin composition constituting the adhesive layer in the cover lay of the present invention is dissolved in a solvent to form an adhesive paint, which is applied onto a halogenated aramid film and dried to form an adhesive layer. It is preferable to apply so that the film thickness of the adhesive layer is 5 to 100 μm. Drying conditions are usually 100 to 200 ° C. and 1 to 5 minutes. Solvents are not particularly limited, but aromatics such as toluene, xylene and chlorobenzene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, aprotics such as dimethylformamide, dimethylacetamide and N methylpyrrolidone, ethanol, methanol and isopropyl alcohol Alcohol solvents such as N-butanol and benzyl alcohol are suitable, and two or more of these may be used.

  (B) The cover layer film of the present invention is formed by laminating a protective film made of polyester or polyolefin having a releasability with a weaker peel strength than the above, if necessary, on the adhesive layer formed by the method described in (a). obtain. When the thickness of the adhesive is further increased, the coating material may be applied again, or the formed adhesive layer may be laminated a plurality of times. Alternatively, an adhesive layer may be prepared on the protective film, and a halogenated aramid film may be laminated to obtain the coverlay film of the present invention. Lamination conditions are a normal temperature of 50 to 160 ° C. and a pressure of 0.1 to 0.5 MPa. After obtaining the coverlay film of the present invention, the degree of cure of the adhesive layer may be adjusted by, for example, heat treatment at 40 to 100 ° C. for about 20 to 300 hours. By adjusting the degree of curing, it is possible to prevent excessive flow of the adhesive when the coverlay film is bonded to a wiring board or the like and to prevent foaming due to moisture during heat curing.

  The electronic component using the cover lay film of the present invention has excellent chemical resistance even in a usage form that is continuously exposed to acid and alkali in the usage environment, and remarkably improves the reliability of the electronic circuit. In addition to being able to achieve this, it is possible to achieve both workability and machining accuracy.

  Although an example of embodiment of this invention is shown below, this invention is not limited to these Examples. First, the evaluation method in an Example and a comparative example is demonstrated.

(1) Measurement of hygroscopic expansion coefficient of base film The base film cut to about 100 mm × 100 mm was conditioned at 23 ° C./55% RH for 24 hours, and the actual dimensions were obtained using a universal projector (Nikon V-16E). Was measured. Subsequently, after performing absolute dry humidity control for 24 hours in a desiccator adjusted to a relative humidity of 0% with diphosphorus pentoxide, the actual dimensions were again measured with a universal projector. The hygroscopic expansion coefficient was calculated from the measured actual dimension value according to the following equation.
Hygroscopic expansion coefficient (ppm /%) = ((actual dimension after humidity control−actual dimension after absolute drying) / (actual dimension after absolute drying × 55)) × 10 ⁶ .

(2) Evaluation of press workability The protective film of Toray film carrier tape # 7100 (trade name) having a base polyimide film thickness of 50 μm is peeled off, and a 25 μm electrolytic copper foil is laminated at 130 ° C. and 0.3 MPa. did. Subsequently, heat treatment was sequentially performed in an air oven at 80 ° C. for 3 hours, at 100 ° C. for 5 hours, and at 150 ° C. for 5 hours to produce an adhesive tape with copper foil. Photoresist film formation, etching, and resist stripping are performed on the copper foil surface of the obtained adhesive tape with copper foil by a conventional method to form a counter electrode circuit having a wiring pitch of 100 μm (conductor width of 50 μm) and a residual copper ratio of 50%. A circuit board for evaluating press workability was obtained.

  After peeling the polyethylene terephthalate film from the cover lay film obtained by the method described in each example or comparative example, the circuit processing surface of the circuit board for press workability evaluation is 100 ° C to 130 ° C, 0.1 MPa, normal pressure. Pressing was performed under atmospheric conditions, and the time required to completely embed the coverlay film adhesive between the circuits without bubbles or imperfectly embedded portions was measured. This was performed for each of the five samples for the examples and comparative examples, and the time during which pressing was possible in the shortest time was defined as the processing time. If the processing time is 120 seconds or less, it can be determined that the workability is good.

(3) Evaluation of flammability The protective film of Toray film carrier tape # 7100 (trade name) having a base polyimide film thickness of 50 μm was peeled off, and then in an air oven at 80 ° C. for 3 hours, at 100 ° C. for 5 hours, 160 A sequential heat treatment was performed at 5 ° C. for 5 hours to obtain a circuit board for evaluation of combustibility.

  The polyethylene terephthalate film is peeled from the coverlay film obtained by the method described in each example or comparative example, and the adhesive surface of the circuit board for flammability evaluation is subjected to conditions of 130 ° C., 0.1 MPa, 180 seconds. Press working was performed. Thereafter, the circuit board on which the cover lay film was pressed was heat-cured in an oven at 160 ° C. for 5 hours to produce a circuit board for flammability evaluation. Using the obtained circuit board for flammability evaluation, a flammability test based on the UL-94V test was performed to measure a corresponding flammability grade. If the flammability in the UL-94V test is V-1 or higher, it can be determined that the flame retardancy is good.

(4) Measurement of curling amount and curling amount change of circuit board with coverlay film The protective film of Toray film carrier tape # 7100 (trade name) having a base polyimide film thickness of 50 μm was peeled off, and an electrolytic copper foil of 25 μm was Lamination was performed at 130 ° C. and 0.3 MPa. Subsequently, heat treatment was sequentially performed in an air oven at 80 ° C. for 3 hours, at 100 ° C. for 5 hours, and at 150 ° C. for 5 hours to produce an adhesive tape with copper foil. Photoresist film formation, etching, and resist stripping are performed on the copper foil surface of the obtained adhesive tape with copper foil by a conventional method to form a counter electrode circuit having a wiring pitch of 100 μm (conductor width of 50 μm) and a residual copper ratio of 50%. A circuit board for evaluating press workability was obtained.

  After peeling the polyethylene terephthalate film from the cover lay film obtained by the method described in each Example or Comparative Example, 130 ° C., 1.0 MPa, normal pressure atmosphere on the circuit processed surface of the circuit board for press workability evaluation, After performing press working under the condition of 180 seconds, the obtained coverlay film-coated circuit board was sequentially heat-treated in an air oven at 80 ° C. for 3 hours, 100 ° C. for 5 hours, and 160 ° C. for 5 hours, The adhesive layer was heat-cured. The obtained cured coverlay film-coated circuit board was cut into 25 mm × 40 mm and humidity-controlled at 23 ° C./55% RH for 24 hours, and then the curled substrate end was left on the glass plate facing upward. In this condition, the maximum height position from the glass plate of the hardened coverlay film coated circuit board was measured with the curl generated with the coverlay on the inside and the curl generated with the coverlay on the outside as the minus. (Curl amount after humidity control). Then, the circuit board on which the cured coverlay film was adhered was dried for 24 hours in a desiccator adjusted to a relative humidity of 0% with diphosphorus pentoxide for 24 hours, and the end of the curled substrate faced upward on the glass plate. The curl generated with the coverlay on the inside is added, and the curl generated with the coverlay on the outside is set to the maximum height position from the glass plate of the cured coverlay film-coated circuit board. (Curl amount after absolutely dry).

Of the measured curl amount after humidity adjustment and curl amount after absolutely dry, the one with a large absolute value was selected, and the absolute value was taken as the absolute value of the curl amount. Further, the change in curl amount was calculated by the following equation.
Curling amount change (mm) = (curling amount after humidity adjustment (mm)) − (curling amount after absolute drying (mm))
If the absolute value of the curl amount is 5 mm or less, it can be judged as good. Further, it can be judged that if the change in curl amount is ± 5 mm or less, it is good, and if it is ± 3 mm or less, it is very good.

Example 1
Dimer acid polyamide resin ("Sunmide" (registered trademark) HT-100G, manufactured by Air Products Japan, amine value 1, melt viscosity 7.0 Pa.s) 100 parts by weight, phosphate ester resin (PX-200, Daihachi Chemical) 20 parts by weight of an industrial company), 80 parts by weight of an epoxy resin (“Epicoat” (registered trademark) YL980, manufactured by Japan Epoxy Resin Co., Ltd.), 50 parts by weight of a phenol resin (CKM2400, manufactured by Showa Polymer Co., Ltd.), a curing accelerator (2 ethyl) -4 methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) 2 parts by weight of ethanol / toluene mixed solvent (mixing weight ratio ethanol 1: toluene 4) is stirred and mixed at 30 ° C., and the adhesive composition has a solid content concentration of 25% by weight. A product was made.

  This adhesive composition was applied to a halogenated aramid film (“Mictron” (registered trademark) manufactured by Toray Industries, Inc.) with a bar coater to a dry thickness of about 40 μm, dried at 150 ° C. for 4 minutes, and protected. A polyethylene terephthalate film (“Film Vina” (registered trademark) GT manufactured by Fujimori Kogyo Co., Ltd.) was attached as a film to obtain a coverlay film. Using the obtained cover lay film, the press workability, the flammability, and the curl amount change of the circuit board to which the cover lay film was adhered were evaluated by the above methods.

(Example 2)
Dimer acid polyamide resin (“Tomide” (registered trademark) TXC-232C, manufactured by Fuji Kasei Kogyo Co., Ltd., amine value 10.0, melt viscosity 24.0 Pa · s) 100 parts by weight, phosphate ester resin (PX-200, large 20 parts by weight of Eight Chemical Industry Co., Ltd., 80 parts by weight of epoxy resin ("Epicoat" (registered trademark) YL980, manufactured by Japan Epoxy Resin Co., Ltd.), 50 parts by weight of phenol resin (CKM2400, manufactured by Showa Polymer Co., Ltd.), curing accelerator ( Ethanol / toluene mixed solvent (mixing weight ratio ethanol 1: toluene 4) is added to 2 parts by weight of 2-ethyl-4-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred and mixed at 30 ° C. to a solid content concentration of 25% by weight. An agent composition was prepared. Using the obtained adhesive composition, a coverlay film was prepared and evaluated in the same manner as in Example 1.

(Example 3)
Dimer acid polyetheramide resin ("Tomide" (registered trademark) PA-200, manufactured by Fuji Kasei Kogyo Co., Ltd., amine value 3, melt viscosity 40.0 Pa · s) 100 parts by weight, phosphate ester resin (PX-200, large 20 parts by weight of Eight Chemical Industry Co., Ltd., 80 parts by weight of epoxy resin ("Epicoat" (registered trademark) YL980, manufactured by Japan Epoxy Resin Co., Ltd.), 50 parts by weight of phenol resin (CKM2400, manufactured by Showa Polymer Co., Ltd.), curing accelerator ( Ethanol / toluene mixed solvent (mixing weight ratio ethanol 1: toluene 4) is added to 2 parts by weight of 2-ethyl-4-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred and mixed at 30 ° C. to a solid content concentration of 25% by weight. An agent composition was prepared. Using the obtained adhesive composition, a coverlay film was prepared and evaluated in the same manner as in Example 1.

Example 4
Dimer acid polyetheramide resin (“Tomide” (registered trademark) PA-200, manufactured by Fuji Kasei Kogyo Co., Ltd., amine number 1, melt viscosity 40.0 Pa · s) and dimer acid polyamide resin (“Tomide” (registered trademark)) PA-100, manufactured by Fuji Kasei Kogyo Co., Ltd., amine value 0, melt viscosity 180.0 Pa · s) and dimer acid polyamide resin (“Tomide” (registered trademark) 535, manufactured by Fuji Kasei Kogyo Co., Ltd., amine value 50, melt viscosity 1) 0.02 Pa · s) 2: 1: 0.5 mixture (amine number 7.1 melt viscosity 80 Pa · s) (dimer acid polyetheramide resin 1) 100 parts by weight, phosphate ester resin (PX-200) , Manufactured by Daihachi Chemical Industry Co., Ltd.) 20 parts by weight, epoxy resin (“Epicoat” (registered trademark) YL980, manufactured by Japan Epoxy Resin Co., Ltd.) 80 parts by weight, phenol tree An ethanol / toluene mixed solvent (mixing weight ratio ethanol 1: toluene 4) was added to 50 parts by weight (made by CKM2400 Showa Polymer Co., Ltd.) and 2 parts by weight of a curing accelerator (2 ethyl-4 methylimidazole, made by Tokyo Chemical Industry Co., Ltd.) The mixture was stirred and mixed at 30 ° C. to prepare an adhesive composition having a solid content concentration of 25% by weight. Using the obtained adhesive composition, a coverlay film was prepared and evaluated in the same manner as in Example 1.

(Example 5)
Dimer acid polyamide resin (“Macromelt” (registered trademark) 6900, manufactured by Henkel Japan, amine value 0, melt viscosity 10 Pa · s) 100 parts by weight, phosphate ester resin (PX-200, manufactured by Daihachi Chemical Industry Co., Ltd.) 20 parts by weight, epoxy resin ("Epicoat" (registered trademark) YL980, manufactured by Japan Epoxy Resin Co., Ltd.) 80 parts by weight, phenol resin (CKM2400, manufactured by Showa Polymer Co., Ltd.), 50 parts by weight, curing accelerator (2-ethyl-4-methylimidazole) (Manufactured by Tokyo Chemical Industry Co., Ltd.) An ethanol / toluene mixed solvent (mixing weight ratio ethanol 1: toluene 4) was added to 2 parts by weight, and the mixture was stirred and mixed at 30 ° C. to prepare an adhesive composition having a solid content concentration of 25% by weight. . Using the obtained adhesive composition, a coverlay film was prepared and evaluated in the same manner as in Example 1.

(Example 6)
Dimer acid polyamide resin (“Tomide” (registered trademark) 1350, manufactured by Fuji Kasei Kogyo Co., Ltd., amine number 10, melt viscosity 3.0 Pa · s) 100 parts by weight, phosphate ester resin (PX-200, Daihachi Chemical Industry Co., Ltd.) 20 parts by weight, epoxy resin (“Epicoat” (registered trademark) YL980, manufactured by Japan Epoxy Resin Co., Ltd.) 80 parts by weight, phenol resin (CKM2400, manufactured by Showa Polymer Co., Ltd.), 50 parts by weight, curing accelerator (2 ethyl-4) Ethanol / toluene mixed solvent (mixed weight ratio ethanol 1: toluene 4) is added to 2 parts by weight of methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred and mixed at 30 ° C. to obtain an adhesive composition having a solid content concentration of 25% by weight. Produced. Using the obtained adhesive composition, a coverlay film was prepared and evaluated in the same manner as in Example 1.

(Example 7)
Dimer acid polyamide resin (“Tomide” (registered trademark) PA-100, manufactured by Fuji Kasei Kogyo Co., Ltd., amine value 0, melt viscosity 180.0 Pa · s) 100 parts by weight, phosphate resin (PX-200, Daihachi Chemical) 20 parts by weight of an industrial company), 80 parts by weight of an epoxy resin (“Epicoat” (registered trademark) YL980, manufactured by Japan Epoxy Resin Co., Ltd.), 50 parts by weight of a phenol resin (CKM2400, manufactured by Showa Polymer Co., Ltd.), a curing accelerator (2 ethyl) -4 methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) 2 parts by weight of ethanol / toluene mixed solvent (mixing weight ratio ethanol 1: toluene 4) is stirred and mixed at 30 ° C., and the adhesive composition has a solid content concentration of 25% by weight. A product was made. Using the obtained adhesive composition, a coverlay film was prepared and evaluated in the same manner as in Example 1.

(Comparative Example 1)
Dimer acid polyamide resin (“Tomide” (registered trademark) PA-100, manufactured by Fuji Kasei Kogyo Co., Ltd., amine value 0, melt viscosity 180.0 Pa · s) 100 parts by weight, phosphate resin (PX-200, Daihachi Chemical) 20 parts by weight of an industrial company), 80 parts by weight of an epoxy resin (“Epicoat” (registered trademark) YL980, manufactured by Japan Epoxy Resin Co., Ltd.), 50 parts by weight of a phenol resin (CKM2400, manufactured by Showa Polymer Co., Ltd.), a curing accelerator (2 ethyl) -4 methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) 2 parts by weight of ethanol / toluene mixed solvent (mixing weight ratio ethanol 1: toluene 4) is stirred and mixed at 30 ° C., and the adhesive composition has a solid content concentration of 25% by weight. A product was made. Using the obtained adhesive composition, a coverlay film was produced in the same manner as in Example 1, and then the halogenated aramid film (“Mictron”) was peeled off from the obtained coverlay film. Instead, an aramid film was used. (“Aramika” (registered trademark) R, manufactured by Teijin Advanced Film Ltd.) was bonded. About the coverlay film which bonded the aramid film, it evaluated similarly to Example 1. FIG.

(Comparative Example 2)
Dimer acid polyamide resin (“Tomide” (registered trademark) 535, manufactured by Fuji Kasei Kogyo Co., Ltd., (amine value 50, melt viscosity 1 Pa · s) 100 parts by weight, phosphate ester resin (PX-200, manufactured by Daihachi Chemical Industry Co., Ltd.) ) 20 parts by weight, epoxy resin (“Epicoat” (registered trademark) YL980, manufactured by Japan Epoxy Resin Co., Ltd.) 80 parts by weight, phenol resin (CKM2400, manufactured by Showa High Polymer Co., Ltd.), 50 parts by weight, curing accelerator (2 ethyl-4 methyl) An ethanol / toluene mixed solvent (mixing weight ratio ethanol 1: toluene 4) is added to 2 parts by weight of imidazole (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred and mixed at 30 ° C. to produce an adhesive composition having a solid content concentration of 25% by weight. Using the obtained adhesive composition, a cover lay film bonded with an aramid film was prepared in the same manner as in Comparative Example 1, and evaluated. It was.

(Comparative Example 3)
Acrylonitrile polybutadiene resin ("Nipol" (registered trademark) 1043, manufactured by Nippon Zeon Co., Ltd., 100 parts by weight), brominated epoxy resin ("Epicoat" (registered trademark) 5050, manufactured by Japan Epoxy Resin Co., Ltd.), 80 parts by weight, phenol resin (CKM2400) Toluene is added to 50 parts by weight of Showa Polymer Co., Ltd. and 2 parts by weight of a curing accelerator (2-ethyl-4methylimidazole, Tokyo Kasei Co., Ltd.), and the mixture is stirred and mixed at 30 ° C. to a solid content concentration of 25% by weight. Using the resulting adhesive composition, a coverlay film having an aramid film bonded thereto was prepared and evaluated in the same manner as in Comparative Example 1.

  The compositions and evaluation results of Examples 1 to 7 and Comparative Examples 1 to 3 are shown in Tables 1 and 2.

Claims (3)

A coverlay film comprising an adhesive layer containing a polyamide resin having a dimer acid residue on a halogenated aramid film. The coverlay film according to claim 1, wherein the halogenated aramid film has a hygroscopic expansion coefficient of 20 ppm /% or less. The coverlay film, wherein the adhesive layer further contains an organic phosphorus compound.