JP2005148098A - Conductive resin composition, conductive resin film, and method for manufacturing electronic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive resin composition having excellent long-term storage property with which a fine pattern or film can be easily formed. <P>SOLUTION: The conductive resin composition contains a photopolymerizable resin containing at least either an acidic group or the salt of an acidic group in a side chain, a photopolymerizable compound, and a conductive resin. As the photopolymerizable compound, a compound containing at least either an acidic group or the salt of an acidic group in a side chain is used. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention generally relates to a conductive film, and more particularly to a conductive resin composition for forming a conductive film.

  Conductive resin with electrical conductivity while being organic is easy to form and remove conductive layers, and can be applied to electrode materials, wiring materials, antistatic, ESD failure prevention, electromagnetic shielding materials, transparent conductive films, etc. Expected.

  With the demand for downsizing, speeding up, and reducing power consumption of electronic devices, miniaturization of electronic elements such as transistors is rapidly progressing. For example, today, ultra-fine MOS transistors having a gate length of less than 0.1 μm have been put into practical use.

  On the other hand, such miniaturized electronic devices are extremely vulnerable to ESD (electrostatic discharge), and therefore measures are required to protect the devices from ESD during the manufacture or mounting of these devices. .

  For this purpose, it is possible to prevent a failure such as ESD by forming a conductive thin film on the element or a substrate on which the element is mounted, for example, and releasing the charge to the conductive thin film. However, for this purpose, it is necessary to form a micropattern capable of maintaining conductivity without causing peeling by heat treatment or cleaning treatment performed in the manufacturing process, mounting process, assembly process, or the like of the electronic element or electronic device. In other words, a film capable of forming a fine pattern and having excellent adhesion, mechanical, thermal strength, solvent resistance, and conductivity is required.

  In view of this requirement, the inventor of the present invention firstly performs a photocuring process in which a conductive resin solution composed of a solvent-soluble conductive resin and an aggregation inhibitor and / or a dopant, and an acidic group or a salt of an acidic group in the side chain. A conductive resin composition was proposed in which the conductive resin was compounded with a conductive resin and the conductive resin was dispersed in the photocurable resin in a substantially molecular form.

  In the above proposal, photoresolving can be achieved by dispersing the conductive resin in a molecular state using a coagulation inhibitor in a photocurable resin having a structure having a high affinity for the conductive resin. A resin composition is obtained. In the above proposal, high conductivity is secured by introducing a conductive resin at a high concentration, while on the other hand, the photocurable resin is provided with patterning characteristics, adhesion, film strength, solvent resistance, and the like. These characteristics are also realized.

As described above, in the conductive resin composition proposed above, a conductive resin that is generally insoluble or difficult to dissolve in a solvent and easily causes aggregation or gelation, has an anti-aggregation agent or a structure having high affinity therewith. By compounding with a photocurable resin, molecular dispersion of the conductive resin is realized.
Japanese Patent Laid-Open No. 03-253143

  By the way, in general, the conductive resin has a rigid molecular structure, does not have adhesiveness itself, and does not cure. Therefore, if the content of the conductive resin is increased in order to further improve the conductivity, the obtained film becomes brittle, and the problem arises that the adhesion and strength of the film are reduced.

  In order to avoid this problem, it is necessary to advance the curing of the photocurable resin containing acidic groups and the like that decrease relatively with the increase in the conductive resin to form a tough film. For this purpose, a photocurable monomer or oligomer having a large number of photosensitive groups (3 or more) is added to increase the three-dimensional crosslinking density, and the mechanical, thermal strength, solvent resistance, etc. of the photocurable resin containing acidic groups and the like. It is necessary to improve. It is also conceivable to impart flexibility and adhesion by adding a photocurable monomer or oligomer having a small number of photosensitive groups (1 to 2). However, ordinary photo-curable monomers or oligomers have low affinity with the conductive resin, so that when added in a large amount, aggregation or gelation of the conductive resin is caused.

  Then, this invention makes it a general subject to provide the novel and useful conductive resin composition which solved the said problem.

  A more specific problem of the present invention is that a conductive resin composition that can easily form a fine pattern or film and that has excellent long-term storage stability, and formed using the conductive resin composition, has conductivity and adhesion. , Conductive resin film and pattern excellent in mechanical strength, thermal strength, solvent resistance, flexibility, etc., pattern forming method capable of efficiently forming the pattern, and electron using such conductive resin composition It is to provide an apparatus and a method for manufacturing the same.

  The present invention provides a conductive resin composition comprising the photopolymerizable resin having at least one of an acidic group and a salt of an acidic group in a side chain, a photopolymerizable compound, and a conductive resin. Then, the photopolymerizable compound is solved by a conductive resin composition characterized in that it has at least one of an acidic group and an acidic group salt in the side chain.

  According to the present invention, the photopolymerizable compound, more specifically, the photocurable monomer or oligomer has an acidic group or acidic group having a high affinity with the conductive resin, similarly to the photopolymerizable resin. By introducing the salt, the affinity with the conductive resin can be improved. As a result, even if the content of the conductive resin is increased, aggregation or gelation does not occur, and mechanical, thermal, A film capable of controlling the mechanical strength, solvent resistance, adhesion, flexibility and the like can be obtained. As a result, according to the present invention, a fine pattern can be formed, and a film having excellent mechanical strength, flexibility, solvent resistance, and good conductivity can be obtained. Such a film or a pattern formed by patterning the film can be used for various purposes such as antistatic.

  In the present invention, the conductivity of the conductive resin is further improved by adding a dopant, and by adding an anti-aggregation agent, the conductive resin composition is stabilized and can be stored for a long time.

[First Embodiment]
Hereinafter, the conductive resin composition according to the first embodiment of the present invention will be described.

  The conductive resin composition of the present invention is (1) a photopolymerizable resin used for forming a film and containing an acidic group or salt of an acidic group in its side chain, and (2) an acidic group or acidic group in its side chain. It contains a photopolymerizable compound containing a salt of a group and (3) a conductive resin, and if necessary, contains a dopant, an aggregation inhibitor, and other appropriately selected components.

  Hereinafter, the photocurable resin, the photopolymerizable compound, and the conductive resin will be individually described.

(1) Photocurable resin containing acidic group or salt of acidic group As the photopolymerizable resin containing acidic group or salt thereof, the side chain has at least one selected from acidic group and salt thereof. However, there is no particular limitation as long as it has photocurability, and it can be appropriately selected according to the purpose.For example, one that can ensure adhesion, heat resistance, solvent resistance, removability, etc. of the formed film. preferable. When the film to be formed is patterned, it is more preferably a photocurable resin or an electron beam sensitive resin.

  For example, unsaturated polyester resins, polyester acrylates, urethane acrylates, epoxy acrylates, polyether acrylates, spirane acrylates, polybutadiene acrylates and other acrylate resins, methacrylate resins, novolac resins, polyvinylphenol resins , Poly (methyl isopropenyl ketone) resin, polyglutarimide resin, poly (olefin sulfone) resin, polyimide resin, etc., side chain, or part of the side chain is acidic group such as sulfone group or carboxyl group, or acidic group Those introduced in the form of a base salt can be selected as the photopolymerizable resin. Moreover, the mixture of the said resin, the mixture of the said resin and other resin, etc. can be used.

(2) Photopolymerizable compound containing acidic group or salt of acidic group As the photopolymerizable compound containing acidic group or salt thereof, the side chain has at least one selected from acidic group and salt thereof. Any monomer or oligomer having photocurability is not particularly limited, and can be appropriately selected from known photocurable monomers or oligomers according to the purpose. For example, acrylic-type, methacryl-type, vinyl-type, imide-type monomers or oligomers which are modified or contained by an acidic group such as a carboxyl group or a sulfone group can be used. These may be used alone or in combination of two or more.

  The content of the monomer or oligomer is not particularly limited, and the characteristics of the formed film or pattern can be appropriately selected to match the purpose. However, the photopolymerizability containing the acidic group or the salt of the acidic group is used. In order to cure the resin strongly and form a tough film, the monomer or oligomer having 3 or more photosensitive groups is preferably contained in an amount of 5% or more, more preferably 10% or more, based on the photopolymerizable resin. In addition, in order to impart flexibility and adhesion to the formed film, for example, a conductive resin film obtained by adding the monomers or oligomers having 1 or 2 photosensitive groups and balancing them can be obtained. It can be adjusted to the characteristics suitable for

(3) Conductive resin The conductive resin is not particularly limited and may be appropriately selected from known conductive resins. For example, polyaniline, polypyrrole, polythiophene, poly (3-alkylthiophene), polythiophene vinylene , Polyfuran, polyselenophene, polyfurylene vinylene, polyparaphenylene, polyparaphenylene vinylene, polythienylene vinylene, polyisothianaphthene, polyacetylene, polynaphthalene, polyanthracene, polypyrene, polyazulene, polynaphthalene vinylene, polyparaphenylene Examples thereof include materials included in the category of so-called conductive polymers such as sulfides and derivatives thereof.

  These may be used alone or in combination of two or more. In particular, polyaniline or a derivative thereof, a mixture thereof, or a mixture of these and the above substances is preferable from the viewpoint that it is solvent-soluble in a form exhibiting conductivity.

  The content of the conductive resin is not particularly limited and may be appropriately selected depending on the purpose.For example, in the solid content of the film or pattern formed by the conductive resin composition, 0.5% by mass or more It is preferable that it is 1.0 mass% or more. When the content is less than 0.5% by mass in the solid content of the film or pattern formed by the conductive resin composition, the conductivity of the formed film or pattern may not be sufficient.

(4) Dopant Next, the dopant used by this invention is demonstrated.

The dopant is not particularly limited, and known acids can be used, but sulfonic acids or polysulfonic acids are preferable, and dodecylbenzenesulfonic acid, naphthalenesulfonic acid, and the like are particularly preferable. These do not easily cause aggregation of the conductive resin at the time of doping, and do not easily volatilize or decompose by heating, so that thermal stability can be imparted to the conductivity of the formed film.

(5) Anti-aggregation agent The anti-aggregation agent is not particularly limited as long as it can prevent aggregation of the conductive resin, and can be appropriately selected depending on the purpose. Suitable examples include cyclic organic substances having a polar portion and a nonpolar portion in the molecule, lipophilic aromatic liquids, primary amines, and the like.

  The cyclic organic liquid can be, for example, the conductive resin or a solvent for dissolving the conductive resin (for example, N-methyl-2-pyrrolidone solution; NMP). By bonding to the conductive resin, the conductive resin is prevented from aggregating even when doping or the like is performed.

  Examples of the polar moiety in the molecule of the cyclic organic material include a ketone group, an amino group, and an imino group, and examples of the nonpolar moiety in the molecule include an alkyl group.

  Examples of the cyclic organic liquid include cyclohexanone and cyclohexylamine, and cyclohexanone is particularly preferable.

  As the lipophilic aromatic liquid, for example, toluene, xylene and the like are preferable.

  Examples of the primary amines include aniline, p-phenylenediamine, o-phenylenediamine, ethylenediamine, and the like, and p-phenylenediamine is particularly preferable.

  These anti-aggregation agents may be used alone or in combination of two or more.

There is no restriction | limiting in particular as content in the said conductive resin composition of the said aggregation inhibitor, According to the objective, it can select suitably.

(6) Other components Next, other components used in the conductive resin composition of the present invention will be described.

  There is no restriction | limiting in particular as another component, Although it can select suitably according to the objective, For example, a photoinitiator, a peeling inhibitor, a solvent, etc. are mentioned.

  The photopolymerization initiator is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include substances generally known as photopolymerization initiators and derivatives thereof or mixtures thereof. For example, benzophenone, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [ 4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2 -Benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -pheny Phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4′-trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, oligo [2-hydroxy-2-methyl- 1- [4- (1-methylvinyl) phenyl] propanone], 2,4,6-trimethylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzoylphosphine oxide, 1- [4- (4- Benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfanyl) propan-1-one, and the like.

  There is no restriction | limiting in particular as content in the said conductive resin composition of the said photoinitiator, According to the objective, it can select suitably.

  The anti-peeling agent is not particularly limited as long as the formed film can be prevented from being peeled off from the substrate, and can be appropriately selected depending on the purpose. For example, lactams, oximes, etc. Preferable examples include coupling agents such as blocked isocyanate compounds blocked with.

  These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as content in the said conductive resin composition of the said peeling inhibitor, According to the objective, it can select suitably.

  The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include N-methyl-2-pyrrolidone, butyloctanone, propylene carbonate, N-ethylpyrrolidone, N-formpiperidine, N- Examples thereof include polar solvents such as methylsuccinimide, 2-pyrrolidone, N-methylcaprolactam, and trimethyloxazole. By dissolving the conductive resin composition in the solvent, a coating solution used in the film forming process is obtained.

  These solvents may be used alone or in combination of two or more, and among these, the conductive resin (especially polyaniline), photocurable resin, dopant, photocurable monomer. -What can melt | dissolve an oligomer and the said other component favorably is preferable, and polar solvents, such as N-methyl- 2-pyrrolidone, are especially preferable.

The coating liquid of the present invention thus formed has excellent long-term storage stability, and can easily form fine patterns with excellent conductivity, adhesion, mechanical strength, thermal strength, solvent resistance, flexibility, etc. Therefore, it can be suitably used as a coating solution for forming an antistatic pattern of various materials.

[Second Embodiment]
Next, a conductive film or pattern forming process and an electronic device using the conductive film according to the second embodiment of the present invention will be described.

  The film or pattern of the present invention is formed using the conductive resin composition of the present invention, and is preferably manufactured by the film or pattern manufacturing method of the present invention.

  1 to 4 show an example of a process for mounting a semiconductor chip while avoiding ESD by forming the conductive film of the present invention on a polyimide substrate.

  Referring to FIG. 1, a wiring pattern 11 </ b> A indicated by a broken line is formed in a polyimide substrate 11, and contact pads 11 a of the wiring pattern 11 </ b> A are exposed on the surface of the substrate 11.

  In the present embodiment, the conductive film 12 is formed by applying the above-described coating solution onto the polyimide substrate 11 and pre-baking in the step of FIG.

  Further, in the step of FIG. 3, the conductive film 12 is exposed and developed, and an opening 12a corresponding to the contact pad 11a is formed so as to expose the contact pad 11a.

  Further, in the step of FIG. 4, the semiconductor chip 13 having bumps on the polyimide substrate 11 on which the conductive film 12 is thus formed is flip-chip so that the bumps are in contact with the contact pads 11a in the openings 12a. Implemented.

  In the process of FIG. 4, since the surface of the polyimide substrate 11 that is easily charged is covered with the conductive film 12 except for the opening 12a, the accumulated charge is immediately dissipated, and therefore the bumps of the semiconductor chip 13 are formed. Even if it contacts the substrate 11 during the mounting process, the semiconductor chip 13 is not damaged by ESD.

  In the present invention, since the conductive film 12 can be patterned by exposure / development, the openings 12a are formed with a size of 50 μm or less, particularly 10 to 20 μm, which is impossible by a screen printing method or the like. Is possible.

  The method for producing a conductive film or pattern of the present invention includes forming a coating film of the conductive resin composition of the present invention, and exposing the coating film to the entire surface or in a pattern shape, and further appropriately depending on the purpose. Includes other selected processes.

  The method for forming the coating film is not particularly limited, and the conductive resin composition is applied by a known coating method such as spin coating, blade coating, bar coating, dip coating, etc., and then dried. And a method of performing pre-baking and the like.

  The exposure method is not particularly limited, and a known exposure method can be appropriately selected according to the purpose. For example, a method of irradiating light, an electron beam, or the like, using a mask pattern as necessary, etc. Is mentioned.

  After the exposure, when a pattern is formed as in the embodiments of FIGS. When the development treatment is performed, unexposed portions in the coating film can be dissolved and removed. Further, after the development processing, post-exposure, post-baking or drying is performed as necessary, whereby the strength and adhesion of a desired pattern can be improved.

As the conductivity in the pattern of the present invention obtained as described above, the surface resistivity is preferably 1 × 10 ¹⁰ Ω / □ or less when the pattern is formed without heat treatment. × 10 ⁹ Ω / □ or less is more preferable, and when the pattern is formed by heat treatment, the volume resistivity is preferably 1 × 10 ¹¹ Ω / □ or less, preferably 1 × 10 ¹⁰ Ω / □. □ is more preferable.

  The volume resistivity can be measured by a known resistance measurement method (for example, JIS-K6911).

  As the flexibility of the pattern, it is preferable that cracks and chips do not occur in a bending test on a flexible film such as polyimide or PET. The bending test can be evaluated as follows, for example. That is, the above-mentioned pattern is formed on a polyimide film, the film is folded 180 degrees, then returned again, and the folded portion is observed with a microscope or the like by magnifying it 100 times to check for cracks or chips.

  The adhesiveness of the pattern is preferably 90% or more, more preferably 95% or more, and particularly preferably 100%, in a tape peel test. The residual rate in the peel test using the tape can be evaluated, for example, as follows. That is, the pattern is formed on a polyimide film, and 10 × 10 (100) crosscuts are made at 1 mm intervals to the pattern, and then the pattern is placed in 2-propanol at 40 ° C. for 20 minutes. After ultrasonic cleaning, drying at 60 ° C. for 5 minutes, applying a tape, and peeling off, the ratio of the number of remaining patterns after peeling can be evaluated as a remaining rate% (number of remaining pattern cuts / 100). it can.

  The pattern of the present invention is excellent in conductivity, adhesion, mechanical strength, thermal strength, solvent resistance, flexibility and the like. For example, for antistatic applications, from hard materials such as circuit boards and silicon substrates, FPC It can be used widely as a protective film for protecting electronic elements and the like from electrostatic disturbances such as ESD.

  As shown in FIG. 5A, it is possible to form a photosensitive multilayer film by forming the conductive film 22 of the present invention on a normal photosensitive film 21 having no conductivity. At that time, it is also possible to form another photosensitive film 23 on the conductive film 22 as shown in FIG. In this case, the photosensitive film 23 is not conductive, but the accumulated charge is dissipated through the conductive film 22 thereunder, so that charging is avoided.

  Examples according to the present invention are shown below, but the present invention is not limited thereto.

Production of Conductive Resin Composition Oxidized dedoped polyaniline synthesized by a chemical polymerization method was dissolved in N-methyl-2-pyrrolidone to prepare a 4% by mass solution. To 100 parts by weight of the resulting conductive resin solution, 100 parts by weight of cyclohexanone as an aggregation inhibitor and 4 parts by weight of dodecylbenzene sulfonic acid as a dopant are mixed, and 20 parts by weight of a sulfonated unsaturated polyester resin (manufactured by Kyotsu Chemical) Dissolved. After this, 10 parts by weight of hexafunctional monomer COOH-modified dipentaerythritol hexaacrylate (Toagosei), 4 parts by weight of monofunctional monomer 2-acryloylethylsuccinic acid (Shin Nakamura Kogyo), photopolymerization initiator ( 7 parts by weight of Nippon Sibel Hegner (Ezacure KIP75LT) was added and stirred for 2 minutes with a stirrer (Sinky Corporation; MX-201) to obtain a conductive resin composition.

When the obtained conductive resin composition was stored in a light-shielding environment, no aggregation or coagulation of oxidized dedoped polyaniline was observed even after 3 months.

Pattern formation The obtained conductive resin composition was applied onto a polyimide film with a bar coater to form a coating film, and this coating film was further pre-baked at 100 ° C for 10 minutes. Thereafter, the coating film is irradiated with light from an ultra-high pressure mercury lamp having a center wavelength of 365 nm through a quartz glass mask having a line-and-space pattern with a width of 10 to 200 μm under the condition of ² J / cm ^2. Was cured. Subsequently, development processing was performed using a 1% sodium borate solution at 40 ° C. to form a pattern. Thereafter, the pattern was washed with water and post-baked at 120 ° C. for 30 minutes to form a resin film having a pattern. The pattern film had a thickness of 2.0 μm, and it was confirmed that a line and space resolution of 20 μm was realized.

The polyimide film thus formed with a pattern was bent 180 degrees and then returned again, and the bent portion was observed with a microscope (Keyence; VH-8000) magnified 100 times, but cracks and chips were observed. There wasn't.

Film Formation In the same manner as the above pattern formation, the conductive resin composition was coated on a polyimide film with a bar coater to form a coating film, and the coating film was pre-baked at 100 ° C. for 10 minutes. Thereafter, the entire surface of the coating film was irradiated with light from an ultrahigh pressure mercury lamp having a center wavelength of 365 nm under the condition of ² J / cm ² to cure the coating film. Next, the same operation and washing with a 1% sodium borate solution at 40 ° C. were performed, followed by post-baking at 120 ° C. for 30 minutes to form a resin film.

When the surface resistivity of the film formed as described above was measured under the condition of 20 ° C. using a resistance measuring instrument (ADVANTEST; R12702A, Keithley; 617), it was 4 × 10 ⁶ Ωcm.

  In addition, the obtained film was subjected to ultrasonic cleaning in 2-propanol at 40 ° C. for 20 minutes, dried at 60 ° C. for 5 minutes, and then 10 × 10 pieces (100 pieces) were cut at 1 mm intervals. A peeling test was performed in which the tape was applied and peeled off. In this test, it was confirmed that the residual rate of the pattern was 100% (100/100).

  A conductive resin composition was prepared in the same manner as in Example 1 except that the COOH-modified dipentaerythritol hexaacrylate used in Example 1 was replaced with the trifunctional monomer COOH-modified pentaerythritol triacrylate. When the obtained conductive resin composition was evaluated in the same manner as in Example 1, the aggregation or coagulation of oxidized dedoped polyaniline was not observed even after 3 months as in Example 1.

  Thereafter, in the same manner as in Example 1, a pattern was formed on the polyimide film. The pattern film had a thickness of 1.2 μm, and a line and space resolution of 20 μm was obtained.

  Further, as a result of performing a bending test on the polyimide film on which the pattern was formed in the same manner as in Example 1, no cracks or chips were observed in the pattern of the bent portion.

Further, the surface resistivity of the resin film formed in the same manner as in Example 1 was 3 × 10 ⁶ Ωcm, and the residual rate in the peel test was 100% (100/100).

  Conductive resin in the same manner as in Example 1 except that the amount of COOH-modified dipentaerythritol hexaacrylate used in Example 1 was changed to 1 part by weight and 2-acryloylethylsuccinic acid a was changed to 1 part by weight. A composition was prepared. When the obtained conductive resin composition was evaluated in the same manner as in Example 1, no aggregation or coagulation of oxidized dedoped polyaniline was observed after 3 months as in Example 1.

  Thereafter, in the same manner as in Example 1, a pattern was formed on the polyimide film. The pattern film had a thickness of 1.0 μm, and a line and space resolution of 30 μm was obtained.

  Further, as a result of performing a bending test on the polyimide film on which the pattern was formed in the same manner as in Example 1, no cracks or chips were observed in the pattern of the bent portion.

Further, the surface resistivity of the resin film formed in the same manner as in Example 1 was 8 × 10 ⁵ Ωcm, and the residual ratio in the peel test was 97% (97/100).
[Comparative Example 1]
The COOH-modified dipentaerythritol hexaacrylate in Example 1 was changed to dipentaerythritol hexaacrylate (Shin Nakamura Chemical Co., Ltd.) which was not acid-modified, 2-acryloylethyl succinic acid was changed to methoxypolyethylene glycol acrylate (AM-30G; new) A conductive resin composition was prepared in the same manner as in Example 1 except that the medium was changed to Nakamura Chemical Co., Ltd. Aggregation of the conductive resin was observed in the obtained composition, and it gelled after one day and night.
[Comparative Example 2]
Conductivity was the same as in Example 1 except that the amount of COOH-modified dipentaerythritol hexaacrylate used in Example 1 was changed to 0.8 parts by weight and 2-acryloylethylsuccinic acid a was changed to 1 part by weight. A functional resin composition was prepared. When the obtained conductive resin composition was evaluated in the same manner as in Example 1, no aggregation or coagulation of oxidized dedoped polyaniline was observed after 3 months as in Example 1.

  Then, when the resin film was formed like Example 1 and the peeling test was done, the residual rate was 68% (68/100).

  Thus, according to the present invention, the photopolymerizable compound, more specifically, the photocurable monomer or oligomer has an acidic group having a high affinity with the conductive resin, similar to the photopolymerizable resin. Alternatively, by introducing a salt of an acidic group, the affinity with the conductive resin can be improved, and as a result, no aggregation or gelation occurs even if the content of the conductive resin is increased. A film capable of controlling mechanical, thermal strength, solvent resistance, adhesion, flexibility and the like can be obtained. As a result, according to the present invention, a fine pattern can be formed, and a film having excellent mechanical strength, flexibility, solvent resistance, and good conductivity can be obtained. Such a film or a pattern formed by patterning the film can be used for various purposes such as antistatic.

Although the present invention has been described with reference to the preferred embodiments, the present invention is not limited to such specific embodiments, and various modifications and changes can be made within the scope of the claims. is there.
(Additional remark 1) The photopolymerizable resin which contains at least any one of the salt of an acidic group and an acidic group in a side chain,
A photopolymerizable compound;
A conductive resin composition containing a conductive resin,
The photopolymerizable compound contains at least one of an acidic group and an acidic group salt in a side chain.
(Additional remark 2) The said photopolymerizable resin is unsaturated polyester resin, acrylate resin, methacrylate resin, novolak resins, polyvinyl phenol resin, poly (methyl isopropenyl ketone) resin, polyglutarimide resin, poly (olefin) The conductive resin composition according to supplementary note 1, wherein the conductive resin composition is selected from sulfone) resins and polyimide resins.
(Additional remark 3) The said photopolymerizable compound consists of a photocurable monomer or photocurable oligomer which has at least any one of an acidic group and the salt of the said acidic group in a side chain, The additional description 1 or 2 characterized by the above-mentioned. Conductive resin composition.
(Supplementary note 4) The conductive resin composition according to supplementary note 3, wherein the photopolymerizable compound is selected from acrylic, methacrylic, vinyl and imide monomers or oligomers and contains an acidic group.
(Additional remark 5) The said acidic group consists of a carboxyl group or a sulfone group, The conductive resin composition of Additional remark 4 (Appendix 6) The said photopolymerizable compound has 3 or more photosensitive groups, 6. The conductive resin composition according to claim 1, wherein the conductive resin composition is included in the conductive resin composition at a ratio of 5% or more with respect to the photocurable resin.
(Additional remark 7) The said photopolymerizable compound is contained in the said conductive resin composition in the ratio of 10% or more, The conductive resin composition of Claim 6 characterized by the above-mentioned.
(Appendix 8) The electroconductive compound according to any one of appendices 3 to 7, wherein the photopolymerizable compound further contains a photocurable monomer or oligomer containing one or two photosensitive groups. Resin composition.
(Supplementary Note 9) The conductive resin is polyaniline, polypyrrole, polythiophene, poly (3-alkylthiophene), polythiophene vinylene, polyfuran, polyselenophene, polyfurylene vinylene, polyparaphenylene, polyparaphenylene vinylene, polythienylene. Either of vinylene, polyisothianaphthene, polyacetylene, polynaphthalene, polyanthracene, polypyrene, polyazulene, polynaphthalene vinylene, polyparaphenylene sulfide, and derivatives thereof, any one of claims 1-8 The conductive resin composition according to one item.
(Additional remark 10) The said conductive resin composition consists of polyaniline or its derivative (s), The conductive resin composition as described in any one of Additional remarks 1-9 characterized by the above-mentioned.
(Additional remark 11) The said conductive resin is contained in the ratio of 0.5 mass%, The conductive resin composition as described in any one of Claims 1-10 characterized by the above-mentioned.
(Additional remark 12) Furthermore, a dopant is contained, The said dopant consists of sulfonic acids or polysulfonic acids, The conductive resin composition as described in any one of Additional remarks 1-11 characterized by the above-mentioned.
(Additional remark 13) The said dopant consists of dodecylbenzenesulfonic acid and naphthalenesulfonic acid, The conductive resin composition of Additional remark 12 characterized by the above-mentioned.
(Appendix 14) The conductive resin composition according to any one of appendices 1 to 13, further comprising an aggregation inhibitor.
(Supplementary note 15) The conductive composition according to supplementary note 17, wherein the aggregation inhibitor is selected from a cyclic organic substance having a polar part and a nonpolar part in a molecule, a lipophilic aromatic liquid, and primary amines.
(Supplementary Note 16) A conductive resin film formed using the conductive resin composition according to any one of Supplementary Notes 1 to 15.
(Supplementary Note 17) The conductive resin film according to Supplementary Note 16, wherein the conductive resin film includes a pattern having a size of 20 μm or less (Supplementary Note 18). Applying a conductive resin composition to form a coating film;
And a step of exposing the coating film and patterning the conductive resin film.

It is FIG. (1) which shows the manufacturing process of the electronic device by the 2nd Embodiment of this invention. It is FIG. (2) which shows the manufacturing process of the electronic device by the 2nd Embodiment of this invention. It is FIG. (3) which shows the manufacturing process of the electronic device by the 2nd Embodiment of this invention. It is FIG. (4) which shows the manufacturing process of the electronic device by the 2nd Embodiment of this invention. (A), (B) is a figure which shows the structure of the photosensitive multilayer conductive film by the modification of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 Polyimide substrate 11A Wiring pattern 11a Contact pad 12 Conductive resin film 12a Opening part 13 Semiconductor chip 21, 23 Photosensitive resin film 22 Conductive resin film

Claims (5)

A photopolymerizable resin having at least one of an acidic group and a salt of an acidic group in a side chain;
A photopolymerizable compound;
A conductive resin composition containing a conductive resin,
The said photopolymerizable compound has at least one among an acidic group and a salt of an acidic group in a side chain, The conductive resin composition characterized by the above-mentioned.   The conductive resin composition according to claim 1, further comprising a dopant.   The conductive resin composition according to claim 1, further comprising an aggregation inhibitor.   A conductive resin film formed using the conductive resin composition according to claim 1. The process of apply | coating the conductive resin composition as described in any one of Claims 1-3, and forming a coating film,
And a step of exposing the coating film and patterning the conductive resin film.

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