TWI515277B - Conductive resin composition and conductive circuit - Google Patents

Description

Conductive resin composition and conductive circuit

The present invention relates to a conductive resin composition and a conductive circuit formed using the conductive resin composition.

A conventional document which discloses a conductive paste for forming a conductive pattern film on a substrate is disclosed in Patent Document 1 and Patent Document 2.

Patent Documents 1 and 2 disclose a conductive paste containing a conductive powder, an organic binder, a photopolymerizable monomer, and a photopolymerization initiator.

The conductive paste is fired at a temperature of 500 ° C or higher to remove organic components in the paste to ensure conductivity of the conductive circuit layer.

Further, in the conductive paste which is fired as described above, generally, the glass frit is contained together with the conductive powder, and the glass frit is melted while the organic component in the paste is removed by firing to ensure the conductivity of the conductive pattern. And adhesion to the substrate.

However, since these photosensitive conductive pastes are fired at a temperature of 500 ° C or higher, it is difficult to use them on a substrate having a weak heat resistance.

Further, in recent years, although the coating film strength of the conductive pattern film has been further improved, the conventional conductive paste has other necessary characteristics. This requirement cannot be fully met.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-280181

[Patent Document 2] Japanese Patent No. 4411113

In order to solve the above problems, the present invention provides a conductive resin composition which can be applied to a substrate having a weak heat resistance and which can ensure excellent conductivity, and a conductive circuit formed using the conductive resin composition.

Further, the present invention provides a conductive resin composition having improved coating film strength and adhesion to a base substrate, and a conductive circuit formed using the conductive resin composition.

In order to solve the above problems, the present invention provides a conductive resin composition comprising a carboxyl group-containing resin, a conductive powder, a reactive diluent, a photopolymerization initiator having an absorption wavelength on the h-line, and a thermosetting component. And, phenothiazine.

Further, the present invention provides a conductive resin composition in which the reactive diluent is a polyfunctional acrylate monomer.

Further, the present invention provides a conductive resin composition in which the above polyfunctional acrylate monomer is a tetrafunctional acrylate monomer.

Moreover, the present invention provides a conductive resin composition in which the tetrafunctional acrylate monomer is an acrylate monomer described in the following chemical formula (I).

In the formula (I), X ¹ represents a group containing an acryloxy group, X ² represents a group containing a methacryloxy group, and X ³ and X ⁴ each independently represent a group containing an acryloxy group, or a group a group based on a propylene oxy group, wherein at least one of X ³ and X ⁴ represents a group containing a methacryloxy group, and L ¹ and L ² each independently represent the following formula

* indicates a bonding site with Z, and Z indicates a binary bond group.

Moreover, the present invention provides L ¹ and L ² in the general formula (I)

(In the formula (III), * represents a conductive resin composition represented by a bonding site with Z).

Moreover, the present invention provides a conductive resin composition in which the tetrafunctional acrylate monomer represented by the general formula (I) is represented by the following formula (IV).

In the formula (IV), Z ¹ represents an alkylene group.

R ¹ represents a hydrogen atom.

R ² represents a methyl group.

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group. However, at least one of R ³ and R ⁴ represents a methyl group.

Moreover, the present invention provides a light concentrating having an absorption wavelength on the h line. The starting agent is the conductivity of 1-[9-ethyl-6-2(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-ethylindenyl) Resin composition.

Moreover, the present invention provides a conductive resin composition in which the thermosetting component is a blocked isocyanate.

Moreover, the present invention provides a resin containing a carboxyl group as a conductive resin composition not containing a double bond.

Moreover, the present invention provides a conductive resin composition containing no carboxyl group-containing resin and no aromatic ring.

Moreover, the present invention provides a conductive resin composition further comprising an organic acid.

Moreover, the present invention provides a conductive resin composition comprising the organic acid as an organic acid having no aromatic ring.

Moreover, the present invention provides a conductive resin composition comprising the organic acid which does not have an aromatic ring and has two or more carboxyl groups.

Furthermore, the present invention provides a conductive circuit formed by coating and drying the conductive resin composition on a substrate.

According to the present invention, it is possible to provide a conductive resin composition which can be applied to a substrate which is weak in heat resistance and which can ensure excellent conductivity, and which is excellent in coating film strength and adhesion to an underlying substrate, and the use of the conductive resin. A conductive circuit formed by the composition.

First, the ingredients to be formulated in the composition of the present invention will be explained.

(components blended with the conductive resin composition) (resin containing carboxyl group)

As the resin containing a carboxyl group, a conventionally known resin compound having a carboxyl group in its molecule can be used.

The resin containing a carboxyl group may be a carboxyl group-containing photosensitive resin containing a double bond, but a carboxyl group-containing resin not containing a double bond is preferred. Since the carboxyl group-containing resin which does not contain a double bond does not react with a reactive diluent, no intermolecular bond is formed. Therefore, the resin containing a carboxyl group does not become a large molecular weight and is easily removed at the time of development. As a result, the conductive powder can be made dense, and the specific resistance value of the conductive pattern film is lowered.

Further, even if the resin containing a carboxyl group has a double bond in a very small proportion, as long as the ratio is in the range of the same effect as the present invention in the case of a resin containing a carboxyl group which does not contain a double bond at all, the carboxyl group containing the double bond is contained. The resin is also included in the "carboxyl group-containing resin which does not contain a double bond" of the present invention. The resin containing a carboxyl group which does not contain a double bond can be, for example, a double bond equivalent of 10,000 or more.

Among the resins containing a carboxyl group, among the resins containing a carboxyl group which does not contain a double bond, a carboxyl group-containing resin which does not contain either a double bond or an aromatic ring is preferable. By forming a structure that does not include an aromatic ring, the light absorption of the resin containing the carboxyl group itself is suppressed, and the photoreactivity of the reactive diluent can be relatively increased.

Specific examples of the carboxyl group-containing resin which does not contain a double bond and an aromatic ring are listed. As described below.

(1) a carboxyl group-containing resin obtained by copolymerizing one or more kinds of unsaturated carboxylic acids such as (meth)acrylic acid and other compounds having an unsaturated double bond, and (2) by maleic anhydride a resin having a carboxyl group obtained by copolymerizing an acid anhydride having an unsaturated double bond with a compound having an unsaturated double bond, and (3) a compound having an unsaturated double bond and an acid compound having an unsaturated double bond a copolymer obtained by reacting a compound having a hydroxyl group to obtain a carboxyl group-containing resin, and (4) a copolymer of a compound having an epoxy group and an unsaturated double bond and a compound having an unsaturated double bond to react a saturated carboxylic acid. The resin containing a carboxyl group obtained by reacting the generated secondary hydroxyl group with a polybasic acid anhydride, and (5) a resin containing a carboxyl group obtained by reacting a polybasic acid anhydride with a polymer having a hydroxyl group, but is not limited thereto.

Further, in the present specification, the term "(meth)acrylic acid" is a generic term for acrylic acid, methacrylic acid, and the like, and the other similar expressions are also the same.

The carboxyl group-containing resin as described above is due to the backbone. The polymer has a plurality of free carboxyl groups on its side chain, so it can be developed by a dilute alkaline aqueous solution.

Further, the acid value of the carboxyl group-containing resin is preferably in the range of 40 to 200 mgKOH/g, more preferably 45 to 120 mgKOH/g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, it is difficult to perform alkali imaging. On the other hand, when it exceeds 200 mgKOH/g, in order to cause exposure to the developing solution The dissolution of the light portion causes the wire to be finer than necessary, and depending on the case, the exposed portion and the unexposed portion are dissolved and peeled off by the developing liquid without any difference, and the drawing of the normal conductive pattern becomes difficult. Not good.

Further, the mass average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, and more preferably in the range of 5,000 to 100,000. When the mass average molecular weight is less than 2,000, there is a problem that the non-adhesive property is deteriorated, and the moisture resistance of the conductive pattern film after exposure is deteriorated, and the film is reduced at the time of development, and the resolution is greatly deteriorated. On the other hand, when the mass average molecular weight exceeds 150,000, there is a problem that the visibility is remarkably deteriorated, and storage stability is deteriorated.

The compounding amount of the carboxyl group-containing resin is preferably from 3 to 50% by mass, and more preferably from 5 to 30% by mass, based on the total of the conductive resin composition. When the amount is less than the above range, the strength of the conductive pattern film is lowered, which is not preferable. On the other hand, when the amount is more than the above range, the viscosity is high, and the coatability and the like are lowered, which is not preferable.

(conductive powder)

First, the material of the conductive powder may be any one as long as it imparts conductivity to the conductive resin composition. Examples of such a conductive powder include Ag, Au, Pt, Pd, Ni, Cu, Al, Sn, Pb, Zn, Fe, Ir, Os, Rh, W, Mo, Ru, etc. good. These conductive powders may be used in the form of the above-mentioned component monomers, or may be used in the form of an alloy or an oxide. Further, tin oxide (SnO ₂ ), indium oxide (In ₂ O ₃ ), ITO (indium tin oxide) or the like can also be used. Further, the conductive powder may be carbon powder such as carbon black, graphite or carbon nanotube. However, it is necessary to pay attention because it reduces light transmission.

The shape of the conductive powder is not particularly limited, and is preferably a needle shape or a spherical shape in addition to the sheet shape. According to this, it is possible to form a conductive pattern film having improved light transmittance and excellent resolution.

In order to form a fine line, the conductive powder preferably has a maximum particle diameter of 30 μm or less. The resolution of the conductive pattern film is improved by setting the maximum particle diameter to 30 μm or less.

Further, in the conductive powder, the average particle diameter of the random 10 conductive powders was observed by an electron microscope (SEM) at 10,000 times, and the range was preferably 0.1 to 10 μm or less. The average particle diameter is smaller than this range, and it is less preferable because the resistance value is increased due to an increase in contact resistance. On the other hand, when the average particle diameter is larger than the above range, when the screen pattern is printed using the screen plate, workability is deteriorated due to clogging of the screen holes, and it is difficult to form a fine line, which is not preferable. Further, it is preferred to use an average particle diameter of 0.5 to 3.5 μm as measured by a particle size analyzer (Microtrac).

The blending ratio of the conductive powder is preferably 800 to 900 parts by mass based on 100 parts by mass of the carboxyl group-containing resin. When the blending ratio of the conductive powder is too small, the electric resistance value of the conductive resin composition becomes high, and sufficient conductivity cannot be obtained. On the other hand, when a large amount of conductive powder is contained, the light transmittance is deteriorated, and the formation of the conductive pattern film by exposure is deteriorated, which is not preferable.

(reactive diluent)

The conductive resin composition of the present invention uses a reactive diluent because it is crosslinked by light. It is preferred to use a (meth) acrylate compound as the reactive diluent. Further, the reactive diluent is preferably polyfunctional. The reason why the polyfunctionality is preferable is that the photoreactivity is improved and the resolution is excellent as compared with the case where the number of the functional groups is one.

The methyl (acrylate) compound may, for example, be a polyfunctional (meth) acrylate monomer or oligomer (a bifunctional or higher (meth) acrylate monomer or oligomer, and specifically, for example, conventionally used Polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, etc. are well known. Specifically, a hydroxyalkyl acrylate such as 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol or the like can be exemplified. Diols of diols; acrylamides such as N,N-dimethyl decylamine, N-methylol acrylamide, N,N-dimethylaminopropyl acrylamide; Aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, and neopentyl a polyol such as an alcohol, dipentaerythritol or trishydroxyethyl isocyanate or such an ethylene oxide adduct, a propylene oxide adduct, or an ε-caprolactone adduct Multivalent acrylic Ester; phenoxy acrylate, bisphenol A diacrylate, and epoxide ethylene oxide adducts of such phenols or polyvalent acrylates such as propylene oxide adducts; glycerol epoxide a polyvalent acrylate of a glycidyl ether such as propyl ether, glycerol triepoxypropyl ether, trimethylolpropane triepoxypropyl ether or triepoxypropyl tripolyisocyanate; not limited to the foregoing, Polyether polyol, polycarbonate diol, hydroxy The polyol having a polybutadiene such as a polybutadiene or a polyester polyol is directly acrylated, or an acrylate and a melamine acrylate which are acrylated with a diisocyanate and a urethane, and a corresponding acrylate At least any one of methacrylates and the like.

Further, a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, an epoxy acrylate resin which reacts with acrylic acid, or a hydroxyl group of the epoxy acrylate resin may be used to make pentaerythritol three. An epoxy urethane acrylate compound or the like which is a reaction of a hydroxy acrylate such as an acrylate with an ethyl urethane compound of a diisocyanate such as isophorone diisocyanate is used as a reactive diluent. Such an epoxy acrylate-based resin can improve the photocurability without reducing the dryness of the touch.

Among them, it is preferred to use a polyfunctional (meth) acrylate monomer, particularly a tetrafunctional (meth) acrylate monomer. The 4-functional (meth) acrylate monomer may, for example, be neopentyltetraol tetraacrylate, neopentyltetraol tetramethacrylate or the like.

The tetrafunctional (meth) acrylate monomer is preferably a tetrafunctional urethane acrylate monomer or ester acrylate described in the chemical formulas (I) and (II).

In the formula (I), X ¹ represents a group containing an acryloxy group.

X ² represents a group containing a methacryloxy group.

X ³ and X ⁴ each independently represent a group containing an acryloxy group or a group containing a methacryloxy group. However, at least one of X3 and X4 represents a group containing a methacryloxy group.

L ¹ and L ² are each independently represented

* indicates the bonding site with Z.

Z represents a divalent linking group.

Further, the acrylate monomer is L ¹ and L ² in the general formula (I)

The urethane acrylate represented is preferred. In the formula (III), * represents a bonding site with Z.

Further, the monomer represented by the formula (I) is preferably urethane acrylate represented by the following formula (IV).

In the formula (IV), Z ¹ represents an alkylene group.

R ¹ represents a hydrogen atom.

R ² represents a methyl group.

R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group. However, at least one of R ³ and R ⁴ is less than a methyl group.

Further, the tetrafunctional acrylate monomer is particularly preferably one-to-one urethane acrylate or acrylate acrylate having an acryl group and a methacryl group.

Such a 4-functional urethane acrylate or ester acrylate, for example, an acrylic acid is added to the epoxy methacrylate, and a hydroxyl group generated at this time is preferably reacted with a diisocyanate or a dicarboxylic acid.

A commercially available product of a 4-functional urethane acrylate can be exemplified by, for example, NK Oligo U-4HA (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.).

Among these tetrafunctional acrylate monomers, a tetrafunctional acrylate monomer represented by the formula (I) is preferred. Because of this 4-functional acrylate single Since the number of the functional groups is large, the photoreactivity is excellent and the resolution is excellent.

Further, since X ¹ and X ^{2 of the} tetrafunctional acrylate monomer are different from each other, the reaction between X1 and X2 in the molecule is slow at the time of photocuring. However, the X ¹ or X ^{2 of the} acrylate monomer reacts faster with the molecules of X ¹ or X ² of the other acrylate monomers than the intramolecular reaction. Thereby, an intermolecular bond is formed between the plural acrylate monomers, and thus the conductive resin composition is further hardened and shrunk. Next, the low-temperature heat treatment is performed to further promote the intermolecular reaction, and the conductive resin composition is sufficiently cured and shrunk. As a result, it is considered that the conductive powder is dense, and the specific resistance value of the conductive pattern film is further lowered.

The amount of the reactive diluent to be added is not particularly limited, and is preferably from 10 to 100 parts by mass, more preferably from 20 to 80 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. When the amount of the compound is less than 10 parts by mass, the photocurability is lowered, and it is difficult to form a pattern of a conductive pattern by alkali imaging after irradiation with an active energy ray, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the solubility in the aqueous alkali solution is lowered to make the conductive pattern film brittle, which is not preferable.

(Photopolymerization initiator with absorption wavelength on h line)

The wavelength of 405 nm is called the h line. The improvement of the adhesion of the subject of the present invention will be described later in detail, but it is possible to increase the thermosetting property by blending a thermosetting component. In the present invention, a photopolymerization initiator having an absorption wavelength on the h-line is used in order to satisfy a higher required characteristic. In other words, since the h line is longer than the i line and the like, the deep hardenability is excellent, and the knot is excellent. As a result, the photohardenability can be improved, and the required characteristics such as the high strength of the coating film can be made sufficient.

The photopolymerization initiator is known, for example, an oxime ester photopolymerization initiator, an acetophenone photopolymerization initiator, a phosphine oxide photopolymerization initiator, a hydroxyphenylketone photopolymerization initiator, and a titanocene. A photopolymerization initiator or the like.

In the present invention, the photopolymerization initiator is not particularly limited as long as it is an optical polymerization initiator having an absorption wavelength on the h-line.

For example, the substance name and commercial product of the photopolymerization initiator with absorption on the h-line: The oxime ester photopolymerization initiator can be exemplified by NCI-831 manufactured by ADEKA Co., Ltd.: 1-[9-ethyl-6-2(2-methylbenzhydryl)-9H-indazol-3-yl]- 1-(O-Ethyl hydrazine), CGI-325 manufactured by BASF Japan Co., Ltd., TOE-04-A3 manufactured by Nippon Chemical Industry Co., Ltd., IrgOXE01:1 manufactured by BASF Japan Co., Ltd. 2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzylidenehydrazine).

The acetophenone photopolymerization initiator can be exemplified by Irg369: 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, Irg379 (acetophenone) ), Irg379EG (acetophenone): 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholinylphenyl)-butanone-1-one.

The phosphine oxide-based photopolymerization initiator can be exemplified by Irg 819 manufactured by BASF Japan Co., Ltd.: bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide, Irg1800: bis (2,6- Dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide and 1-hydroxy-cyclohexyl-phenyl-one, LucirinTPO, BASF Japan, manufactured by BASF Japan Co., Ltd. Company) SpeedCureTPO: 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide, Darocure 4265 by BASF Japan Co., Ltd.: 2,4,6-trimethylbenzhydryl-diphenyl-oxidation Phosphine and 2-hydroxy-2-methyl-1-phenyl-propan-1-one.

The hydroxyphenyl ketone photopolymerization initiator can be exemplified by Irg127: 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl manufactured by BASF Japan Co., Ltd. Base]-phenyl}-2-methyl-propan-1-one.

The titanocene-based photopolymerization initiator can be exemplified by Irg784 (titanocene system) manufactured by BASF Japan Co., Ltd.: bis(n5-2,4-cyclopentadien-1-yl)-bis (2.6-two) Fluorin-3-(1H-pyrrol-1-yl)-phenyl)titanium.

Among the photopolymerization initiators exemplified above, especially 1-[9-ethyl-6-2(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O- Ethyl hydrazine is preferred.

Further, these photopolymerization initiators may be used alone or in combination of two or more.

The amount of the photopolymerization initiator which has an absorption wavelength in the h-line is not particularly limited, but is preferably 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. The scope is appropriate. When the amount of the photopolymerization initiator is less than 0.01 parts by mass, the photocurability is insufficient, or the conductive pattern film is peeled off, and the properties of the conductive pattern film such as chemical resistance are lowered, which is not preferable. On the other hand, when it exceeds 30 parts by mass, the photopolymerization initiator has a high light absorption on the surface of the conductive pattern film, and the deep curing property tends to be lowered, which is not preferable.

Further, in order to enhance the sensitivity of the photopolymerization initiator, it is preferred to formulate a sensitizer. Such sensitizers can be exemplified by DETX-S: alkyl sultone, EAB: 4, 4'-bis(diethylamino)benzophenone, NF-TMC (coumarin) Wait.

The amount of the sensitizer to be added is not particularly limited, but is preferably in the range of 0.1 to 1 part by mass based on 100 parts by mass of the photopolymerization initiator.

(thermosetting component)

The conductive resin composition of the present invention contains a thermosetting component in order to enhance the toughness of the cured film and the adhesion to the underlying substrate. The thermosetting component used in the present invention may be an amine resin such as a melamine resin or a benzoguanamine resin, a blocked isocyanate compound (a compound having a blocked isocyanate group in one molecule), or a ring having two or more molecules in the molecule. a compound of an ether group and/or a cyclic thioether group (hereinafter referred to as a cyclic (thio)ether group), a cyclic carbonate compound, a polyfunctional epoxy compound, a polyfunctional oxetane compound, an episulfide resin A thermosetting resin which is conventionally used, such as a melamine derivative. The block isocyanate compound is particularly preferable for improving the toughness of the cured film obtained from the conductive resin composition and the adhesion to the underlying substrate.

The blocked isocyanate group contained in the blocked isocyanate compound is protected by reacting the isocyanate group with the blocking agent to temporarily become an inert group. Upon heating to a specific temperature, the blocking agent dissociates to form an isocyanate group.

The block cyanate compound is an addition reaction product of an isocyanate compound and an isocyanate blocking agent. The isocyanate compound obtained by the reaction with a blocking agent is exemplified by an isocyanurate type, a biuret type, addition molding, and the like. The isocyanate As the acid ester compound, for example, the same aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate as described above is used.

The isocyanate blocking agent is exemplified by a phenolic terminal blocking agent such as phenol, cresol, xylenol, chlorophenol or ethylphenol; ε-caprolactam, δ-valeroguanamine, γ-butyrolactone and An internal amide-based blocking agent such as β-propionylamine; an active methylene-based blocking agent such as ethyl acetoxyacetate or acetonitrile; methanol, ethanol, propanol, butanol, pentanol, and B Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, An alcohol-based terminal blocking agent such as methyl lactate or ethyl lactate; an anthraquinone blocking agent such as formaldehyde oxime, acetaldehyde oxime, acetamidine, methyl ethyl ketone oxime, diethyl hydrazino monohydrazine or cyclohexane hydrazine; Mercaptan-based blocking agent such as butyl mercaptan, hexyl mercaptan, tert-butyl mercaptan, thiophene, methyl thiophene or ethyl thiophene; acid amide amine blocking agent such as decylamine or benzamidine; amber A quinone imine blocking agent such as quinone and maleimine; an amine blocking agent such as xylidine, aniline, butylamine or dibutylamine; an imidazole seal such as imidazole or 2-ethylimidazole Terminal agent Imine and propylene imine imine extending capping agent.

The blocked isocyanate compound may be a commercial one, and may be, for example, 7950, 7951, 7960, 7961, 7982, 7990, 7991, 7992 (above, manufactured by Baxenden, trade name) Sumidur BL-3175, BL-4165, BL -1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmosome 2170, Desmosome 2265 (above, made by Sumitomo Bayeramide, trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above is manufactured by Japan Polyurethane Industrial Co., Ltd., trade name), B-830, B-815, B-846, B-870, B-874, B-882 (manufactured by Mitsui Takeda Chemical Co., Ltd., Name), TPA-B80E, 17B-60PX, E402-B80T, MF-B60B, MF-K60B, SBN-70D (product name manufactured by Asahi Kasei Chemicals Co., Ltd.), Carens MOI-BM (product name of Showa Denko Co., Ltd., trade name), and the like. Further, Sumidur BL-3175 and BL-4265 were obtained by using methyl ethyl hydrazine as a terminal blocking agent.

The above-mentioned compound having a blocked isocyanate group may be used alone or in combination of two or more.

The compounding amount of the compound having a blocked isocyanate group is preferably from 1 to 100 parts by mass, more preferably from 2 to 70 parts by mass, per 100 parts by mass of the resin containing a carboxyl group. When the amount of the above formulation is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the storage stability is lowered, which is not preferable.

Although the dissociation temperature of the block isocyanate blocking agent is not particularly limited, it is desirable that the blocking agent does not react at a pre-drying temperature (for example, 80 to 90 ° C), and is reacted at the final heat treatment, so that it is pre-dried. The temperature at which the temperature is high is, for example, 100 ° C or more. Further, when a polyester resin is used as the substrate, for example, if the heat treatment temperature is too high, the substrate becomes discolored, and therefore the dissociation temperature of the blocking isocyanate blocking agent prevents the discoloration of the substrate, for example, 140 ° C or lower. It is preferred to carry out the heat treatment at a temperature at which the substrate does not change color.

A thermosetting component having two or more cyclic ether groups and/or a cyclic thioether group (hereinafter, simply referred to as a cyclic (thio)ether group) in a molecule is a molecule a compound having two or more cyclic ether groups or cyclic thioether groups of two or more members, or a compound of two types, for example, having at least two or more epoxy groups in the molecule. a compound, that is, a polyfunctional epoxy compound, a compound having at least two or more oxetanyl groups in a molecule, that is, a polyfunctional oxetane compound, and a compound having two or more thioether groups in a molecule, That is, an episulfide resin or the like.

Examples of the polyfunctional epoxy compound include, for example, jER828, jER834, jER1001, and jER1004 manufactured by Mitsubishi Chemical Corporation, Epiclon 840, Epiclon 850, Epiclon 1050, and Epiclon 2055 manufactured by DIC Corporation, and Epotohto YD-011, YD-013, and YD manufactured by Dongdu Chemical Co., Ltd. -127, YD-128, DER317, DER331, DER661, DER664 manufactured by The Dow Chemical Company, SUMI-EPOXY ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Industries, Ltd. Asahi Kasei Industrial Co., Ltd. AER330, AER331, AER661, AER664, etc. (both trade names) of bisphenol A epoxy resin; Mitsubishi Chemical Corporation's jERYL903, DIC company's Epiclon152, Epiclon165, Dongdu Chemical Company Epotohto YDB-400, YDB-500, DER542 manufactured by Dow Chemical Co., Ltd., SUMI-EPOXY ESB-400, ESB-700 manufactured by Sumitomo Chemical Industries, AER711, AER714, etc. by Asahi Kasei Industrial Co., Ltd. Brominated epoxy resin for the trade name; jER152, jER154 manufactured by Mitsubishi Chemical Corporation, DEN431, DEN438 manufactured by Dow Chemical Co., Ltd., Epiclon N-730, Epiclon N-770, Epiclon N-865 manufactured by DIC Corporation, Dong Duhua Corporation of Epotohto YDCN-701, YDCN-704, manufactured by Nippon Kayaku Co., of EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, SUMI-EPOXY ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Industries, Ltd., AERECN-235, ECN-299, manufactured by Asahi Kasei Corporation And other phenolic varnish type epoxy resins (all of which are trade names); Epiclon 830 manufactured by DIC Corporation, jER807 manufactured by Mitsubishi Chemical Corporation, Epotohto YDF-170, YDF-175, YDF-2004 manufactured by Dongdu Chemical Co., Ltd. (all are trade names) Bisphenol F type epoxy resin; hydrogenated bisphenol A type epoxy resin such as Epotohto ST-2004, ST-2007, ST-3000 (trade name) manufactured by Dongdu Chemical Co., Ltd.; jER604 manufactured by Mitsubishi Chemical Corporation, Epotohto YH-434 manufactured by Dongdu Chemical Co., Ltd., SUMI-EPOXY ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. (both trade names), epoxy propylamine epoxy resin; Equinone urethane epoxy resin; Daicel Aliphatic epoxy resin of CELOXIDE 2021 (both trade names) manufactured by Chemical Industry Co., Ltd.; YL-933 manufactured by Mitsubishi Chemical Corporation, TEN, EPPN-501, EPPN-502, etc. by Dow Chemical Co., Ltd. Trade name) trishydroxyphenylmethane type epoxy resin; YL-6056, YX-4000, YL-6121 manufactured by Mitsubishi Chemical Corporation Product name) bis-xylenol type or biphenol type epoxy resin or a mixture thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., EXA-1514 manufactured by DIC Corporation Bisphenol S-type epoxy resin, etc.; bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; jERYL-931 manufactured by Mitsubishi Chemical Corporation (all are trade names) Tetrahydroxyphenylethane type epoxy resin; heterocyclic epoxy resin of TEPIC (both trade name) manufactured by Nissan Chemical Industries Co., Ltd.; second ring of BLEMMER DGT manufactured by Nippon Oil & Fats Co., Ltd. Oxypropyl phthalate resin; tetra-epoxypropyl dimethyl phenol ethane resin such as ZX-1063 manufactured by Dongdu Chemical Co., Ltd.; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032 manufactured by DIC Corporation, Epoxy resin containing naphthalene group such as EXA-4750 and EXA-4700; epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC Corporation; CP-50S and CP manufactured by Nippon Oil Co., Ltd. -50M epoxy methacrylate copolymerized epoxy resin; further copolymerized epoxy resin of cyclohexylmaleimide and epoxypropyl methacrylate; epoxy modified polybutadiene A rubber derivative (for example, PB-3600 manufactured by Daicel Chemical Industry Co., Ltd.), a CTBN modified epoxy resin (for example, YR-102 manufactured by Tosho Kasei Co., Ltd., YR-450, etc.), and the like, but is not limited thereto. These epoxy resins may be used alone or in combination of two or more. Among these, a novolac type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture of these is preferable.

The above polyfunctional oxetane compound can be exemplified by bis[(3-methyl-3-oxetanylmethoxy)methyl]ether, bis[(3-ethyl-3-oxetanylmethoxy). Methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3-ethyl-3-oxetanylmethoxy) Methyl]benzene, (3-methyl-3-oxetanyl) acrylate, (3-ethyl-3-oxetanyl) acrylate, (3-methyl-3) -oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl methacrylate or polyfunctional oxetane of such oligomers or copolymers In addition to alkane, oxetane and novolak resins, poly(p-hydroxystyrene), Cardo type bisphenols, calixarenes, cup-resorcinol aromatics, or half An etherified product of a resin having a hydroxyl group such as a decane or the like. In addition, it is also possible to exemplify the presence of an oxetane ring. A copolymer of a saturated monomer and an alkyl (meth) acrylate, or the like.

The compound having two or more cyclic thioether groups in the molecule may, for example, be bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Further, an episulfide resin obtained by substituting an oxygen atom of an epoxy group of a novolac type epoxy resin with a sulfur atom by the same synthesis method may be used.

Further, in the conductive resin composition of the present invention, in order to improve the curability of the conductive resin composition and the toughness of the obtained cured film, it is possible to add two or more isocyanate groups in one molecule together with the above-mentioned blocked isocyanate. Compound. The compound having two or more isocyanate groups in one molecule is exemplified by a compound having two or more isocyanate groups in one molecule, that is, a polyisocyanate compound.

As the polyisocyanate compound, for example, an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate can be used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, and o-di Toluene diisocyanate, m-xylene diisocyanate and 2,4-toluene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, and 4,4-methylene double (ring). Hexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate may be exemplified by bicycloheptane triisocyanate. And an adduct of an isocyanate compound, a biuret body, and a trimeric isocyanate body exemplified above.

Such a compound having two or more isocyanate groups in one molecule The blending amount is preferably from 1 to 100 parts by mass, more preferably from 2 to 70 parts by mass, per 100 parts by mass of the resin containing a carboxyl group. When the amount of the above formulation is less than 1 part by mass, sufficient toughness of the coating film cannot be obtained, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the storage stability is lowered, which is not preferable.

(phenothiazine)

As described above, by using a photopolymerization initiator having an absorption wavelength on the h-line, it is possible to promote an improvement in characteristics such as adhesion due to an increase in photocurability. On the other hand, on the other hand, since the above-mentioned photopolymerization initiator is added, the resolution has a halo phenomenon, so phenothiazine is added. In other words, since phenothiazine has an absorption wavelength in a long wavelength region of 400 nm or more, the absorbance at the time of using the coating film of the composition can be adjusted, and as a result, the adhesion property is maintained, and halo phenomenon is not generated, and adhesion is improved. Sex.

That is, since phenothiazine has a function as a photopolymerization inhibitor, by adding this substance, the radical polymerization which occurs inside the conductive resin composition by exposure can suppress the type of the corresponding polymerization inhibitor and One of the added amounts is a quantitative amount of free radical polymerization. Thereby, light reaction to weak light such as scattered light can be suppressed. Further, since phenothiazine has a function as a thermal polymerization inhibitor, by adding this substance, a line of a finer conductive pattern film can be clearly formed by preventing polymerization of heat or polymerization over time, and as a result, While maintaining the adhesion characteristics, the resolution can also be improved.

The amount of the phenothiazine added is preferably 0.001 to 3 parts by mass, more preferably 0.01 to 2 parts by mass, per 100 parts by mass of the carboxyl group-containing resin. Within the scope. When the amount is smaller than this range, the effect of suppressing polymerization cannot be exhibited, and even a low exposure amount due to light scattering is hardened, and the shape of the line is likely to become coarse. Moreover, if it is more than this range, the sensitivity is lowered, and a large amount of exposure is required, so attention should be paid.

(organic acid)

The type of the organic acid is not limited, and is preferably an organic acid having no aromatic ring, and more preferably an organic acid having no aromatic ring and having two or more carboxyl groups. By using such an organic acid, the light absorption property of the organic acid itself can be suppressed, and the photoreactivity of the reactive diluent can be relatively increased, and excellent resolution can be obtained. Further, a composition having a lower specific resistance can be obtained.

If such an organic acid is exemplified, a dicarboxylic acid, a tricarboxylic acid, a tetracarboxylic acid, a pentacarboxylic acid, a hexacarboxylic acid, especially a dicarboxylic acid is preferred. Specific examples of the dicarboxylic acid include 2,2'-sulfinic acid, adipic acid, glutaric acid, oxalic acid, tartaric acid, malic acid, maleic acid, fumaric acid, malonic acid, and succinic acid. Specific examples of the tricarboxylic acid include aconitic acid, citric acid, isocitric acid, and oxalic acid succinic acid. Specific examples of the tetracarboxylic acid include 1,2,3,4-butanetetracarboxylic acid, ethylenetetracarboxylic acid, and the like. The hexacarboxylic acid can be exemplified by 1,2,3,4,5,6-cyclohexacarboxylic acid.

In the present invention, the organic acid may be contained in an amount of 0.1 to 5 parts by mass, based on 100 parts by mass of the conductive powder. When the amount of the organic acid is less than 0.1 part by mass based on 100 parts by mass of the conductive powder, the reaction between the conductive powder and the carboxyl group-containing resin causes a long-term storage stability, and the above-described blending is performed. When the amount exceeds 5 parts by mass, it is easy to suck The moisture in the wet air is not so good.

In order to further enhance the effects of the present invention, or to further exhibit other effects within a range that does not impair the effects of the present invention, the conductive resin composition of the present invention is compatible with the above-mentioned carboxyl group-containing resin, conductive powder, reactive diluent, The photopolymerization initiator, the thermosetting component, the phenothiazine, and the appropriately formulated organic acid having an absorption wavelength on the h-line may contain other components exemplified below.

(Dispersant)

By dispersing the dispersant, the dispersibility and sedimentation property of the conductive resin composition can be improved.

Examples of the dispersing agent are, for example, ANTI-TERRA-U, ANTI-TERRA-U100, ANTI-TERRA-204, ANTI-TERRA-205, DISPERBYK-101, DISPERBYK-102, DISPERBYK-103, DISPERBYK-106, DISPERBYK-108, DISPERBYK -109, DISPERBYK-110, DISPERBYK-111, DISPERBYK-112, DISPERBYK-116, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164 DISPERBYK-166, DISPERBYK-167, DISPERBYK-168, DISPERBYK-170, DISPERBYK-171, DISPERBYK-174, DISPERBYK-180, DISPERBYK-182, DISPERBYK-183, DISPERBYK-185, DISPERBYK-184, DISPERBYK-191, DISPERBYK -192, DISPERBYK-2000, DISPERBYK-2001, DISPERBYK- 2009, DISPERBYK-2020, DISPERBYK-2025, DISPERBYK-2050, DISPERBYK-2070, DISPERBYK-2095, DISPERBYK-2096, DISPERBYK-2150, BYK-P104, BYK-P104S, BYK-P105, BYK-9076, BYK-9077, BYK-220S (made by BYK Japan Co., Ltd.), DISPARLON 2150, DISPARLON 1210, DISPARLON KS-860, DISPARLON KS-873N, DISPARLON 7004, DISPARLON 1830, DISPARLON 1860, DISPARLON 1850, DISPARLON DA-400N, DISPARLON PW-36, DISPARLON DA-703-50 (made by Nanben Chemical Co., Ltd.), FLOREN G-450, FLOREN G-600, FLOREN G-820, FLOREN G-700, FLOREN DOPA-44, FLOREN DOPA-17 Limited company).

In order to achieve the above object, the content of the dispersant is preferably 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, per 100 parts by mass of the conductive powder.

(filler)

In the conductive resin composition of the present invention, the physical strength of the coating film is increased, and the filler may be formulated as needed. Although such a filler may be a conventionally used inorganic or organic filler, it is preferred to use barium sulfate, cerium oxide, hydrotalcite and talc.

(thermosetting catalyst)

The conductive resin composition of the present invention has two of the above molecules. In the case of the thermosetting component of the above cyclic (thio)ether group, a thermosetting catalyst is preferred. The thermosetting catalyst can be exemplified by, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethylidene. Imidazole derivatives such as phenyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodiamide, benzyldimethylamine, 4- (Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzyl An amine compound such as an amine, a ruthenium compound such as diammonium adipate or bismuth sebacate; a phosphorus compound such as triphenylphosphine or the like. In addition, for example, 2MZ-A, 2MZ-good, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole-based compounds) manufactured by Shikoku Chemical Industry Co., Ltd., U-CAT manufactured by SAN-APRO Co., Ltd. (registered trademark) 3503N, U-CAT3502T (all trade names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic guanidine compounds and their salts), etc. . It is not particularly limited to those of the above, as long as it is a thermosetting catalyst of an epoxy resin or an oxetane compound, or a reaction which promotes the reaction of an epoxy group and/or an oxetanyl group with a carboxyl group, and is used alone or in combination 2 All of the above are fine. Further, guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-triazine, 2-vinyl-2,4 can be used. -diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine ‧ iso-cyanuric acid adduct, 2,4-diamino-6-methyl propylene An S-triazine derivative such as a methoxyethyl-S-triazine ‧ an isocyanuric acid addition product, preferably a compound which functions as the adhesion imparting agent and the aforementioned thermosetting catalyst And use it.

The amount of these thermosetting catalysts is sufficient in the proportion of the usual amount. For example, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, per 100 parts by mass of the thermosetting component having a carboxyl group-containing resin or two or more cyclic (thio)ether groups in the molecule. .

(chain transfer agent)

In the conductive resin composition of the present invention, well-known N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazoles and the like can be used as the chain transfer agent for the purpose of improving the sensitivity. Specific examples of the chain transfer agent, for example, a chain transfer agent having a carboxyl group such as mercapto succinic acid, thioglycolic acid, mercaptopropionic acid, methionine, photocysteine, thiosalicylic acid, and derivatives thereof; a chain transfer agent having a hydroxyl group such as ethanol, mercaptopropanol, mercaptobutanol, mercaptopropanediol, mercaptobutanediol, hydroxybenzenethiol and derivatives thereof; 1-butanethiol, butyl-3-mercaptopropyl Acid ester, methyl-3-mercaptopropionate, 2,2-(extended ethylenedioxy)diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propane Mercaptan, butyl mercaptan, pentyl mercaptan, 1-octyl mercaptan, cyclopentyl mercaptan, cyclohexyl mercaptan, thioglycerol, 4,4-thiobisbenzenethiol, and the like.

Further, a polyfunctional thiol compound can be used, and it is not particularly limited, and for example, hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, or the like can be used. An aromatic thiol such as an aliphatic thiol such as dimercapto diethyl thioether, xylene dithiol, 4,4'-dimercaptodiphenyl sulfide or 1,4-benzenedithiol; Ethylene glycol bis(mercaptoacetate), polyethylene glycol bis(mercaptoacetate), propylene glycol bis(mercaptoacetate), glycerol ginseng (mercaptoacetate), trimethylolethane sulfhydryl Acetate), trimethylolpropane ginseng Poly(mercaptoacetate) of polyhydric alcohols such as esters, neopentyl quinone oxime (mercaptoacetate), dipentaerythritol tertyl (mercaptoacetate); ethylene glycol bis(3-mercaptopropyl acrylate) Acid ester), polyethylene glycol bis(3-mercaptopropionate), propylene glycol bis(3-mercaptopropionate), glycerol ginseng (3-mercaptopropionate), trimethylolethane sulfonate Dimers of acid esters, trimethylolpropane ginseng (3-mercaptopropionate), neopentyl quinone oxime (3-mercaptopropionate), dipentaerythritol tert-(trimethylpropionate) Poly(3-mercaptopropionate) of alcohol; 1,4-bis(3-mercaptobutoxy)butane, 1,3,5-gin(3-mercaptobutyloxyethyl)-1 , poly(indenyl butyrate) such as 3,5-triazine-2,4,6(1H,3H,5H)-trione or neopentyl sterol (3-mercaptobutyrate).

Such commercially available products can be exemplified by, for example, BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP, and TEMPIC (above, 堺Chemical Industries, Inc.), CarensMT-PE1, CarensMT-BD1, and Carens-NR1 (above is Showa Denko (share) system) and so on.

Further, as the heterocyclic compound having a mercapto group which functions as a chain transfer agent, for example, mercapto-4-butyrolactone (alias: 2-mercapto-4-butanolide), 2-mercapto-4-methyl group 4-butyrolactone, 2-mercapto-4-ethyl-4-butyrolactone, 2-mercapto-4-thiobutyrolactone (butyrothiolactone), 2-mercapto-4-butylidene, N- Methoxy-2-mercapto-4-butylidene, N-ethoxy-2-mercapto-4-butylidene, N-methyl-2-mercapto-4-butylidene, N- Ethyl-2-mercapto-4-butylidene, N-(2-methoxy)ethyl-2-mercapto-4-butylidene, N-(2-ethoxy)ethyl-2 - mercapto-4-butylidene, 2-mercapto-5-valerolactone, 2-mercapto-5-pentalinamide, N-methyl-2-indolyl-5-pentalamine, N-ethyl-2-mercapto-5-pentalinamide, N-(2-methoxy)ethyl-2-mercapto-5-pentalinamide, N-(2-ethoxy)ethyl -2-mercapto-5-valeroinamide, 2-mercaptobenzothiazole, 2-mercapto-5-methylthio-thiadiazole, 2-mercapto-6-caprolactam, 2,4,6 -Tridecyl-s-triazine (manufactured by Sankyo Chemical Co., Ltd.: trade name ZISNET F), 2-dibutylamino-4,6-dimercapto-s-triazine (manufactured by Sankyo Chemical Co., Ltd.) : Trade name: ZISNET DB), and 2-anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Chemical Co., Ltd.: trade name: ZISNET AF).

In particular, as a heterocyclic compound having a mercapto group as a chain transfer agent which does not impair the development of a conductive resin composition, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole ( Product name: Kawaguchi Chemical Industry Co., Ltd. AXEL M), 3-mercapto-4-methyl-4H-1,2,4-triazole, 5-methyl-1,3,4-thiadiazole-2 - Mercaptan, 1-phenyl-5-mercapto-1H-tetrazole is preferred. These chain transfer agents may be used alone or in combination of two or more.

(antifoaming agent)

In the conductive resin composition of the present invention, an antifoaming agent can be formulated for defoaming of the coating film. The antifoaming agent is not particularly limited, and examples thereof include an organic system such as a polyfluorene-based or non-polyoxynoxy-based acrylic resin. The antifoaming agents may be used alone or in combination of two or more. For the commercial product of the antifoaming agent, for example, BYK (registered trademark) - 054, -055, -057, -1790 manufactured by BYK Japan Co., Ltd., which is a non-polyoxygenated foaming polymer solution, is used. Etc., BYK (registered trademark)-063, -065, -066N, -067A, -077, and BYK Japan, which are examples of polyoxygenated defoamers, can be used. KS-66 (trade name), etc.

The amount of the antifoaming agent to be added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the carboxyl group-containing resin.

(leveling agent)

In the conductive resin composition of the present invention, a leveling agent can be formulated for the smoothness of the surface of the coating film. The leveling agent is not particularly limited, but may, for example, be a polyacrylate polymer, a polyether modified dimethyl polyoxyalkylene copolymer, a polyester modified dimethyl polyoxyalkylene copolymer, or a polyether modified product. A methacrylic polyalkylene oxide copolymer, an aralkyl modified methyl alkyl polyoxyalkylene copolymer, a polyether modified methyl alkyl polyoxyalkylene copolymer, and the like. The leveling agents may be used alone or in combination of two or more. For the commercial product of the leveling agent, for example, BYK (registered trademark)-350, -352, -354, -356, -361N, -392 manufactured by BYK Japan Co., Ltd., POLYFLOW series manufactured by Kyoeisha Chemical Co., Ltd., and the like can be exemplified.

The amount of the leveling agent to be added is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, per 100 parts by mass of the carboxyl group-containing resin.

(coupling agent)

In the conductive resin composition of the present invention, a coupling agent can be adjusted in order to improve the adhesion to the base material. The coupling agent may, for example, be a decane coupling agent, a titanate coupling agent, an aluminate coupling agent or the like. The coupling agent may be used alone or in combination of two or more. Among them, more visible and visible A quinone coupling agent having a sexual effect is preferred. The decane coupling agent is not particularly limited, and examples thereof include a general epoxy decane coupling agent, an amino decane coupling agent, a cationic decane coupling agent, a vinyl decane coupling agent, an acrylonitrile coupling agent, and a mercapto decane. A coupling agent, a composite coupling agent of the like, and the like. Commercial products of the coupling agent can be exemplified by, for example, KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE. -502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-9103, KBM-573, KBM-575, KBM-6123 , KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007 (all are trade names, manufactured by Shin-Etsu Chemical Co., Ltd.), Silquest A-186, Silquest A-187 (all are Trade name, manufactured by Momentive Performance Materials). These may be used alone or in combination of two or more.

The amount of the decane coupling agent to be added is suitably 1 to 20 parts by mass based on 100 parts by mass of the carboxyl group-containing resin.

(other added ingredients)

In the conductive resin composition of the present invention, it is of course possible to suitably mix well-known components such as a tackifier, an antioxidant, a rust preventive agent, and the like as needed.

(formation of conductive circuit)

Next, the formation of the conductive resin composition using the present invention will be described. An example of a method of conducting a circuit.

In the conductive resin composition of the present invention, each of the above-mentioned essential components and optional components can be dispersed by mechanical kneading using a triaxial roll or a mixer.

The dispersed conductive resin composition is applied onto a substrate by a suitable coating method such as a screen printing method, a bar coater, or a blade coater. Then, in order to obtain the dryness of the touch, a hot air circulation type drying furnace, a far-infrared drying oven, or the like is dried at a temperature at which the carboxyl group-containing resin is not thermally decomposed, for example, at about 60 to 120 ° C for 5 to 40 minutes to evaporate the organic solvent. , to obtain a non-stick coating film.

Further, the conductive resin composition may be formed into a film in advance, and in this case, the film may be laminated on the substrate.

Next, contact exposure or non-contact exposure is performed using a negative mask having a specific exposure pattern. As the exposure light source, a halogen lamp, a high pressure mercury lamp, a laser beam, a metal halide lamp, a black lamp, an electrodeless lamp or the like is used. The exposure amount may be a low light amount in which the cumulative light amount is 200 mJ/cm 2 or less. Further, it is also possible to form a pattern on the coating film by using a laser direct imaging device without using a mask.

Next, the coating film is patterned by a development method such as a spray method or a dipping method. As the developing solution, a metal alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium citrate or an aqueous amine solution such as monoethanolamine, diethanolamine or triethanolamine can be suitably used, especially about 1.5% by mass. The dilute alkaline aqueous solution of the following concentration may be obtained by saponifying the carboxyl group of the carboxyl group-containing resin in the conductive resin composition, and removing the uncured portion (unexposed portion), and is not limited to the above-described developing solution. Also, in order to remove the image, do not The developing solution is preferably subjected to water washing or acid neutralization.

Next, the resulting conductive pattern film is dried at a temperature at which the carboxyl group-containing resin is not thermally decomposed. According to this, a conductive circuit having a low resistance and having a fine conductive pattern film can be formed. The drying temperature is preferably 150 ° C or lower, more preferably 140 ° C or lower, and even more preferably 130 ° C or lower.

In these steps, since the substrate is not fired at a temperature of, for example, 500 ° C, a base material (film material) made of a resin having no heat resistance can be used as the substrate. Specifically, the resin substrate may, for example, be a polyimide, a polyester resin, a polyether oxime (PES), a polystyrene (PS), a polymethyl methacrylate (PMMA), or a polycarbonate (PC). Polyamide (PA), polypropylene (PP), polyphenylene ether (PPO), etc., polyester resin can be preferably used. Further, it may be a glass substrate or the like.

[Examples]

Hereinafter, the present invention will be specifically described based on examples. However, the invention is not limited to such embodiments.

(mixing ingredients) [Resin containing carboxyl group] Synthesis Example 1

In a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux cooler, methyl methacrylate and methacrylic acid were fed at a molar ratio of 0.87:0.13, and dipropylene glycol monomethyl ether as a solvent was added as a catalyst. The azobisisobutyronitrile was stirred at 80 ° C for 6 hours under a nitrogen atmosphere to obtain a resin solution containing a carboxyl group. Mass average score of this carboxyl group-containing resin The amount is about 10,000 and the acid value is 74 mgKOH/g. In addition, the mass average molecular weight of the resin containing a carboxyl group is a pump LC-6AD manufactured by Shimadzu Corporation and a pipe column Shodex (registered trademark) KF-804, KF-803, KF which are connected to three Showa Denko Electric Co., Ltd. -802 high speed liquid chromatography assay. Hereinafter, the resin solution containing a carboxyl group is referred to as A-1 varnish. Further, the carboxyl group-containing resin does not contain a double bond and does not contain an aromatic ring.

[conductive powder]

Spherical conductive powder: Ag powder (maximum particle size 30 μm or less, average particle diameter 2 μm (SEM)))

[Reactive diluent]

4-functional (meth) acrylate monomer: trade name; NK Oligo U-4HA (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[Photopolymerization initiator]

Refer to Table 1

[phenothiazine]

Phthathiazine (made by Kanto Chemical Co., Ltd.)

[organic acid]

2'2-thiodiacetic acid; aliphatic dicarboxylic acid (manufactured by Kanto Chemical Co., Ltd.)

[thermosetting component]

‧trade name: 7982 (Baxenden company) isocyanate HDI3 polymer block isocyanate Dimethyl pyrazole

‧trade name: jER828 (made by Mitsubishi Chemical Corporation) bisphenol A type epoxy resin

[Dispersant]

Product name: DISPERBYK-111 (BYK Japan company)

(evaluation method) Test film production:

Each of the conductive resin compositions for evaluation was applied to the entire surface of the substrate made of polyester resin using a 300 mesh polyester screen, followed by drying at 80 ° C for 30 minutes in a hot air circulating drying oven to form Touch the film with good dryness. Subsequently, a high-pressure mercury lamp is used as a light source, and a negative type mask is passed through so that the cumulative amount of light (the exposure amount of the ladder plate 5 stages) on the conductive resin composition is 200 mJ/cm ² or 200 mJ/cm ² . After the pattern exposure, development was carried out using a 0.4 mass% Na ² CO ³ aqueous solution having a liquid temperature of 30 ° C, followed by water washing. Finally, it was dried at 140 ° C for 30 minutes to prepare a test piece in which a conductive pattern film (L/S = 20/20 um pattern) was formed.

Resolution: The minimum line width of the test piece produced by the above method was evaluated.

Those whose line width is less than 25um are evaluated as good, and those above 25um are evaluated as bad.

Note: Because it is usually slightly negative (not more than +5um) When using a 20um negative film, it is actually good if it is less than 25um, and it is bad if it is 25um or more.

Specific resistance value: A pattern of 4 mm × 10 cm was formed by the above method, and the specific resistance value was calculated by measuring the resistance value and the film thickness.

Adhesion: A pattern of L/S=30/30 um was formed, and a scotch tape (registered trademark) was peeled off, and a defect-free one was evaluated as "good". Those who have a defect are assessed as "bad".

Coating film strength: L/S=30/30um pattern formation, using the device described in JIS K5600-5-4: pencil hardness tester with a load of 1Kg, no line breakage when scratching the side of the line vertically The assessment was "good". The defective person is evaluated as "bad". The pencil used was Mitsubishi Hi-uni (manufactured by Mitsubishi Pencil Co., Ltd., hardness: 3H).

(test results)

Regarding Examples 1 to 5 and Comparative Examples 1 to 5 contained in the scope of the present invention (not used in the h-line non-absorptive photopolymerization initiator, or without the use of phenothiazine), the experimental conditions and evaluation results are summarized in Table 1 (Examples) and Table 2 (Comparative Examples) are shown below.

Although the comparative examples all have a photopolymerization initiator, Comparative Example 1 does not contain "photopolymerization initiator which absorbs in h line" and does not contain "phenothiazine", and Comparative Example 2 does not contain "photopolymerization initiator which absorbs in h line" but contains "phenolic thiophene" "Zi"", Comparative Example 3 does not contain "photopolymerization initiator which absorbs on h line" but contains "phenothiazine", and Comparative Example 4 contains "photopolymerization initiator which absorbs on h line" but does not contain " "Phenothiazine", Comparative Example 5 does not contain "photopolymerization initiator which absorbs in h line" but contains "phenothiazine", and Comparative Example 6 does not contain "photopolymerization initiator which absorbs in h line" but Contains "phenothiazine".

It is confirmed from Examples 1 to 6 that the conductive resin composition of the present invention can be applied to a substrate having a weak heat resistance, and excellent conductivity and resolution are ensured, and the adhesion to the underlying substrate is excellent. Further, it is excellent in thermal resolvability, and a conductive resin composition having a low specific resistance value can be obtained. In particular, the peel strength at a high load of "strength 1 kg and load 3H" was "good", and it was confirmed that the coating film strength was further improved.

On the other hand, in Comparative Examples 1 to 3, 5, and 6, desired desirability and adhesion were obtained, but a desired peel strength was not obtained. In Comparative Example 4, although the desired adhesion and peel strength were obtained, the desired resolution was not obtained.

Claims (14)

A conductive resin composition for non-baking characterized by comprising a carboxyl group-containing resin, a conductive powder, a polyfunctional (meth) acrylate compound, a photopolymerization initiator having an absorption wavelength on the h-line, and thermosetting Sexual ingredients, and, phenothiazine. The conductive resin composition for non-baking according to claim 1, wherein the polyfunctional (meth) acrylate compound is a polyfunctional (meth) acrylate monomer. The conductive resin composition for non-baking according to claim 2, wherein the polyfunctional (meth) acrylate monomer is a tetrafunctional (meth) acrylate monomer. The non-sintering conductive resin composition according to claim 3, wherein the tetrafunctional (meth) acrylate monomer is a (meth) acrylate monomer represented by the following chemical formula (I). In the formula (I), X ¹ represents a group containing an acryloxy group, X ² represents a group containing a methacryloxy group, and X ³ and X ⁴ each independently represent a group containing an acryloxy group, or a group a group based on a propylene oxy group, wherein at least one of X ³ and X ⁴ represents a group containing a methacryloxy group, and L ¹ and L ² each independently represent the following formula * indicates a bonding site with Z, and Z indicates a binary bond group. The conductive resin composition for non-firing according to claim 4, wherein L ¹ and L ² in the general formula (I) are as follows (In the formula (III), * indicates a bonding site with Z). The conductive resin composition for non-baking according to claim 4, wherein the (meth) acrylate monomer of the tetrafunctional group represented by the general formula (I) is represented by the following formula (IV). In the formula (IV), Z ¹ represents an alkylene group, R ¹ represents a hydrogen atom, R ² represents a methyl group, and R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, but at least one of R ³ and R ⁴ Indicates a methyl group. The conductive resin composition for non-firing according to claim 1, wherein the photopolymerization initiator having an absorption wavelength on the h-line is 1-[9-ethyl-6-2(2-methylbenzhydrazide). Base)-9H-carbazol-3-yl]-1-(O-ethylindenyl). The conductive resin composition for non-baking according to claim 1, wherein the thermosetting component is a blocked isocyanate. The conductive resin composition for non-baking according to claim 1, wherein the carboxyl group-containing resin does not contain a double bond. The conductive resin composition for non-baking according to claim 9, wherein the carboxyl group-containing resin which does not contain a double bond further does not have an aromatic ring. The non-baking conductive resin composition of claim 1, which further comprises an organic acid. The conductive resin composition for non-firing according to claim 11, wherein the organic acid does not have an aromatic ring. The conductive resin composition for non-baking according to claim 11, wherein the organic acid does not have an aromatic ring and has two or more carboxyl groups. A conductive circuit comprising a non-baking conductive resin composition according to any one of claims 1 to 13 which is coated on a substrate and dried.