JP2015125189A - Conductive resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive resin composition which can improve its coating film strength and adherence.SOLUTION: A conductive resin composition comprises hydroxy group- and carboxyl group-containing resin, conductive powder, reactive diluent, photopolymerization initiator, and thermosetting component, wherein the total hydroxyl equivalent of the hydroxy group- and carboxyl group-containing resin is 300 or more and 3000 or less.

Description

  The present invention relates to a conductive resin composition and a cured product formed using this resin composition.

  Patent Documents 1 and 2 are known documents that disclose a conductive paste for forming a conductive pattern film on a substrate.

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

  These conductive pastes are fired at a temperature of 500 ° C. or higher to remove organic components in the paste, thereby ensuring the conductivity of the cured product layer.

  In addition, the baking type conductive paste as described above generally contains glass frit together with the conductive powder, and by baking, the organic components in the paste are removed and the glass frit is melted to conduct the conductive pattern. And adhesion between the substrate and the substrate are ensured.

  However, since such a photosensitive conductive paste is baked at a temperature of 500 ° C. or higher, there is a problem that it is difficult to apply it on a heat-sensitive substrate.

Japanese Patent Laid-Open No. 2003-280181 Japanese Patent No. 4411113

  This invention is made | formed in order to eliminate the said problem, and provides the hardened | cured material formed using the conductive resin composition applicable to the base material weak to a heat | fever, and this conductive resin composition. There is.

  Furthermore, this invention is providing the conductive resin composition which can improve both coating-film intensity | strength and adhesiveness with a base material, and the hardened | cured material formed using this conductive resin composition. .

  In order to solve the above problems, the present invention includes a hydroxyl group and carboxyl group-containing resin, a conductive powder, a reactive diluent, a photopolymerization initiator, and a thermosetting component, and the hydroxyl group and carboxyl group-containing resin. The total of the hydroxyl equivalents is 300 or more and 3000 or less.

  Alternatively, the present invention includes two or more resins selected from the group consisting of a hydroxyl group and carboxyl group-containing resin, a hydroxyl group-containing resin, and a carboxyl group-containing resin, a conductive powder, a reactive diluent, a photopolymerization initiator, and Provided is a conductive resin composition containing a thermosetting component, wherein the total of hydroxyl equivalents of the two or more resins is 300 or more and 3000 or less.

  In the conductive composition of the present invention, the thermosetting component is preferably a polyfunctional epoxy resin.

  The conductive resin composition of the present invention is preferably used for forming a conductive circuit.

  And this invention provides the hardened | cured material formed by using this conductive resin composition on a base material.

  According to the present invention, a conductive resin composition that can be applied to a heat-sensitive substrate and that is excellent in both coating film strength and adhesion to a base substrate, and formed using this conductive resin composition Cured product can be provided.

  First, the component mix | blended in the composition based on this invention is demonstrated.

(Hydroxyl group and carboxyl group-containing resin having a hydroxyl group equivalent of 300 to 3000)
The hydroxyl group- and carboxyl group-containing resin has a hydroxyl group, and by specifying the total of the hydroxyl group equivalents in the range of 300 to 3,000, the coating film strength and the adhesion to the base substrate are particularly excellent. it can. The reason why the total of hydroxyl equivalents is specified to be 300 or more and 3000 or less is that when it is within this range, the coating film strength is improved and the contact resistance value with ITO is lowered.

In the present specification, the “total hydroxyl group equivalent of the resin” refers to a value defined as follows.
(1) When the resin is composed of one kind of resin, “total of hydroxyl equivalents of the resin” = hydroxyl equivalent of the resin used.
(2) When the resin is composed of a plurality of types of resins and all the resins contain a hydroxyl group, “total of hydroxyl group equivalents of resin” = [hydroxyl group equivalent of specific resin × mixing ratio of specific resin to all resins (mass%) / 100 ] Total ... Formula 2
(3) When the resin is composed of a plurality of types of resins and contains a resin not containing a hydroxyl group, “total of hydroxyl equivalents of the resin” = total of hydroxyl equivalents of the resin containing hydroxyl groups × 100 / mixing ratio of the resin containing hydroxyl groups (mass %) ... Formula 3

  As this hydroxyl group- and carboxyl group-containing resin, known and commonly used resin compounds can be used. Specific examples of this resin are listed below.

(1) One or more types of unsaturated carboxylic acid such as (meth) acrylic acid and other compounds having an unsaturated double bond (for example, lower alkyl (meth) acrylate), hydroxyl group and (meth) acrylic group A hydroxyl group- and carboxyl group-containing resin obtained by copolymerizing a compound having a hydroxyl group (for example, hydroxy lower alkyl (meth) acrylate) and the like,
(2) a hydroxyl group- and carboxyl group-containing resin obtained by reacting a compound having a hydroxyl group with a copolymer of an acid anhydride having an unsaturated double bond and another compound having an unsaturated double bond;
(3) A saturated carboxylic acid is reacted with a copolymer of an epoxy group, a compound having an unsaturated double bond, and a compound having an unsaturated double bond, and a polybasic acid anhydride is reacted with the resulting secondary hydroxyl group. Hydroxyl group and carboxyl group-containing resin obtained by
(4) A hydroxyl group- and carboxyl group-containing resin obtained by reacting a hydroxyl group-containing polymer with a polybasic acid anhydride is not limited thereto.

  In addition, in this specification, (meth) acrylic acid is a term that collectively refers to acrylic acid, methacrylic acid, and mixtures thereof, and the same applies to other similar expressions.

  Since the hydroxyl group- and carboxyl group-containing resin as described above has a large number of free carboxyl groups in the side chain of the backbone polymer, development with a dilute aqueous alkali solution is possible.

  Moreover, it is preferable that the acid value of said hydroxyl group and carboxyl group containing resin is the range of 40-200 mgKOH / g, More preferably, it is the range of 45-120 mgKOH / g. If the acid value of the hydroxyl group- and carboxyl group-containing resin is less than 40 mgKOH / g, alkali development becomes difficult. On the other hand, if it exceeds 200 mgKOH / g, dissolution of the exposed part by the developer proceeds, so the line may be thinner than necessary. In some cases, the exposed portion and the unexposed portion are not distinguished from each other by dissolution and peeling with a developer, which makes it difficult to draw a normal conductive pattern.

  Further, the mass average molecular weight of the hydroxyl group- and carboxyl group-containing resin varies depending on the resin skeleton, but is preferably in the range of 10,000 to 150,000, more preferably 15,000 to 100,000. If the mass average molecular weight is less than 10,000, the tack-free performance may be inferior, the moisture resistance of the conductive pattern film after exposure may be poor, the film may be reduced during development, and the resolution may be greatly inferior. On the other hand, when the mass average molecular weight exceeds 150,000, developability may be remarkably deteriorated, and storage stability may be inferior.

  The amount of the hydroxyl group- and carboxyl group-containing resin is preferably 3 to 50% by mass, more preferably 5 to 30% by mass in the total conductive resin composition. When the amount is less than the above range, the strength of a cured film such as a conductive pattern film is lowered, which is not preferable. On the other hand, when the amount is larger than the above range, the viscosity becomes high or the coating property and the like are lowered, which is not preferable.

  As mentioned above, although the case where a hydroxyl group and carboxyl group containing resin are mix | blended is demonstrated, it can replace with said hydroxyl group and carboxyl group containing resin, and can use together hydroxyl group containing resin and carboxyl group containing resin. . Alternatively, at least one of a hydroxyl group-containing resin and a carboxyl group-containing resin can be used in combination with the hydroxyl group- and carboxyl group-containing resin. In this case as well, as in the case of the “hydroxyl and carboxyl group-containing resin”, the total of hydroxyl equivalents of these resins is set to 300 to 3000. Further, when the resin is mixed as described above, suitable acid value, mass average molecular weight, blending amount and the like are the same as those of the above-mentioned “hydroxyl and carboxyl group-containing resin”.

  As this hydroxyl group-containing resin, a known and commonly used resin compound can be used. In the present specification, the “hydroxyl group-containing resin” does not contain a carboxyl group. Specific examples of this resin are listed below.

  (1) It is obtained by copolymerizing a compound having a hydroxyl group and a (meth) acryl group (for example, hydroxy lower alkyl (meth) acrylate) or the like and an unsaturated group-containing compound such as lower alkyl (meth) acrylate or isobutylene. Examples include, but are not limited to, functional group hydroxyl group-containing resins.

  Examples of the hydroxyl group-containing resin include Toa Gosei ARUFON UH-2000 series (UH-2000, etc.).

  Moreover, a well-known and usual resin compound can also be used for carboxyl group-containing resin. In the present specification, the “carboxyl group-containing resin” does not contain a hydroxyl group. Specific examples of this resin are listed below.

(1) Carboxyl obtained by copolymerizing with unsaturated carboxylic acid such as (meth) acrylic acid and one or more of other compounds having unsaturated double bonds (for example, lower alkyl (meth) acrylate) Group-containing resin,
(2) Carboxylic group-containing resins obtained by copolymerizing an acid anhydride having an unsaturated double bond such as maleic anhydride and a compound having an unsaturated double bond other than these, It is not limited to.

  Examples of the carboxyl group-containing resin include Toa Gosei ARUFON UC-3000 series.

  As described above, in the conductive resin composition of the present invention, “hydroxyl group and carboxyl group-containing resin” may be used, or “from the group of hydroxyl group and carboxyl group-containing resin, hydroxyl group-containing resin, and carboxyl group-containing resin”. Two or more selected resins "may be used.

  As the hydroxyl group- and carboxyl group-containing resin, hydroxyl group-containing resin, and carboxyl group-containing resin, those having a urethane bond in the main chain can be used.

  Any of the above hydroxyl group- and carboxyl group-containing resins, hydroxyl group-containing resins, and carboxyl group-containing resins preferably does not have an aromatic ring, and if it does not have an aromatic ring, the light absorption of the resin is suppressed, which will be described later. The photoreactivity of the reactive diluent can be improved relatively.

(Conductive powder)
As the conductive powder, any conductive powder may be used as long as it imparts conductivity in the conductive resin composition. Examples of such conductive powder include Ag, Au, Pt, Pd, Ni, Cu, Al, Sn, Pb, Zn, Fe, Ir, Os, Rh, W, Mo, Ru, and the like. Among these, Ag is preferable. These conductive powders may be used in the form of a single component, but may be used in the form of an alloy or oxide. Furthermore, tin oxide (SnO ₂ ), indium oxide (In ₂ O ₃ ), ITO (Indium Tin Oxide), or the like can also be used. The conductive powder may be carbon powder such as carbon black, graphite, or carbon nanotube. However, use of these powders requires attention because the light transmittance is lowered.

  The shape of these powders is not particularly limited, but is preferably other than flakes, particularly preferably acicular or spherical. As a result, a light-transmitting property can be improved and a pattern film having excellent resolution can be formed.

  Such a powder preferably has a maximum particle size of 30 μm or less in order to form fine lines. By setting the maximum particle size to 30 μm or less, the resolution of the cured product is improved.

  The powder is an average particle diameter of 10 random powders observed at 10,000 times using an electron microscope (SEM), and the range is preferably 0.1 to 10 μm or less. If the average particle size is smaller than this range, the resistance value increases due to an increase in contact resistance, which is not preferable. On the other hand, when the average particle size is larger than the above range, when a conductor pattern is printed using a mesh screen plate, workability is deteriorated due to clogging of the screen, and formation of fine lines becomes difficult, which is not preferable. In addition, it is preferable to use the thing of the magnitude | size of 0.5-3.5 micrometers in the average particle diameter measured with the micro track | truck.

  The blending ratio of the conductive powder is preferably 800-1500 parts by mass, more preferably 800-1200 parts by mass, and 800-900 parts by mass with respect to 100 parts by mass of the hydroxyl group- and carboxyl group-containing resin. Is more preferable. When there are too few compounding ratios, there exists a possibility that resistance value of a conductive resin composition may become high, and sufficient electroconductivity may not be obtained. On the other hand, when a large amount of powder is contained, the light transmittance is deteriorated and the formation of the pattern film by exposure is deteriorated, which is not preferable. In the case where “hydroxyl group-containing resin and carboxyl group-containing resin” is blended, and in addition to “hydroxyl group and carboxyl group-containing resin”, at least one of “hydroxyl group-containing resin” and “carboxyl group-containing resin” is blended Also, the blending ratio of the conductive powder is preferably 800 to 1500 parts by weight, more preferably 800 to 1200 parts by weight with respect to 100 parts by weight of the total amount of these resins. More preferably, it is made into a mass part.

  Hereinafter, with respect to the blending amount of these resins, the “hydroxyl group and carboxyl group-containing resin” will be described as a representative. However, the blending amount shown therein, when “hydroxyl group-containing resin” and “carboxyl group-containing resin” is blended, The present invention is also applied to the case where at least one of “hydroxyl group-containing resin” and “carboxyl group-containing resin” is blended together with “hydroxyl group and carboxyl group-containing resin”.

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

  Examples of the (meth) acrylate compound include polyfunctional (meth) acrylate monomers or oligomers (bifunctional or higher (meth) acrylate monomers or oligomers). Specific examples include conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate, and the like. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; N, N-dimethylacrylamide Acrylamides such as N-methylol acrylamide and N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like; Polyhydric acrylates such as lenoxide adducts, propylene oxide adducts, or ε-caprolactone adducts; polyvalent acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide or propylene oxide adducts of these phenols Acrylates; glyceryl diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyglycerides of glycidyl ether such as triglycidyl isocyanurate; not limited to the above, polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, Directly acrylated polyol such as polyester polyol, or urethane acrylate via diisocyanate Acrylates and melamine acrylates, and at least one of each methacrylate corresponding to the acrylate.

  Of these, polyfunctional (meth) acrylate monomers are preferably used, and tetrafunctional (meth) acrylate monomers are particularly preferable. Examples of tetrafunctional (meth) acrylate monomers include pentaerythritol tetraacrylate and pentaerythritol tetramethacrylate.

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

In formula (I),
X ¹ represents a group containing an acryloyloxy group.
X ² represents a group containing a methacryloyloxy group.
X ³ and X ⁴ each independently represent a group containing an acryloyloxy group or a group containing a methacryloyloxy group. However, at least one of X ³ and X ⁴ represents a group containing a methacryloyloxy group.

を表す。 L ¹ and L ² are each independently

Represents.

* Represents a binding site with Z.
Z represents a divalent linking group.

で表されるウレタンアクリレートであることが好ましい。式（ＩＩＩ）中、＊はＺとの結合部位を表す。 As the acrylate monomer, L1 and L2 in the general formula (I) are

It is preferable that it is urethane acrylate represented by these. In formula (III), * represents a binding site with Z.

  Furthermore, as a monomer represented by general formula (I), urethane acrylate represented by the following formula (IV) is preferable.

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

  Furthermore, urethane acrylate or ester acrylate in which acrylic and methacryl are in a one-to-one relationship is particularly preferable as the tetrafunctional acrylate monomer.

  As such a 4-functional urethane acrylate or ester acrylate, for example, a product obtained by adding acrylic acid to glycidyl methacrylate and reacting the generated hydroxyl group with diisocyanate or dicarboxylic acid is preferable.

  Examples of commercially available products of tetrafunctional urethane acrylate include NK Oligo U-4HA (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.).

  Of these polyfunctional (meth) acrylate monomers, tetrafunctional acrylate monomers represented by the formula (I) are preferred. Since this tetrafunctional acrylate monomer has a large number of functional groups, it has excellent photoreactivity and excellent resolution.

In addition, since X ¹ and X ² of the tetrafunctional acrylate monomer are different from each other, the reaction between X ¹ and X ² in the molecule is slow during photocuring. However, the acrylate monomer X ¹ or X ² reacts faster than the intramolecular reaction between the other acrylate monomers X ¹ or X ² . Thereby, since an intermolecular bond is formed between a plurality of acrylate monomers, the conductive resin composition is further cured and contracted. And only by heat-processing at low temperature, intermolecular reaction is further accelerated | stimulated and the conductive resin composition fully cures and shrinks. As a result, it is considered that the conductive powder becomes dense and the specific resistance value of the conductive pattern film is further lowered.

  The compounding amount of such a reactive diluent is not particularly limited, but is selected from the group of the “hydroxyl group and carboxyl group-containing resin” or the “hydroxyl group and carboxyl group-containing resin, hydroxyl group-containing resin, and carboxyl group-containing resin”. The ratio of 10 to 100 parts by mass, more preferably 20 to 80 parts by mass is appropriate for 100 parts by mass of “two or more kinds of resins”. When the blending amount is less than 10 parts by mass, the photocurability is lowered, and formation of a conductive pattern line may be difficult due to alkali development after irradiation with active energy rays. On the other hand, when the amount exceeds 100 parts by mass, the solubility in an alkaline aqueous solution is lowered, and the conductive pattern film may become brittle.

(Photopolymerization initiator)
The photopolymerization initiator is not particularly limited, and may be a benzoin type or a phosphine oxide type, but is represented by the oxime ester type having a group represented by the following general formula (V) or the following general formula (VI). It is preferable to use an acetophenone-based photopolymerization initiator having the above group.

  In formula (V), R6 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R7 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

  In formula (VI), R8 and R9 each independently represent an alkyl group having 1 to 12 carbon atoms or an arylalkyl group, and R10 and R11 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Or R10 and R11 may combine to form a cyclic alkyl ether group.

  Among the oxime ester photopolymerization initiators, BASF Japan CGI-325, IRGACURE OXE01, IRGACURE OXE02, ADEKA N-1919, NCI-831, Nippon Kagaku Kogyo TOE-004, etc. are preferable. . Further, IRGACURE 389 may be used as a photopolymerization initiator. In addition, these photoinitiators can be used individually or in combination of 2 or more types.

  Examples of the acetophenone photopolymerization initiator having a group represented by the general formula (VI) include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2. -Dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] Examples include -1-butanone and N, N-dimethylaminoacetophenone. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by BASF Japan.

  The amount of such a photopolymerization initiator is not particularly limited, but is selected from the group of the “hydroxyl group and carboxyl group-containing resin” or the “hydroxyl group and carboxyl group-containing resin, hydroxyl group-containing resin, and carboxyl group-containing resin”. The range of 0.01 to 30 parts by mass, preferably 0.5 to 15 parts by mass is appropriate for 100 parts by mass of “two or more types of resins” (hereinafter, these resins are also collectively referred to as a binder resin). It is. When the blending amount of the photopolymerization initiator is less than 0.01 parts by mass, the photocurability is insufficient, the conductive pattern film is peeled off, and the characteristics of the conductive pattern film such as chemical resistance and the coating strength are reduced. It is not preferable because there is a case. On the other hand, if it exceeds 30 parts by mass, light absorption on the surface of the conductive pattern film of the photopolymerization initiator becomes violent, which is not preferable because deep part curability and coating film strength may be reduced.

(Thermosetting component)
The conductive resin composition of the present invention contains a thermosetting component in order to improve the toughness of the cured film and the adhesion to the base substrate. Examples of the thermosetting component used in the present invention include amine resins such as melamine resins and benzoguanamine resins, blocked isocyanate compounds (compounds having a blocked isocyanate group in one molecule), cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional compounds. Known and commonly used thermosetting resins such as oxetane compounds, compounds having two or more cyclic thioether groups in the molecule, episulfide resins, and melamine derivatives can be used. In order to improve the toughness of the cured film obtained from the conductive resin composition and the adhesion to the base substrate, a polyfunctional epoxy resin is particularly preferable.

  Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840 manufactured by DIC, Epicron 850, Epicron 1050, Epicron 2055, Epototo YD-011, YD manufactured by Tohto Kasei Co., Ltd. -013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.E. E. R. 664, Sumitomo Epoxy ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Mitsubishi Chemical, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., manufactured by Dow Chemical Of D. E. R. 542, Sumitomo Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd., EPPN-201, EOCN-1025, EOCN manufactured by Nippon Kayaku Co., Ltd. -1020, EOCN-104S, RE-306, Sumitomo Epoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Co., Ltd. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Mitsubishi Chemical Co., Ltd. Epototo YDF-170, YDF-175, YDF-2004 manufactured by Tohto Kasei Co., Ltd. (All trade names) bisphenol F-type epoxy resin; hydrogenated bisphenol A-type epoxy resins such as Epototo ST-2004, ST-2007, ST-3000 (trade name) manufactured by Toto Kasei Co., Ltd .; jER604, Etototo YH-434 manufactured by Tohto Kasei Co., Ltd. Sumitomo Chemical Co., Ltd. Sumi-epoxy ELM-120, etc. (all trade names) glycidylamine type epoxy resin; Hydantoin type epoxy resin; 2021 etc. (all trade names) alicyclic epoxy resin; Y manufactured by Mitsubishi Chemical Corporation -933, manufactured by Dow Chemical Company of T. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all trade names) Type or biphenol type epoxy resin or a mixture thereof; bisphenol S type epoxy resin such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., EXA-1514 manufactured by DIC Co., Ltd .; Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by KK; tetraphenylolethane type epoxy resin such as jERYL-931 (all trade name) manufactured by Mitsubishi Chemical; TEPIC manufactured by Nissan Chemical Industries, Ltd. ( All are trade names) heterocyclic epoxy resins; Nigiri such as Bremer DGT manufactured by Nippon Oil & Fats Co., Ltd. Zylphthalate resin; Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Tohto Kasei Co., Ltd .; Naphthalene such as ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by DIC Group-containing epoxy resin; epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; glycidyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by NOF Corporation; and cyclohexyl Copolymerized epoxy resin of maleimide and glycidyl methacrylate; epoxy-modified polybutadiene rubber derivative (for example, PB-3600 manufactured by Daicel Chemical Industries), CTBN-modified epoxy resin (for example, YR-102, YR-450 manufactured by Toto Kasei Co., Ltd.), etc. Is mentioned But, the present invention is not limited to these. These epoxy resins can 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 thereof is particularly preferable.

  Examples of the polyfunctional oxetane compound include 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) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin, Poly (p-hydroxystyrene), cardo-type bisphenol Le ethers, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the compound having two or more cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Mitsubishi Chemical Corporation. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

  The amount of such a polyfunctional epoxy compound, polyfunctional oxetane compound, or compound having two or more cyclic thioether groups in the molecule is 1 to 100 parts by mass, more preferably 100 parts by mass of the binder resin. A ratio of 2 to 70 parts by mass is appropriate. When the amount 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 mass parts, storage stability falls and it is not preferable.

  The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily inactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.

  As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As this isocyanate compound, for example, the same aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate as described above is used.

  Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene 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, lactic acid And alcohol-based blocking agents such as ethyl lactate; oxime-based blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, Mercaptan block agents such as methylthiophenol and ethylthiophenol; Acid amide block agents such as acetic acid amide and benzamide; Imide block agents such as succinimide and maleic imide; Amines such as xylidine, aniline, butylamine and dibutylamine Blocking agents; imidazole blocking agents such as imidazole and 2-ethylimidazole; imine blocking agents such as methyleneimine and propyleneimine It is.

  The block isocyanate compound may be commercially available, for example, 7950, 7951, 7960, 7961, 7982, 7990, 7991, 7992 (above, trade name, manufactured by Baxenden) Sumijour BL-3175, BL-4165, BL-1100, BL-1265, Death Module TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (supplied by Nippon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B-846, B-870, B-874, B-882 (Mitsui Takeda Chemical Co., trade name), TPA -B80E, 17 -60PX, E402-B80T, MF-B60B, MF-K60B, SBN-70D (manufactured by Asahi Kasei Chemicals Corporation, trade name), Karenz MOI-BM (manufactured by Showa Denko KK, trade name) and the like. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

  The compounds having a blocked isocyanate group can be used alone or in combination of two or more.

  The compounding amount of such a compound having a blocked isocyanate group is suitably 1 to 100 parts by mass, more preferably 2 to 70 parts by mass with respect to 100 parts by mass of the binder resin. When the amount is less than 1 part by mass, sufficient toughness of the coating film may not be obtained, which is not preferable. On the other hand, when it exceeds 100 mass parts, storage stability may fall and it is not preferable.

  Although the dissociation temperature of the blocking agent of the blocked isocyanate is not particularly limited, it is desirable that the blocking agent does not react at the temporary drying temperature (for example, 80 to 90 ° C.) but reacts at the final heat treatment. A temperature higher than the temporary drying temperature, for example, 100 ° C. or higher is preferable. In addition, when a polyester-based resin is used as the base material, for example, the dissociation temperature of the blocking agent of the blocked isocyanate can be prevented from being discolored, for example, 140, because the base material is easily discolored if the heat treatment temperature is too high. It is preferable that heat treatment can be performed at a temperature at which the base material is not discolored at a temperature not higher than ° C.

  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 cured film obtained, two or more in one molecule together with the thermosetting component described above. A compound having an isocyanate group can be added. Examples of such a compound having two or more isocyanate groups in one molecule include compounds having two or more isocyanate groups in one molecule, that is, polyisocyanate compounds.

  As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies, and isocyanurate bodies of the isocyanate compounds listed above may be mentioned.

  In order to further improve the effects of the present invention, or to exhibit further effects within a range that does not impair the effects of the present invention, the conductive resin composition of the present invention includes the above-described hydroxyl group-containing resin and conductive powder. In addition to the polyfunctional (meth) acrylate monomer, the photopolymerization initiator, and the thermosetting component, other components exemplified below can be included.

(Organic acid)
As the organic acid, an organic acid having no aromatic ring is preferable. By blending an organic acid that does not have an aromatic ring, the light absorption of the organic acid itself is suppressed, the photoreactivity of the reactive diluent is relatively improved, and excellent resolution can be obtained.

  Specific examples of organic acids include 2,2′-thiodiacetic acid, adipic acid, isobutyric acid, formic acid, citric acid, glutaric acid, acetic acid, oxalic acid, tartaric acid, lactic acid, pyruvic acid, malonic acid, butyric acid, Carboxylic acids such as malic acid, salicylic acid, benzoic acid, phenylacetic acid, acrylic acid, maleic acid, fumaric acid, crotonic acid; dibutyl phosphite, butyl phosphite, dimethyl phosphite, methyl phosphite, phosphorous acid Mono- or diesters of phosphorous acid such as dipropyl, propyl phosphite, diphenyl phosphite, phenyl phosphite, diisopropyl phosphite, isopropyl phosphite, phosphorous acid-n-methyl-2-ethylhexyl; phosphorus Dibutyl phosphate, butyl phosphate, dimethyl phosphate, methyl phosphate, dipropyl phosphate, propyl phosphate, diphenyl phosphate, phenyl phosphate, Examples thereof include mono- or diesters of phosphoric acid such as diisopropyl phosphate, isopropyl phosphate, and phosphoric acid-n-butyl-2-ethylhexyl. As the organic acid, 2,2'-thiodiacetic acid is preferable.

  As a compounding quantity of the said organic acid, it is preferable that it is the range of 0.1-5 mass parts with respect to 100 mass parts of said binder resins. When the blending amount of the organic acid is less than 0.1 parts by mass with respect to 100 parts by mass of the conductive powder, the reaction between the conductive powder and the carboxyl group-containing resin occurs, and the long-term storage stability is reduced. When the amount exceeds 5 parts by mass, it is not preferable because moisture in the air is easily absorbed.

(Dispersant)
By mix | blending a dispersing agent, the dispersibility and sedimentation property of a conductive resin composition can be improved.

  Examples of the dispersant include 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 (by Big Chemie Japan), Disparon 2150, Disparon 1210, Disparon KS-860, Disparon KS-873N, Disparon 7004, Disparon 1830, Disparon 1860, Disparon 1850, Disparon DA-400N, Disparon PW-36, Disparon DA-703-50 (manufactured by Enomoto Kasei), Floren G-450, Floren G-600, Floren G-820, Examples include Floren G-700, Floren DOPA-44, and Floren DOPA-17 (manufactured by Kyoeisha Chemical Co., Ltd.).

  The content of the dispersant is preferably 0.1 to 10 parts by mass, and preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the binder resin in order to effectively achieve the above object.

(Photopolymerization inhibitor)
By adding the photopolymerization inhibitor, it is possible to suppress a certain amount of radical polymerization in accordance with the type of polymerization inhibitor and the amount of the addition among the radical polymerization that occurs inside the conductive resin composition by exposure. Thereby, the photoreaction with respect to weak light like scattered light can be suppressed. Therefore, since a finer line of the conductive pattern film can be formed sharply, it can be preferably used. The photopolymerization inhibitor is not particularly limited as long as it can be used as a photopolymerization inhibitor. For example, p-benzoquinone, naphthoquinone, di-t-butyl paracresol, hydroquinone monomethyl ether, α-naphthol, acetamidine acetate Hydrazine hydrochloride, trimethylbenzylammonium chloride, dinitrobenzene, picric acid, quinonedioxime, pyrogallol, tannic acid, resorzine, cuperone, phenothiazine, and the like.

  The addition amount of the photopolymerization inhibitor is preferably 0.001 to 3 parts by mass, more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the binder resin. If it is less than this range, the effect of inhibiting polymerization is not exhibited, and even a low exposure amount due to light scattering is cured, and the line shape tends to be thickened. Also, if it exceeds this range, the sensitivity is lowered and a large amount of exposure is required, so care must be taken.

(Filler)
In the conductive resin composition of the present invention, a filler can be blended as necessary in order to increase the physical strength of the coating film. As such a filler, publicly known and commonly used inorganic or organic fillers can be used, and barium sulfate, silica, hydrotalcite and talc are particularly preferably used.

(Thermosetting catalyst)
When using the thermosetting component which has a 2 or more cyclic (thio) ether group in the said molecule | numerator in the conductive resin composition of this invention, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, the present invention is not limited to these, and any epoxy resin or oxetane compound thermosetting catalyst, or any one that promotes the reaction of a carboxyl group with at least one of an epoxy group and an oxetanyl group, alone or 2 A mixture of seeds or more may be used. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with the thermosetting catalyst.

  The blending amount of these thermosetting catalysts is sufficient at a normal quantitative ratio, for example, preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the binder resin. It is.

(Thermal polymerization inhibitor)
The thermal polymerization inhibitor can be used to prevent thermal polymerization or temporal polymerization of the conductive resin composition of the present invention. Examples of thermal polymerization inhibitors include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil. , Naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4 -Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

(Chain transfer agent)
In the conductive resin composition of the present invention, known N-phenylglycines, phenoxyacetic acids, thiophenoxyacetic acids, mercaptothiazole and the like can be used as chain transfer agents in order to improve sensitivity. Specific examples of chain transfer agents include, for example, chain transfer agents having a carboxyl group such as mercaptosuccinic acid, mercaptoacetic acid, mercaptopropionic acid, methionine, cysteine, thiosalicylic acid and derivatives thereof; mercaptoethanol, mercaptopropanol, mercaptobutanol Chain transfer agents having a hydroxyl group, such as 1-butanethiol, butyl-3-mercaptopropionate, methyl-3-mercaptopropionate, 2, 2 -(Ethylenedioxy) diethanethiol, ethanethiol, 4-methylbenzenethiol, dodecyl mercaptan, propanethiol, butanethiol, pentanethiol, 1-octanethiol, cyclo Ntanchioru, cyclohexane thiol, thioglycerol, 4,4-thiobisbenzenethiol like.

  A polyfunctional mercaptan-based compound can be used and is not particularly limited. For example, hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, dimercaptodiethylsulfide. Aliphatic thiols such as xylylene dimercaptan, 4,4′-dimercaptodiphenyl sulfide, and aromatic thiols such as 1,4-benzenedithiol; ethylene glycol bis (mercaptoacetate), polyethylene glycol bis (mercaptoacetate), Propylene glycol bis (mercaptoacetate), glycerin tris (mercaptoacetate), trimethylolethane tris (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), pentaerythritol Poly (mercaptoacetate) polyhydric alcohols such as rutetrakis (mercaptoacetate) and dipentaerythritol hexakis (mercaptoacetate); ethylene glycol bis (3-mercaptopropionate), polyethylene glycol bis (3-mercaptopropionate) ), Propylene glycol bis (3-mercaptopropionate), glycerin tris (3-mercaptopropionate), trimethylolethane tris (mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), penta Poly (3-mercaptopropionate) of polyhydric alcohol such as erythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) G) 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H) , 3H, 5H) -trione, poly (mercaptobutyrate) s such as pentaerythritol tetrakis (3-mertabutbutyrate) can be used.

  Examples of these commercially available products include BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP, and TEMPIC (above, manufactured by Sakai Chemical Industry Co., Ltd.), Karenz MT-PE1, Karenz MT-BD1, and Karenz -NR1 (above, Showa Denko)

  Further, examples of the heterocyclic compound having a mercapto group acting as a chain transfer agent include mercapto-4-butyrolactone (also known as 2-mercapto-4-butanolide), 2-mercapto-4-methyl-4-butyrolactone, and 2-mercapto. -4-ethyl-4-butyrolactone, 2-mercapto-4-butyrothiolactone, 2-mercapto-4-butyrolactam, N-methoxy-2-mercapto-4-butyrolactam, N-ethoxy-2-mercapto-4- Butyrolactam, N-methyl-2-mercapto-4-butyrolactam, N-ethyl-2-mercapto-4-butyrolactam, N- (2-methoxy) ethyl-2-mercapto-4-butyrolactam, N- (2-ethoxy) Ethyl-2-mercapto-4-butyrolactam, 2-mercapto-5-va Lolactone, 2-mercapto-5-valerolactam, N-methyl-2-mercapto-5-valerolactam, N-ethyl-2-mercapto-5-valerolactam, N- (2-methoxy) ethyl-2-mercapto- 5-valerolactam, N- (2-ethoxy) ethyl-2-mercapto-5-valerolactam, 2-mercaptobenzothiazole, 2-mercapto-5-methylthio-thiadiazole, 2-mercapto-6-hexanolactam, 2 , 4,6-Trimercapto-s-triazine (Sankyo Kasei Co., Ltd .: trade name Gisnet F), 2-dibutylamino-4,6-dimercapto-s-triazine (Sankyo Kasei Co., Ltd .: trade name Gisnet DB) , And 2-anilino-4,6-dimercapto-s-triazine (manufactured by Sankyo Kasei Co., Ltd .: trade name: DYSNET AF).

  In particular, as a heterocyclic compound having a mercapto group that is a chain transfer agent that does not impair the developability of the conductive resin composition, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade names: Accelerator M), 3-mercapto-4-methyl-4H-1,2,4-triazole, 5-methyl-1,3,4-thiadiazole-2-thiol, 1-phenyl-5-mercapto -1H-tetrazole is preferred. These chain transfer agents can be used alone or in combination of two or more.

(Defoamer)
An antifoaming agent can be blended in the conductive resin composition of the present invention for defoaming the coating film. Although it does not specifically limit as an antifoamer, For example, organic types, such as an acrylic type, are mentioned as a silicone type and a non-silicone type. An antifoamer may be used alone or in combination of two or more. Examples of commercially available antifoaming agents include BYK (registered trademark) -054, -055, -057, and -1790 manufactured by Big Chemie Japan as antifoaming agents made of a non-silicone-based foam-breaking polymer solution. Examples of silicone-based antifoaming agents include BYK (registered trademark) -063, -065, -066N, -067A, -077 manufactured by Big Chemie Japan, and KS-66 (trade name) manufactured by Shin-Etsu Silicone. Is mentioned.
The blending amount of such an antifoaming agent is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the binder resin.

(Leveling agent)
A leveling agent can be mix | blended with the conductive resin composition of this invention for the smoothness of the coating-film surface. The leveling agent is not particularly limited. For example, a polyacrylate polymer, a polyether-modified dimethylpolysiloxane copolymer, a polyester-modified dimethylpolysiloxane copolymer, a polyether-modified methylalkylpolysiloxane copolymer, and an aralkyl-modified polymer. Examples thereof include a methyl alkyl polysiloxane copolymer and a polyether-modified methyl alkyl polysiloxane copolymer. Leveling agents may be used alone or in combination of two or more. Examples of commercially available leveling agents include BYK (registered trademark) -350, -352, -354, -356, -361N, -392, manufactured by Big Chemie Japan, and polyflow series manufactured by Kyoeisha Chemical Co., Ltd. It is done.
The blending amount of such a leveling agent is preferably 0.1 to 20 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

(Coupling agent)
A coupling agent can be mix | blended with the conductive resin composition of this invention for the adhesive improvement with a base material. Examples of the coupling agent include a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent. As for a coupling agent, only 1 type may be used and 2 or more types may be used together. Among these, a silane coupling agent that exhibits a remarkable adhesion effect is preferable. Although it does not specifically limit as a silane coupling agent, For example, generally an epoxy silane coupling agent, an aminosilane coupling agent, a cationic silane coupling agent, a vinyl silane coupling agent, an acrylic silane coupling agent, a mercapto Examples thereof include silane coupling agents and composite coupling agents thereof. Examples of commercially available coupling agents include 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 trade names, manufactured by Shin-Etsu Silicone), Silquest A-186, Silquest A-187 (all Product Name, Momentive Performance Material Al's Co., Ltd.), and the like. These may be used alone or in combination of two or more.

  The blending amount of such a silane coupling agent is suitably 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

(Other additive components)
Needless to say, the conductive resin composition of the present invention can be appropriately blended with known and commonly used components such as thickeners, antioxidants, rust inhibitors and the like as necessary.

(Formation of cured product)
Next, an example of a method for forming a cured product using the conductive resin composition according to the present invention will be described.

  With respect to the conductive resin composition of the present invention, a machine such as a three-roll roll or a blender is used for kneading and dispersing the above-described essential components and optional components.

  The conductive resin composition thus dispersed is applied onto the substrate by an appropriate application method such as a screen printing method, a bar coater, or a blade coater. Next, in order to obtain dryness to the touch, the organic solvent is removed by drying at a temperature at which the carboxyl group-containing resin is not thermally decomposed, for example, about 60 to 120 ° C. for about 5 to 40 minutes in a hot air circulation drying oven, a far infrared drying oven or the like Evaporate to obtain a tack-free coating.

  Note that the conductive resin composition can 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 predetermined 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. As the exposure amount, the integrated light amount can be a low light amount of 200 mJ / cm ² or less. In addition, you may form a pattern in a coating film with a laser direct imaging apparatus, without using a mask.

  Next, the coating film is formed into a pattern by development such as spraying or dipping. Developers include aqueous alkali metal solutions such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and sodium silicate, and aqueous amine solutions such as monoethanolamine, diethanolamine and triethanolamine, especially about 1.5% by mass or less. A dilute alkaline aqueous solution having a concentration of 1 is preferably used, as long as the carboxyl group of the carboxyl group-containing resin in the conductive resin composition is saponified and the uncured part (unexposed part) is removed, as described above. The developer is not limited to such a developer. Moreover, it is preferable to perform washing with water and acid neutralization in order to remove an unnecessary developer after development.

  Then, the obtained cured product is cured at a temperature at which the carboxyl group-containing resin is not thermally decomposed. The curing temperature is preferably in the range of 100 ° C to 400 ° C, more preferably 120 to 400 ° C. Since the conductive resin composition of the present invention can obtain a cured product (for example, a conductive pattern film) by curing at a relatively low temperature of 400 ° C. or lower, it can be used on a substrate having low heat resistance or a material having low heat resistance. Can be used.

(Base material)
In these steps, since baking is not performed at a high temperature of 500 ° C., a resin base material having no heat resistance can be used as the base material. Specifically, as a resin base material, for example, a polyester resin such as polyimide, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), or polyethersulfone (PES). , Polystyrene (PS), polymethyl methacrylate (PMMA), polycarbonate (PC), polyamide (PA), polypropylene (PP), polyphenylene oxide (PPO), etc., preferably using a polyester resin Can do. A glass substrate or the like may be used.

  The present invention will be specifically described below based on examples. However, the present invention is not limited to these examples.

(Compounding ingredients)
Synthesis example of binder A [hydroxyl and carboxyl group-containing resin]
In a flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser, methyl methacrylate, methacrylic acid, and 2-hydroxyethyl acrylate are charged in a molar ratio of 47:15:38, and dipropylene glycol monomethyl ether as a solvent. Azobisisobutyronitrile was added as a catalyst and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere to obtain a “hydroxyl and carboxyl group-containing resin” varnish. The hydroxyl group- and carboxyl group-containing resin had a hydroxyl group equivalent of 300.

  Hereinafter, this “hydroxyl group and carboxyl group-containing resin” varnish is referred to as binder A-1 (A-1).

  Moreover, the compounding quantity of each component of the synthesis example of A-1 was changed, and the hydroxyl group equivalent "hydroxyl group and carboxyl group containing resin" varnish different from A-1 was created. These are designated as binders A-2 to A-5.

  Table 1 shows the hydroxyl equivalents (preparation ratio and calculated value) of binders A-1 to A-5, the molar ratio of methyl methacrylate, methacrylic acid, and 2-hydroxyethyl acrylate, and the acid value.

Synthesis example of binder B [Hydroxyl-containing resin, but no carboxyl group]
A flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser is charged with methyl methacrylate, t-butyl methacrylate, and 2-hydroxyethyl acrylate in a molar ratio of 62:15:23, and dipropylene glycol monomethyl ether as a solvent. Azobisisobutyronitrile was added as a catalyst, and the mixture was stirred at 80 ° C. for 6 hours under a nitrogen atmosphere to obtain a “hydroxyl group-containing resin” varnish. This hydroxyl group-containing resin had a hydroxyl group equivalent of 500.

  Hereinafter, this “hydroxyl group-containing resin” varnish is referred to as binder B-1 (B-1).

  Moreover, the compounding quantity of each component of the synthesis example of B-1 was changed, and the "hydroxyl group containing resin" varnish of the hydroxyl group equivalent different from B-1 was created. This is designated as Binder B-2 (B-2).

  Table 2 shows the hydroxyl equivalents (preparation ratio and calculated value) of binders B-1 to B-2, the molar ratio of methyl methacrylate, t-butyl methacrylate, and 2-hydroxyethyl acrylate, and the acid value.

Synthesis example of binder C [carboxyl group-containing resin, but does not have a hydroxyl group]
A flask equipped with a thermometer, a stirrer, a dropping funnel, and a reflux condenser is charged with methyl methacrylate, methacrylic acid, and t-butyl methacrylate in a molar ratio of 74:15:11. Dipropylene glycol monomethyl ether as a solvent, catalyst Azobisisobutyronitrile was added and stirred at 80 ° C. for 6 hours under a nitrogen atmosphere to obtain a “carboxyl group-containing resin” varnish. This carboxyl group-containing resin does not contain a hydroxyl group.

  Hereinafter, this “carboxyl group-containing resin” varnish is referred to as binder C-1 (C-1).

  Table 3 shows the hydroxyl equivalent (preparation ratio and calculated value) of binder C-1, the molar ratio of methyl methacrylate, t-butyl methacrylate and 2-hydroxyethyl acrylate, and the acid value, respectively.

[Conductive powder]
Spherical conductive powder: Ag powder (maximum particle size 30 μm or less, average particle size 2 μm (SEM))
[Reactive diluent]
Tetrafunctional (meth) acrylate monomer: Trade name; NK Oligo U-4HA (manufactured by Shin-Nakamura Chemical Co., Ltd.)
[Photopolymerization initiator]
Product Name: IRGACURE 379EG (BASF Japan), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone
[Thermosetting component]
Product name BI7982 (manufactured by Baxenden) Isocyanate HDI trimer Block isocyanate Dimethylpyrazole
Product name: jER828 (Mitsubishi Chemical Corporation) Bisphenol A type epoxy resin
[Organic acid]
2,2'-thiodiacetic acid
[Dispersant]
Product name DISPERBYK-111 (by Big Chemie Japan)

(Evaluation method)
Specimen creation:
Each conductive resin composition for evaluation was applied on the entire surface of a polyester resin substrate using a 300-mesh polyester screen, and then dried in a hot-air circulating drying oven at 80 ° C. for 30 minutes to touch. A coating film having good drying property was formed. Thereafter, using a high-pressure mercury lamp as a light source, pattern exposure was performed through a negative mask so that the integrated light amount on the conductive resin composition was 200 mJ / cm ^2, and then 0.4 mass% Na ₂ CO at a liquid temperature of 30 ° C. Development was performed using ₃ aqueous solutions and washed with water. Finally, it was dried at 140 ° C. for 30 minutes to prepare a test piece on which a conductive pattern film was formed.

  Coating film strength: L / S = 30/30 μm pattern formation was performed under the above-mentioned test piece preparation conditions, and a load of 750 g was applied using a pencil hardness tester which is an apparatus described in JIS K5600-5-4. The case where the line was not broken when scratched perpendicularly to the side of the line was evaluated as “good”. Those with defects were evaluated as “bad”. The pencil used was Mitsubishi High Uni (Mitsubishi Pencil Co., Ltd., hardness: 3H).

  Contact resistance value: On an ITO film with a sheet resistance value of 150Ω, I-type lines with a length of 50mm and a width of 100um are formed at intervals of 5mm, and pattern formation is performed under the conditions for creating the test piece described above, and a tester is placed on the center of the pattern It was measured.

  Adhesion: L / S = 30/30 μm pattern was formed, cellotape (registered trademark) peel was performed, and no defect was evaluated as “good”. Those with defects were evaluated as “bad”.

  Resolution: A line pattern was formed under the conditions for preparing the test piece, and the minimum line width was evaluated.

  Specific resistance value: Pattern formation of 4 mm × 10 cm was performed under the above-mentioned test piece preparation conditions, and the specific resistance value was calculated by measuring the resistance value and film thickness. In the minimum line, a sample having no defect was evaluated as “good”.

  About Examples 1-8 included in the scope of the present invention and Comparative Examples 1-6 outside the scope of the present invention, the blending amount (parts by mass) of each component of the conductive resin composition, the hydroxyl equivalent, and the evaluation results are shown respectively. The results are summarized in Table 4 and Table 5 below.

*1 水酸基を含まないことの意

* 1 Meaning that it does not contain a hydroxyl group

*1 水酸基を含まないことの意

* 1 Meaning that it does not contain a hydroxyl group

  From Examples 1 to 8, the conductive resin composition according to the present invention can be applied to a heat-sensitive substrate, can ensure excellent conductivity and resolution, and can be applied even under more severe conditions. It was confirmed that a conductive resin composition excellent in both film strength and adhesion to the base substrate can be obtained.

Claims (5)

  It contains a hydroxyl group and carboxyl group-containing resin, a conductive powder, a reactive diluent, a photopolymerization initiator, and a thermosetting component, and the total hydroxyl group equivalent of the hydroxyl group and carboxyl group-containing resin is 300 or more and 3000 or less. A conductive resin composition characterized by the above.   Contains two or more resins selected from the group of hydroxyl and carboxyl group-containing resins, hydroxyl group-containing resins, and carboxyl group-containing resins, conductive powders, reactive diluents, photopolymerization initiators, and thermosetting components. The conductive resin composition, wherein the total of hydroxyl equivalents of the two or more resins is 300 or more and 3000 or less.   The conductive resin composition according to claim 1, wherein the thermosetting component is a polyfunctional epoxy resin.   The conductive resin composition according to claim 1, wherein the conductive resin composition is for forming a conductive circuit.   Hardened | cured material formed by apply | coating and drying the resin composition in any one of Claims 1-4 on a base material.