JP5463498B1 - Photosensitive conductive ink and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive conductive ink which is excellent in photosensitivity and developability, and can form a conductive layer excellent in electroconductivity, adhesion, wet heat resistance and the like.
A photosensitive conductive ink containing a photosensitive resin (A), conductive particles (B) and a photopolymerization initiator (C), wherein the photosensitive resin (A) is an epoxy compound (a). A compound having a polybasic acid anhydride (d), an epoxy group or an oxetane group, and an ethylenically unsaturated group (c) having a hydroxyl group in the side chain formed by reacting a phenol compound (b) with f) and a polybasic acid anhydride (g), which is a photosensitive resin (A-1) or (A-2) having a carboxyl group and an ethylenically unsaturated group in the side chain. A photosensitive conductive ink characterized by
[Selection figure] None

Description

  The present invention relates to a conductive ink excellent in photosensitivity to active energy rays and developability with a dilute alkaline aqueous solution, and a laminate with a conductive pattern obtained using the conductive ink.

  In general, an etching method and a printing method are known as an electronic component, a thin film forming unit for electromagnetic wave shielding, or a conductive circuit forming unit. The etching method means a processing technique in a broad sense including a surface treatment of a metal by dissolving or removing the surface or shape of the metal chemically or electrochemically. Etching is a kind of chemical processing, and is mainly performed to obtain a desired pattern shape on a metal film. However, the process is generally complicated and waste liquid treatment is required in the subsequent process, so the cost is also high. There are many problems. In addition, since the conductive circuit formed by the etching method is formed of a metal material such as aluminum or copper, there is a problem that the conductive circuit is weak against physical impact such as bending.

  Therefore, in order to solve these problems and form a conductive circuit at a lower cost, conductive ink has attracted attention. A conductive circuit can be easily formed by printing conductive ink. Furthermore, since electronic components can be expected to be smaller and lighter, improve productivity, and reduce costs, research and development on printable conductive ink has been energetically made, and many proposals have been made (for example, patents). Literature 1-9).

  Moreover, the method of forming a pattern using the photosensitive conductive composition is proposed (patent documents 10-12).

  Further, Patent Documents 13 to 14 disclose that a non-conductive photosensitive resin composition is used for a solder resist or the like.

Japanese Patent Application Laid-Open No. 06-68924 WO2003 / 103352 brochure JP 2003-238876 A JP 2001-234106 A JP 2005-29639 A JP 2006-310022 A JP 2003-68139 A JP 2003-331648 A JP-A-2005-183301 JP 05-271576 A JP 2003-162921 A WO2004 / 061006 pamphlet JP 2011-93999 A JP 2013-0033207 A

However, it is difficult to achieve high definition equivalent to etching by a method using only a printing process as described in Patent Documents 1 to 9.
In addition, in the methods described in Patent Documents 10 to 12, it is difficult to achieve both photolithography process (active energy ray photosensitivity and alkali developability) adaptability, adhesion, and conductivity.

  Furthermore, in recent years, the items required for the conductive circuit pattern used in touch screen panels that are frequently used in mobile terminals such as mobile phones and game machines, personal computers, etc. are only the above-mentioned high definition. In addition, the resistance value is stable even when the touch panel is exposed to a high temperature and high humidity environment. In particular, conductive inks that have been proposed in the past for high definition using the photolithographic method have major problems in maintaining the stability and adhesion of resistance against such environmental loads, making it difficult to ensure the durability and reliability of the touch panel. ing.

  Patent Document 13 does not describe the use of a carboxyl group-containing resin for conductive ink.

  The present invention is excellent in photosensitivity to active energy rays, can form a fine pattern by development with a dilute alkaline aqueous solution, and has a cured coating film obtained through a post-curing (post-cure) process having conductivity, adhesion, and heat and humidity resistance. In particular, it is intended to provide a photosensitive conductive ink used for forming a fine electric circuit by a photolithographic process, a cured product thereof, and a laminate after forming a rough pattern by various printing methods. .

  In order to solve the above problems, the present inventors have found that a photosensitive resin composition containing a specific photosensitive resin (A) can solve the above problems as a result of intensive studies. It came to complete.

That is, the first invention is a photosensitive conductive ink containing a photosensitive resin (A), conductive particles (B) and a photopolymerization initiator (C),
The photosensitive resin (A) is
Epoxy compound having at least two epoxy groups in a molecule formed by a combination of a bisphenol type epoxy resin and polyethylene glycol diglycidyl ether and (a), a phenol compound having at least two phenolic hydroxyl groups in the molecule (B) is reacted to produce a resin (c) having a hydroxyl group in the side chain;
Reacting at least part of the hydroxyl groups in the resin (c) having a hydroxyl group in the side chain with a polybasic acid anhydride (d) to produce a resin (e) having a carboxyl group in the side chain;
A part of the carboxyl group in the resin (e) having a carboxyl group in the side chain is reacted with the epoxy group or oxetane group in the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group. A photosensitive resin (A-1) having a carboxyl group and an ethylenically unsaturated group in the side chain,
The present invention relates to a photosensitive conductive ink.

The second invention is a photosensitive conductive ink comprising a photosensitive resin (A), conductive particles (B), and a photopolymerization initiator (C),
The photosensitive resin (A) is
Epoxy compound having at least two epoxy groups in a molecule formed by a combination of a bisphenol type epoxy resin and polyethylene glycol diglycidyl ether and (a), a phenol compound having at least two phenolic hydroxyl groups in the molecule (B) is reacted to produce a resin (c) having a hydroxyl group in the side chain;
Reacting at least a part of the hydroxyl groups in the resin (c) having a side chain hydroxyl group with the polybasic acid anhydride (d) to produce a carboxyl group-containing resin (e) in the side chain;
By reacting at least part of the carboxyl group in the carboxyl group-containing resin (e) with the epoxy group or oxetane group in the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group. Producing a resin (AA-1) having a hydroxyl group and an ethylenically unsaturated group in the chain;
Further, at least a part of the hydroxyl group in the resin (AA-1) having a hydroxyl group and an ethylenically unsaturated group in the side chain is reacted with the acid anhydride group in the polybasic acid anhydride (g). The present invention relates to a photosensitive conductive ink, which is a photosensitive resin (A-2) having a carboxyl group and an ethylenically unsaturated group in a side chain.

Moreover, 3rd invention is related with the photosensitive resin composition of the invention of any one of 1-2 whose acid value of the photosensitive resin (A) is 10-200 mgKOH / g.
The fourth invention relates to the photosensitive conductive ink according to any one of the first to third inventions, wherein the photosensitive resin (A) has an ethylenically unsaturated group equivalent of 200 to 5000 g / eq.
The fifth invention relates to the photosensitive conductive ink according to any one of the first to fourth inventions, wherein the photosensitive resin (A) has a weight average molecular weight of 1,000 to 100,000.

The sixth invention relates to a cured product obtained by curing the photosensitive conductive ink of any one of the first to fifth inventions.

Moreover, 7th invention comprises a base material and the conductive pattern formed on the said base material, The said conductive pattern is formed with the conductive ink as described in any one of the 1st- 5th invention. It is related with the laminated body with a conductive pattern.
Moreover, 8th invention is related with the laminated body with a conductive pattern of 7th invention which further comprises the insulating layer laminated | stacked so that the said conductive pattern might be covered.
The invention of ninth, the at the lower layer side of the conductive pattern, the other conductive film having the conductive pattern and electrically connected to the predetermined pattern is further formed on the substrate, the seventh It relates to a laminate with a conductive pattern according to any one of -8 .
The tenth invention relates to a laminate with a conductive pattern according to the ninth invention, wherein the other conductive film is a transparent conductive film mainly composed of indium oxide doped with tin.
The eleventh invention relates to a laminate with a conductive pattern according to any of the seventh to tenth inventions used for touch screen panel applications.

In the present invention, the following may be abbreviated. That is,
Resin (c) having a hydroxyl group in the side chain is a side chain hydroxyl group-containing resin (c),
Resin (e) having a carboxyl group in the side chain is a side chain carboxyl group-containing resin (e),
A photosensitive resin (A-1) having a carboxyl group and an ethylenically unsaturated group in the side chain, a side chain carboxyl group-containing photosensitive resin (A-1) or a photosensitive resin (A-1),
Resin (AA-1) having a hydroxyl group and an ethylenically unsaturated group in the side chain, a side chain hydroxyl group-containing resin (AA-1) or a photosensitive resin (AA-1);
Photosensitive resin (A-2) having a carboxyl group and an ethylenically unsaturated group in the side chain may be abbreviated as side chain carboxyl group-containing photosensitive resin (A-2) or photosensitive resin (A-2). is there.
Alternatively, the “side chain” may be omitted.

  According to the present invention, it has excellent photosensitivity to active energy rays, and a fine pattern can be formed by development with a dilute alkaline aqueous solution, and a cured coating film obtained through a post-curing (post-cure) process has conductivity, adhesion, and heat and humidity resistance. In particular, it is possible to provide a photosensitive conductive ink used for forming a fine electric circuit by a photolithography process, a cured product thereof, and a laminate after creating a pattern by various printing methods. It was. The photosensitive conductive ink of the present invention is suitably used as a photosensitive conductive ink for the formation of a fine conductive circuit formed on the frame of a touch screen panel or a fine metal mesh sheet having both transparency and low surface resistance. Can be used.

It is a schematic sectional block diagram of the principal part of an example of the resistive film type touch screen panel which applied the conductive ink of this invention to the wiring structure, and is equivalent to the AA 'cut line of FIG. It is a perspective view which shows the lamination | stacking state of a suitable resistive film type touch screen panel by applying the conductive ink of this invention to a wiring structure.

In the photosensitive conductive ink of the present invention, the photosensitive resin (A) does not have an ester bond derived from half esterification with a dibasic acid anhydride or a urethane bond derived from the reaction of an isocyanate group and a hydroxyl group in the main chain. Therefore, since the main chain is chemically stable, the resulting cured coating film has excellent resistance to various coating films and maintains excellent durability and conductivity even after being exposed to high temperature conditions and high temperature and humidity. .
Although the detailed mechanism is not clear, the absence of an ester bond or urethane bond in the main chain limits the adsorption of the photosensitive resin (A) to the conductive particles (B), and the photosensitive resin (A ) Is suppressed, the aggregation of the conductive particles is promoted during heating and drying, and the conductivity is considered to be improved.
Furthermore, since the photosensitive resin (A) used in the present invention has a photosensitive group and a carboxyl group in the side chain, even if the amount of the photosensitive group and the carboxyl group is small, a very excellent photosensitivity. Property, resolution, and developability. These functional groups are more reactive when introduced into the side chain than when directly attached to the main chain. In addition, when these functional groups are introduced into the side chain as compared with the case where they are introduced only at the ends of the main chain, the introduction amount can be arbitrarily adjusted, so that excellent photosensitivity, resolution, developability, and The coating film resistance can be exhibited. Hereinafter, the photosensitive resin (A) and the photosensitive resin composition of the present invention will be described.

The photosensitive resin (A) used in the present invention is a side chain carboxyl group-containing photosensitive resin (A-1) or a side chain carboxyl group-containing photosensitive resin (A-2) shown below.
The side chain carboxyl group-containing photosensitive resin (A-1) includes, as a first step, an epoxy compound (a) having at least two epoxy groups in one molecule and at least two phenolic compounds in one molecule. A side chain hydroxyl group-containing resin (c) is prepared by reacting with a phenol compound (b) having a hydroxyl group.
The phenolic hydroxyl group in the phenol compound (b) undergoes an addition reaction with the epoxy group in the epoxy compound (a), and the epoxy group is opened, resulting in an ether bond and a secondary hydroxyl group. The main chain in the side chain hydroxyl group-containing resin (c) is a structure in which the structure derived from the epoxy compound (a) and the structure derived from the phenol compound (b) are linked by an ether bond. The hydroxyl group in the side chain hydroxyl group-containing resin (c) is located in the side chain with respect to the main chain linked by an ether bond.

Next, as a second step, a part of the hydroxyl groups in the side chain hydroxyl group-containing resin (c) is reacted with the polybasic acid anhydride (d) to prepare a carboxyl group-containing resin (e). . In this case, the carboxyl group-containing resin (e) also has an unreacted hydroxyl group in the side chain.
Alternatively, the carboxyl group-containing resin (e) can be prepared by reacting all of the hydroxyl groups in the side chain hydroxyl group-containing resin (c) with the polybasic acid anhydride (d).

Furthermore, as a third step, an epoxy group or oxetane group in the compound (f) having a part of the carboxyl group in the carboxyl group-containing resin (e) and an epoxy group or oxetane group and an ethylenically unsaturated group. Can be reacted to obtain a side chain carboxyl group-containing photosensitive resin (A-1). The side chain carboxyl group-containing photosensitive resin (A-1) has a carboxyl group derived from the carboxyl group-containing resin (e).
Further, the side chain carboxyl group-containing photosensitive resin (A-1) has a hydroxyl group newly generated by a reaction between a carboxyl group and an epoxy group or an oxetane group in the side chain. In addition, when using what also has an unreacted hydroxyl group in a side chain as carboxyl group containing resin (e), side chain carboxyl group containing photosensitive resin (A-1) is a side chain hydroxyl group containing resin (A-1). It also has a hydroxyl group derived from c). Therefore, it can be said that the side chain carboxyl group-containing photosensitive resin (A-1) is a photosensitive resin (A-1) having a carboxyl group, a hydroxyl group, and an ethylenically unsaturated group in the side chain.

The side chain carboxyl group-containing photosensitive resin (A-2) used in the present invention is obtained from four steps.
The first and second steps are the same as in the case of obtaining the side chain carboxyl group-containing photosensitive resin (A-1).
In the third step in obtaining the side chain carboxyl group-containing photosensitive resin (A-2), all of the carboxyl groups in the carboxyl group-containing resin (e) are converted to epoxy groups or oxetane groups and ethylenically unsaturated groups. Is slightly different from the third step in obtaining the side chain carboxyl group-containing photosensitive resin (A-1) in that it may be reacted with an epoxy group or an oxetane group in the compound (f). . That is, when all of the carboxyl groups in the carboxyl group-containing resin (e) are reacted with the compound (f), the resulting photosensitive resin (AA-1) has a hydroxyl group in the side chain, There is no carboxyl group in the chain.
On the other hand, when a part of the carboxyl groups in the carboxyl group-containing resin (e) is reacted with the compound (f), the resulting photosensitive resin (AA-1) has hydroxyl groups and carboxyl groups in the side chain. Therefore, it is synonymous with the photosensitive resin (A-1) having a hydroxyl group and a carboxyl group in the side chain.
Therefore, hereinafter, the photosensitive resin (A-1) and the photosensitive resin (AA-1) may be collectively referred to as “side chain hydroxyl group-containing photosensitive resin (A-1)”. .

Next, in the side chain carboxyl group-containing photosensitive resin (A-2) used in the present invention, as a fourth step, at least a part of the hydroxyl groups in the side chain hydroxyl group-containing resin (AA-1) is contained. It can be obtained by reacting with an acid anhydride group in the basic acid anhydride (g). All of the hydroxyl groups in the side chain hydroxyl group-containing resin (AA-1) can also be reacted with the polybasic acid anhydride (g).
The side chain carboxyl group-containing photosensitive resin (A-2) has a carboxyl group derived from the polybasic acid anhydride (g). Furthermore, the side chain carboxyl group-containing photosensitive resin (A-2) can also have a carboxyl group derived from the polybasic acid anhydride (d) constituting the carboxyl group-containing resin (e).
Hereinafter, the manufacturing method of photosensitive resin (A) is demonstrated in detail.

First, the side chain hydroxyl group-containing resin (c) obtained in the first step of the present invention will be described.
The side chain hydroxyl group-containing resin (c) reacts an epoxy compound (a) having at least two epoxy groups in one molecule with a phenol compound (b) having at least two phenolic hydroxyl groups in one molecule. Can be obtained. The epoxy group and the phenolic hydroxyl group are preferably reacted at a molar ratio of epoxy group: phenolic hydroxyl group = 1: 1 to 1: 2.5. By making the phenolic hydroxyl group in the phenol compound (b) 1 mol or more with respect to 1 mol of the epoxy group in the epoxy compound (a), it becomes easy to obtain an appropriate molecular weight, and the heat resistance is further improved. On the other hand, by making the phenolic hydroxyl group in the phenol compound (b) 2.5 mol or less, the amount of the terminal epoxy group can be made more appropriate, so the polybasic acid anhydride (d) is reacted in the next step. It becomes easier to control the reaction.

  In addition, the molar ratio as used in the field of this invention is a molar ratio with which functional groups actually react, and various starting materials use the quantity which enables reaction by the said molar ratio. Therefore, for example, in the reaction of “epoxy compound (a) having at least two epoxy groups in one molecule” and “phenol compound (b) having at least two phenolic hydroxyl groups in one molecule”, When the starting material is charged, “having at least two phenolic hydroxyl groups in one molecule” with respect to 1.0 mol of epoxy groups in “epoxy compound (a) having at least two epoxy groups in one molecule”. The phenolic hydroxyl group in the “phenolic compound (b)” may be charged in an amount exceeding 2.5 mol (preferably charged at an upper limit of 2.7 mol).

The epoxy compound (a) having at least two epoxy groups in one molecule used in the present invention is not particularly limited as long as it is preferably a compound containing two epoxy groups in the molecule.
Specifically, examples of the compound containing two epoxy groups in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and tetramethylene glycol diglycidyl ether. , Polytetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenol type epoxy resin, polyglycidyl ether of glycerin / epichlorohydrin adduct, resorcinol Diglycidyl ether, polybutadiene diglycidyl ether, hydroquinone diglycidyl ether, dibromoneopentylglycol Rudiglycidyl ether, neopentyl glycol diglycidyl ether, hexahydrophthalic acid diglycidyl ester, hydrogenated bisphenol A type diglycidyl ether, dihydroxyanthracene type epoxy resin, polypropylene glycol diglycidyl ether, diphenylsulfone diglycidyl ether, dihydroxybenzophenone diglycidyl Ether, biphenol diglycidyl ether, diphenylmethane diglycidyl ether, bisphenol fluorenediglycidyl ether, biscresol fluorenediglycidyl ether, bisphenoxyethanol fluorenediglycidyl ether, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N , N-diglycidyl aniline, N, N-diglycidyl tolu Epoxy compounds such as gin and the like.

Among these, polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether are used for the flexibility of the conductive layer formed from the photosensitive conductive ink containing the finally obtained photosensitive resin (A) and the alkaline developer. It is preferable at the point which can improve solubility. Particularly preferred is polyethylene glycol diglycidyl ether.
Moreover, the bisphenol type epoxy resin is preferable in that the heat resistance of the ink layer formed from the photosensitive conductive ink containing the finally obtained photosensitive resin (A) can be improved. As the bisphenol type epoxy resin, Bisphenol A type epoxy resin is more preferable.
In particular, it is more preferable to use a bisphenol type epoxy resin and polyethylene glycol diglycidyl ether in combination. When used in combination, the bisphenol-type epoxy resin and the polyethylene glycol diglycidyl ether can be adjusted at an arbitrary weight ratio, and the physical properties of the finally obtained conductive layer can be adjusted according to the charged weight ratio. For example, it is preferable that the charging weight ratio of the bisphenol type epoxy resin and the polyethylene glycol diglycidyl ether is 20/80 to 80/20. By being in the above range, it is possible to improve the conductivity and adhesion, and the conductivity and developability, which tend to be a trade-off, in a well-balanced manner.

  Examples of the bisphenol type epoxy resin that can be suitably used in the present invention include a bisphenol A type epoxy compound (YD8125, epoxy equivalent 173 g / eq, manufactured by Nippon Steel Chemical Co., Ltd.), a bisphenol F type epoxy compound (YDF8170C, epoxy). Equivalent 160 g / eq, manufactured by Nippon Steel Chemical Co., Ltd.).

  Examples of polyethylene glycol diglycidyl ether that can be suitably used in the present invention include “EX861”: Epoxy equivalent 575 g / eq, “EX830”: Epoxy equivalent 268 g / eq, manufactured by Nagase ChemteX Corporation. Examples of polypropylene glycol diglycidyl ether that can be used in the present invention include “EX931” manufactured by Nagase ChemteX Corporation: epoxy equivalent of 493 g / eq.

  Further, as a compound containing 3 or more epoxy groups in the molecule, trishydroxyethyl isocyanurate triglycidyl ether, triglycidyl isocyanurate, “Epicoat 1031S”, “Epicoat 1032H60”, “Epicoat 604” manufactured by Mitsubishi Chemical Corporation In addition to “Epicoat 630”, phenol novolac type epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, ethylene glycol / epichlorohydrin adduct disclosed in JP-A No. 2001-240654 Polyglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenedi Amines and the like. Moreover, the compound which has other thermosetting groups other than an epoxy group can also be used. For example, the silane modified epoxy resin currently disclosed by Unexamined-Japanese-Patent No. 2001-59011 and 2003-48953 is mentioned.

  Since these compounds containing 3 or more epoxy groups in the molecule can be used in combination with a compound containing 2 epoxy groups in the molecule, a branched structure can be introduced into the main chain. The cohesive strength of the film increases, and adhesion and heat resistance can be improved without adversely affecting storage stability and coating film flexibility.

  Other epoxy compounds (a) having at least two epoxy groups in one molecule are disclosed in JP-A Nos. 2004-156024, 2004-315595, and 2004-323777. Examples thereof include an epoxy compound having excellent flexibility and an epoxy compound having a structure represented by the following formulas (1) to (3).

Formula (1)

Formula (2)

Formula (3)

As described above, in the present invention, the epoxy compound (a) having at least two epoxy groups in one molecule can be selected according to the purpose, and these may be used alone or in combination. Use in combination is also preferred.

The phenol compound (b) having at least two phenolic hydroxyl groups in one molecule used in the present invention is preferably a compound containing two phenolic hydroxyl groups in the molecule, and is not particularly limited. Absent.
For example, 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A) is a representative example.
Bis (4-hydroxyphenol) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -n-propane, 1,1-bis (4-hydroxyphenyl) -N-butane, 1,1-bis (4-hydroxyphenyl) -n-pentane, 1,1-bis (4-hydroxyphenyl) -n-hexane, 1,1-bis (4-hydroxyphenyl) -n -Heptane, 1,1-bis (4-hydroxyphenyl) -n-octane, 1,1-bis (4-hydroxyphenyl) -n-nonane, 1,1-bis (4-hydroxyphenyl) -n-decane Bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxyphenyl) tolylmethane, bis (4-hydroxy) Phenyl)-(4-ethylphenyl) methane, bis (4-hydroxyphenyl)-(4-n-propylphenyl) methane, bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane, bis (4-hydroxy) Phenyl)-(4-n-butylphenyl) methane, bis (4-hydroxyphenyl)-(4-pentylphenyl) methane, bis (4-hydroxyphenyl)-(4-hexylphenyl) methane, bis (4-hydroxy) Phenyl)-(4-fluorophenyl) methane, bis (4-hydroxyphenyl)-(4-chlorophenyl) methane, bis (4-hydroxyphenyl)-(2-fluorophenyl) methane, bis (4-hydroxyphenyl)- (2-Chlorophenyl) methane, bis (4-hydroxyphenyl) tetrafur Rophenylmethane, bis (4-hydroxyphenyl) tetrachlorophenylmethane, bis (3-methyl-4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3-ethyl-4 -Hydroxyphenyl) methane, bis (3-isobutyl-4-hydroxyphenyl) methane, bis (3-tert-butyl-4-hydroxyphenyl) -1-phenylmethane, bis (3-phenyl-4-hydroxyphenyl)- 1-phenylmethane, bis (3-fluoro-4-hydroxyphenyl) methane, bis (3,5-difluoro-4-hydroxyphenyl) methane, bis (3-chloro-4-hydroxyphenyl) methane, bis (3 5-dichloro-4-hydroxyphenyl) methane, 1,1-bis (3-methyl-4- Hydroxyphenyl) ethane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) ethane, 1,1-bis (3-ethyl-4-hydroxyphenyl) ethane, 1,1-bis (3-isobutyl) -4-hydroxyphenyl) ethane, 1,1-bis (3-fluoro-4-hydroxyphenyl) ethane, 1,1-bis (3,5-difluoro-4-hydroxyphenyl) ethane, 1,1-bis ( Bisphenols in which a hydrogen atom is bonded to a central carbon such as 3-chloro-4-hydroxyphenyl) ethane and 1,1-bis (3,5-dichloro-4-hydroxyphenyl) ethane;

  2,2-bis (4-hydroxyphenyl) -n-butane, 2,2-bis (4-hydroxyphenyl) -n-pentane, 2,2-bis (4-hydroxyphenyl) -n-hexane, 2, 2-bis (4-hydroxyphenyl) -n-heptane, 2,2-bis (4-hydroxyphenyl) -n-octane, 2,2-bis (4-hydroxyphenyl) -n-nonane, 2,2- Bis (4-hydroxyphenyl) -n-decane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane (commonly called bisphenol P), 1,1-bis (4-hydroxyphenyl) -1-naphthylethane 1,1-bis (4-hydroxyphenyl) -1-toluylethane, 1,1-bis (4-hydroxyphenyl) -1- (4-ethylphenyl) ethane, 1,1-bis (4 Hydroxyphenyl) -1- (4-n-propylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (4-isopropylphenyl) ethane, 1,1-bis (4-hydroxyphenyl)- 1- (4-n-butylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (4-pentylphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (4 -Hexylphenyl) ethane, 1,1-bis (3-tert-butyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (3-phenyl-4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1- (4-fluorophenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (4-chlorophenyl) 1,1-bis (4-hydroxyphenyl) -1- (2-fluorophenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1- (2-chlorophenyl) ethane, 1,1-bis Bisphenols in which one methyl group is bonded to the central carbon such as (4-hydroxyphenyl) -1-tetrafluorophenylethane, 1,1-bis (4-hydroxyphenyl) -1-tetrachlorophenylethane;

  2,2-bis (3-methyl-4-hydroxyphenyl) propane (commonly called bisphenol C), 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-ethyl) -4-hydroxyphenyl) propane, 2,2-bis (3-isobutyl-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3 Central carbon such as 5-difluoro-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane Bisphenols having two methyl groups bonded to each other;

  Bis (4-hydroxyphenyl) -1,1-diphenylmethane, bis (3-methyl-4-hydroxyphenyl) -1,1-diphenylmethane, bis (3-t-butyl-4-hydroxyphenyl) -1,1- Bisphenols which are diphenylmethane derivatives such as diphenylmethane, bis (3-phenyl-4-hydroxyphenyl) -1,1-diphenylmethane, bis (3-chloro-4-hydroxyphenyl) -1,1-diphenylmethane;

1,1-bis (4-hydroxyphenyl) cyclohexane (commonly called bisphenol Z), 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxy) Phenyl) cyclohexane, 1,1-bis (3-ethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-isobutyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-fluoro-4-) Hydroxyphenyl) cyclohexane, 1,1-bis (3,5-difluoro-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-chloro-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5 Bisph is a cyclohexane derivative such as -dichloro-4-hydroxyphenyl) cyclohexane Nord like;
1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1- Bis (3,5-dimethyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-ethyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1, 1-bis (3-isobutyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-fluoro-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1, -3,3,5-trimethylsilane such as 1-bis (3,5-difluoro-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane Bisphenols is Rohekisan derivatives;
9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) fluorene, 9 , 9-bis (3-ethyl-4-hydroxyphenyl) fluorene, 9,9-bis (3-isobutyl-4-hydroxyphenyl) fluorene, 1,1-bis (3-fluoro-4-hydroxyphenyl) fluorene, Bisphenols which are fluorene derivatives such as 9,9-bis (3,5-difluoro-4-hydroxyphenyl) fluorene;

1,1-bis (4-hydroxyphenyl) -cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclooctane, 1,1-bis (4 Bisphenols which are cycloalkane derivatives such as -hydroxyphenyl) cyclononane, 1,1-bis (4-hydroxyphenyl) cyclodecane;
Biphenols directly linked with aromatic rings such as 4,4′-biphenol;
Bis (4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3-ethyl-4-hydroxyphenyl) sulfone, Bisphenols which are sulfone derivatives such as bis (3-isobutyl-4-hydroxyphenyl) sulfone, bis (3-fluoro-4-hydroxyphenyl) sulfone, bis (3,5-difluoro-4-hydroxyphenyl) sulfone;

  Bis (4-hydroxyphenyl) ether, bis (3-methyl-4-hydroxyphenyl) ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3-ethyl-4-hydroxyphenyl) ether, Bisphenols having an ether bond such as bis (3-isobutyl-4-hydroxyphenyl) ether, bis (3-fluoro-4-hydroxyphenyl) ether, bis (3,5-difluoro-4-hydroxyphenyl) ether;

Bis (4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3-ethyl-4-hydroxyphenyl) sulfide, Bisphenols having a sulfide bond such as bis (3-isobutyl-4-hydroxyphenyl) sulfide, bis (3-fluoro-4-hydroxyphenyl) sulfide, bis (3,5-difluoro-4-hydroxyphenyl) sulfide;
Bis (4-hydroxyphenyl) sulfoxide, bis (3-methyl-4-hydroxyphenyl) sulfoxide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfoxide, bis (3-ethyl-4-hydroxyphenyl) sulfoxide, Bisphenols which are sulfoxide derivatives such as bis (3-isobutyl-4-hydroxyphenyl) sulfoxide, bis (3-fluoro-4-hydroxyphenyl) sulfoxide, bis (3,5-difluoro-4-hydroxyphenyl) sulfoxide;

Bisphenols having a heteroatom-containing aliphatic ring such as phenolphthalein;
Bis (2,3,5,6-tetrafluoro-4-hydroxyphenyl) difluoromethane, 1,1-bis (2,3,5,6-tetrafluoro-4-hydroxyphenyl) perfluoroethane, 2,2 -Bisphenols having a carbon-fluorine bond such as bis (2,3,5,6-tetrafluoro-4-hydroxyphenyl) perfluoropropane and 2,2-bis (4-hydroxyphenyl) hexafluoropropane be able to.
And dihydroxybenzenes such as hydroquinone, resorcinol, catechol, methylhydroquinone;
Examples thereof include dihydroxynaphthalenes such as 1,5-dihydroxynaphthalene and 2,6-dihydroxynaphthalene.
Among these, bisphenol A and bisphenol F are preferable from the viewpoint of easy availability of industrial products, various coating film resistances, heat resistance, and moist heat resistance.

  Examples of the compound containing three or more phenolic hydroxyl groups in the molecule include bis (3,4-dihydroxy-6-methylphenyl) phenylmethane, tris (4-hydroxyphenyl) methane, and bis (4-hydroxy-3). -Methylphenyl) -4-hydroxy-3-methoxyphenylmethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 2,6-bis (4-hydroxy-3,5- Dimethylbenzyl) -4-methylphenol, 2,6-bis (2,4-dihydroxybenzyl) -4-methyl-phenol, 2,2-bis [4-hydroxy-3,5-bis (2-hydroxy-5) -Methylbenzyl) phenyl] propane, 1,1,2,2-tetrakis (4-hydroxyphenyl) -ethane, α, α, α ′, α′-tetra Scan (4-hydroxyphenyl)-p-xylene, 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, phenol aralkyl resins.

  Since these compounds containing 3 or more phenolic hydroxyl groups in the molecule can be used in combination with a compound containing 2 phenolic hydroxyl groups in the molecule, a branched structure can be introduced into the main chain. The cohesive strength of the cured coating film increases, and adhesion, heat resistance, and heat and humidity resistance can be improved without adversely affecting storage stability, processing stability, and coating film flexibility.

In the present invention, the conditions for synthesizing the side chain hydroxyl group-containing resin (c) are not particularly limited, and can be performed under known conditions. For example, an epoxy compound (a) having at least two epoxy groups in one molecule, a phenol compound (b) having at least two phenolic hydroxyl groups in one molecule, and a solvent are charged into a flask while stirring. The side chain hydroxyl group-containing resin (c) can be obtained by heating at 100 to 150 ° C. At this time, a catalyst such as triphenylphosphine or a tertiary amino group-containing compound may be used as necessary.
In the reaction between the epoxy compound (a) and the phenol compound (b), the epoxy compound is added to the phenolic hydroxyl group of the phenol compound (b) so that no epoxy group remains in the epoxy compound (a). It is preferable to use a little less epoxy group in the compound (a). For example, it is preferable to react the epoxy group in the epoxy compound (a) in the range of 0.8 to 0.99 mol with respect to 1 mol of the phenolic hydroxyl group of the phenol compound (b).

The weight average molecular weight of the side chain hydroxyl group-containing resin (c) thus obtained is preferably 1000 to 100,000, and more preferably 3000 to 60000. When the weight average molecular weight is small, viscosity at the time of coating, handling, and developability after photocuring can be improved. On the other hand, when the weight average molecular weight is large, the heat resistance, moist heat resistance and the like of the finally obtained coating film can be improved. In addition, by increasing the weight average molecular weight, flexibility can be improved, and adhesion to a substrate for which it is difficult to ensure adhesion can be improved.
The hydroxyl value of the side chain hydroxyl group-containing resin (c) is preferably 50 to 200 mgKOH / g, more preferably 70 to 170 mgKOH / g. Since the hydroxyl value of the side chain hydroxyl group-containing resin (c) is 50 to 200 mg KOH / g, the degree of freedom for adjusting the reaction rate of side chain modification in the subsequent second, third and fourth steps is increased. It is easy to impart excellent photosensitivity, resolution and developability.

Next, the side chain carboxyl group-containing resin (e) obtained in the second step will be described.
The carboxyl group-containing resin (e) is obtained by reacting at least part of the hydroxyl groups in the side chain hydroxyl group-containing resin (c) with the polybasic acid anhydride (d). The hydroxyl group in the side chain hydroxyl group-containing resin (c) and the acid anhydride group in the polybasic acid anhydride (d) are hydroxyl groups / acid anhydride groups = 1 / 0.1 to 1/1 moles. It is preferable to make it react by ratio. By making the acid anhydride group in the polybasic acid anhydride (d) 0.1 mol or more with respect to 1 mol of the hydroxyl group in the side chain hydroxyl group-containing resin (c), it is easy to form an appropriate cross-link. And solubility in an alkaline developer. On the other hand, by making it 1 mol or less, the reaction control when reacting with the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group in the next step is facilitated.

The polybasic acid anhydride (d) used in the present invention is not particularly limited as long as it is a compound containing at least one acid anhydride group in the molecule. For example,
Methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl nadic acid anhydride, nadic anhydride, hydrogenated methyl nadic anhydride, stilendostyrene styrene tetrahydrophthalic anhydride, trialkyltetrahydro Alicyclic dibasic acid anhydrides such as phthalic anhydride;
Alicyclic polybasic acid anhydrides of tribasic acid or more such as hydrogenated trimellitic acid anhydride, hydrogenated pyromellitic acid anhydride;
Aromatic dibasic acid anhydrides such as phthalic anhydride and tetrabromophthalic anhydride;
Aromatic polybasic acid anhydrides of three or more basic acids such as trimellitic anhydride, biphenyltetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride;
Succinic anhydride, maleic anhydride, glutaric anhydride, butyl succinic anhydride, hexyl succinic anhydride, octyl succinic anhydride, dodecyl succinic anhydride, butyl maleic anhydride, pentyl maleic anhydride, hexyl maleic acid Anhydride, octylmaleic acid anhydride, decylmaleic acid anhydride, dodecylmaleic acid anhydride, butylglutamic acid anhydride, hexylglutamic acid anhydride, heptylglutamic acid anhydride, octylglutamic acid anhydride, decylglutamic acid anhydride, dodecylglutamic acid anhydride And the like, and the like. In the present invention, the polybasic acid anhydride (d) may be used alone or in combination.

  Of these, succinic anhydride, tetrahydrophthalic anhydride, and the like are particularly preferable in the present invention because of their excellent developability, pattern formability, and coating film resistance.

  In the present invention, the conditions for synthesizing the carboxyl group-containing resin (e) in the side chain are not particularly limited, and can be performed under known conditions. For example, a side chain hydroxyl group-containing resin (c), a polybasic acid anhydride (d), and a solvent are charged into a flask and heated at 25 to 150 ° C. with stirring to obtain a carboxyl group-containing resin (e). be able to. This reaction proceeds even without a catalyst, but a catalyst such as a tertiary amino group-containing compound may be newly added as necessary.

Next, the 3rd process of obtaining resin (A-1) which has a carboxyl group and an ethylenically unsaturated bond in a side chain is demonstrated.
The carboxyl group-containing resin (A-1) reacts a part of the carboxyl groups in the carboxyl group-containing resin (e) with a compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group. Let me get it. The carboxyl group in the carboxyl group-containing resin (e) and the epoxy group or oxetane group in the compound (f) are carboxyl group: epoxy group or oxetane group = 1: 0.1 to 1: 0.95. It is preferable to make it react by molar ratio. The amount of double bonds that function as a photocrosslinking point is appropriate by setting the epoxy group or oxetane group in the compound (f) to 0.1 mol or more with respect to 1 mol of the carboxyl group in the carboxyl group-containing resin (e). Therefore, heat resistance and coating film resistance are further improved. On the other hand, by setting the epoxy group or oxetane group to 0.95 mol or less, unreacted carboxylic acid can be left in the side chain, so that the resolution and developability of the final coating film are increased. In addition, it is possible to further improve the adhesion to a substrate that is difficult to ensure adhesion, such as a transparent conductive film mainly composed of indium oxide (ITO) doped with tin.

The compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group used in the present invention may be any compound containing at least one epoxy group or oxetane group and an ethylenically unsaturated group in the molecule. There is no particular limitation.
As the compound (f), for example,
Glycidyl (meth) acrylate, glycidyl cinnamic acid, 4-hydroxybutyl (meth) acrylate glycidyl ether, glycidyl allyl ether, 2,3-epoxy-2-methylpropyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl ( (Meth) acrylate, 4-vinyl-1-cyclohexene-1,2-epoxide, 1,3-butadiene monoepoxide, oxetanyl (meth) acrylate, oxetanyl cinnamic acid,
In addition, a polyfunctional acrylate group-containing monoepoxide obtained by reacting a hydroxyl group of a hydroxyl group-containing polyfunctional acrylic monomer such as pentaerythritol triacrylate with epichlorohydrin,
A polyepoxy group-containing monoepoxide obtained by modifying most of the epoxy groups of a phenol novolac type epoxy resin to an acrylate group with acrylic acid or the like, leaving one epoxy group in one molecule on average,
Examples include a polyfunctional acrylate group-containing monoepoxide obtained by reacting a carboxyl group of a carboxyl group-containing polyfunctional acrylic monomer with a part of the epoxy group of a compound having two or more epoxy groups in the molecule.
In the present invention, as the compound (f), only one of the above compounds may be used alone, or a plurality of them may be used in combination.
Among them, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, etc. are particularly preferred in the present invention from the viewpoint of easy availability of industrial products, carboxyl group and reactivity, and excellent photosensitivity. preferable.

In the present invention, a compound having no ethylenically unsaturated group and having an epoxy group or oxetane group is used in combination with the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group. You can also. In this case, it is possible to control the photosensitivity of the photosensitive resin (A) of the present invention more widely.
Examples of the compound having no ethylenically unsaturated group and having an epoxy group or an oxetane group include:
Styrene oxide, phenyl glycidyl ether, o-phenylphenol glycidyl ether, p-phenylphenol glycidyl ether, glycidyl cinnamate, methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether Glycidol, N-glycidyl phthalimide, 1,3-dibromophenyl glycidyl ether, Celoxide 2000 (manufactured by Daicel Chemical Industries, Ltd.), oxetane alcohol and the like.

  In the present invention, the conditions for synthesizing the side chain carboxyl group-containing resin (A-1) are not particularly limited, and can be performed under known conditions. For example, a side chain carboxyl group-containing resin (e), an epoxy group or an oxetane group and an ethylenically unsaturated group compound (f), and a solvent are charged in a flask in the presence of oxygen, and the mixture is stirred for 25 to 150. The side chain carboxyl group-containing resin (A-1) can be obtained by heating at ° C. At this time, an ethylenically unsaturated group may be added so as not to add a reaction catalyst such as a tertiary amino group-containing compound or the like to promote the reaction, or to cause gelation due to polymerization reaction or progress of polymerization. It is also possible to use a polymerization inhibitor or molecular oxygen.

  As the polymerization inhibitor, hydroquinone, methylhydroquinone, pt-butylcatechol, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, trimethylhydroquinone, methoxyhydroquinone, p-benzoquinone, 2,5- Di-t-butylbenzoquinone, naphthoquinone, phenothiazine, N-oxyl compound and the like can be used. Further, even if molecular oxygen is present in the reaction vessel, there is an effect of inhibiting polymerization. For example, air or a mixed gas of air and an inert gas such as nitrogen may be blown into the reaction vessel so-called bubbling. In order to enhance the polymerization inhibition effect, it is preferable to use a polymerization inhibitor and molecular oxygen in combination.

Next, the resin (AA-1) having a hydroxyl group and an ethylenically unsaturated bond in the side chain will be described.
As described above, the resin (AA-1) having a hydroxyl group and an ethylenically unsaturated bond in the side chain includes at least a part of the carboxyl group in the carboxyl group-containing resin (e), an epoxy group or an oxetane group, and ethylene. It is obtained by reacting an epoxy group or an oxetane group in the compound (f) having a polymerizable unsaturated group. That is, a resin having a hydroxyl group, a carboxyl group, and an ethylenically unsaturated bond in the side chain except that all of the carboxyl groups in the carboxyl group-containing resin (e) may be reacted with the compound (f) ( The same as in the case of A-1). The carboxyl group in the carboxyl group-containing resin (e) and the epoxy group or oxetane group in the compound (f) are in a molar ratio of carboxyl group: epoxy group or oxetane group = 1 / 0.1 to 1/1. It is preferable to make it react with.

Next, the photopolymer (A-2) having a carboxyl group and an ethylenically unsaturated bond in the side chain obtained in the fourth step will be described.
The carboxyl group-containing photosensitive resin (A-2) is obtained by reacting at least part of the hydroxyl groups in the hydroxyl group-containing resin (AA-1) with a polybasic acid anhydride (g). The hydroxyl group in the hydroxyl group-containing resin (AA-1) and the acid anhydride group in the polybasic acid anhydride (d) are hydroxyl group: acid anhydride group = 1: 0.01 to 1: 1. It is preferable to make it react by the molar ratio. By making the acid anhydride group 0.01 mol or more with respect to 1 mol of the hydroxyl group, the developability with a dilute alkaline aqueous solution at the time of pattern formation can be further improved, and further a carboxyl group that functions as a thermal crosslinking point Since it becomes suitable, heat resistance and coating-film resistance can be improved more. On the other hand, by setting the acid anhydride group to 1 mol or less with respect to 1 mol of the hydroxyl group, the excess acid anhydride is eliminated, and deterioration of resolution and film formability due to the excess acid anhydride is suppressed. Can do.

  The polybasic acid anhydride (g) used in the present invention can be exemplified by the same polybasic acid anhydride (d) described above. As the polybasic acid anhydride (g), succinic anhydride, tetrahydrophthalic anhydride and the like are particularly preferable in the present invention because of their excellent developability, pattern forming property and coating film resistance.

  In the present invention, the synthesis condition of the carboxyl group-containing photosensitive resin (A-2) is not particularly limited, and the hydroxyl group-containing resin (A-1) is added to the flask in the presence of oxygen in the same manner as in the third step. ), A polybasic acid anhydride (g), and a solvent are charged, and the reaction is preferably performed by heating and stirring at 25 to 150 ° C., and if necessary, a suitable reaction catalyst and ethylenically unsaturated group A polymerization inhibitor can be newly added.

  Photosensitive resin (A) obtained by the above steps, that is, resin (A-1) having a carboxyl group and an ethylenically unsaturated bond in the side chain, or resin having a carboxyl group and an ethylenically unsaturated bond in the side chain The acid value of (A-2) is preferably 10 to 200 mgKOH / g, more preferably 30 to 150 mgKOH / g. When designing in a range close to 10 mgKOH / g, the flexibility and adhesion of the resulting coating film can be improved. On the other hand, when designing in a range close to 200 mgKOH / g, the heat resistance is further improved because the number of crosslinking points increases. Moreover, since the solubility of the coating film with respect to a developing solution also improves, when leaving the photocured part as a pattern, it becomes easy to control the shape of a pattern.

It is preferable that the ethylenically unsaturated group equivalent of the photosensitive resin (A) in this invention is 200-5000 g / eq, More preferably, it is 300-3000 g / eq. When the ethylenically unsaturated group equivalent is designed in a range close to 200 g / eq, the photosensitivity of the resulting coating film is increased, so that a good pattern shape can be easily obtained during development. On the other hand, when designing in a range close to 5000 g / eq, since it becomes an appropriate photocrosslinking point, the adhesion to a base material that makes it difficult to ensure adhesion by increasing the flexibility of the finally obtained coating film, etc. Can be improved.
The “ethylenically unsaturated group equivalent” as used in the present invention is a theoretical value calculated from the weight of raw materials used during the synthesis of the resin, and the weight of the resin is the ethylenically unsaturated group present in the resin. It is divided by the number of groups and corresponds to the weight of the resin per mole of ethylenically unsaturated groups, that is, the reciprocal of the ethylenically unsaturated group concentration.

It is preferable that the weight average molecular weights of the photosensitive resin (A) in this invention are 1000-100000, More preferably, it is 3000-60000. When the weight average molecular weight is small, viscosity at the time of coating, handling, and developability after photocuring can be improved. On the other hand, when the weight average molecular weight is large, the heat resistance, moist heat resistance and the like of the finally obtained coating film can be improved. In addition, by increasing the weight average molecular weight, flexibility can be improved, and adhesion to a substrate for which it is difficult to ensure adhesion can be improved.
In addition, the contribution of the side chain part in the weight average molecular weight of the photosensitive resin (A) is small. That is, the weight average molecular weight of the photosensitive resin (A) is almost the same as the weight average molecular weight of the main chain, that is, the weight average molecular weight of the side chain hydroxyl group-containing resin (c).

The solvent used for the synthesis of the photosensitive resin (A) can be appropriately selected according to the end use and the solubility of the reactant.
For example, when used in a process of forming a fine pattern by photolithography after forming a pattern by screen printing, it is necessary to suppress ink solidification on the screen mesh due to solvent drying in the screen printing process. It is preferable to use the solvent. Examples of the high boiling point solvent in this case include ethylene glycol monohexyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, and dipropylene glycol monobutyl ether. Examples include dialkylene glycol monoalkylene ether compounds, trialkylene glycol monoalkylene ether compounds such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether.

  In the present invention, these solvents may be used alone or in combination, if necessary, and may be used in combination. Or a solvent may be added.

  The photosensitive conductive ink in the present invention may contain a resin other than the above-described (A) as necessary. Examples of resins other than (A) include acrylic resins, polyester resins, urethane resins, urea resins, urethane urea resins, epoxy resins, polyamide resins, and polyimide resins. Those containing a carboxyl group are preferred from the viewpoint of developability, and those containing an ethylenically unsaturated group are preferred from the viewpoint of resolution. In this invention, when it contains resin other than (A), it can be used individually or in combination.

[Conductive particles (B)]
Examples of the conductive particles used in the conductive ink of the present invention include gold, silver, copper, silver-plated copper powder, silver-copper composite powder, silver-copper alloy, amorphous copper, nickel, chromium, palladium, rhodium, ruthenium, Metal powder such as indium, silicon, aluminum, tungsten, morphbutene, platinum, inorganic powder coated with these metals, powder of metal oxide such as silver oxide, indium oxide, tin oxide, zinc oxide, ruthenium oxide, these Inorganic powders coated with metal oxides, carbon black, graphite and the like can be used. These conductive particles may be used alone or in combination of two or more. Among these conductive particles, silver is preferable because of its cost, high conductivity, and little increase in resistivity due to oxidation.

The shape of the conductive particles is not particularly limited as long as the above properties are satisfied, and an indeterminate shape, an aggregated shape, a scale shape, a microcrystalline shape, a spherical shape, a flake shape, and the like can be appropriately used. From the viewpoint of the printability of the high-definition pattern and the adhesiveness of the conductor pattern to the substrate, a spherical or small aggregate having a small particle size is preferable as a relatively small aggregate.
The D50 particle diameter of the conductive particles used in the conductive ink according to the present invention is 0.5 to 8 μm, preferably in the range of 1 to 5 μm, and more preferably in the range of 2 to 4 μm.
Further, BET specific surface area of 0.3 to 5 m ² / g, preferably in the range of 0.8~2.3m ² / g, still in the range of 0.8~2m ² / g preferable.

If the D50 particle diameter of the conductive particles is less than 0.5 μm, the dispersibility of the conductive particles deteriorates when the conductive ink is used, resulting in poor contact between the conductive particles, resulting in a large printed resistance value. There is a possibility. In addition, the cost of the conductive particles increases.
On the other hand, if the D50 particle diameter exceeds 8 μm, the printability of the high-definition pattern may be inferior.
In addition, the D50 particle diameter of the conductive particles was determined by measuring the cumulative particle size (D50) of the volume particle size distribution using a laser diffraction particle size distribution measuring device “SALAD-3000” manufactured by Shimadzu Corporation.

When the BET specific surface area of the conductive particles is less than 0.3 m ² / g, the contact point between the conductive particles decreases, and the contact resistance increases.
In addition, when the BET specific surface area exceeds 5 m ² / g, a large amount of resin is required to coat the surface of the conductive particles. Therefore, the wetness with respect to the epoxy resin as the binder resin is inferior, and the conductive ink is used. This is not preferable because the fluidity is deteriorated and the leveling property of the surface of the printed coating film is lowered. Moreover, since many resin is required to coat | cover the surface of electroconductive particle, the adhesiveness of the electroconductive pattern with respect to a base material also falls.
BET specific surface area is a method of adsorbing molecules whose adsorption occupation area is known to the powder particle surface at the temperature of liquid nitrogen, and obtaining the specific surface area of the sample from the amount, using low-temperature low-humidity physical adsorption of inert gas This is the BET method. The BET specific surface area is defined as a value calculated using the following formula (11), which is a surface area measured using a flow type specific surface area measuring device “Flowsorb II” manufactured by Shimadzu Corporation.
Formula (11) Specific surface area (m ² / g) = surface area (m ² ) / powder mass (g)

  In the photosensitive conductive ink of the present invention, metal fine particles (B ′) can be used in combination with the above-mentioned relatively large particles for the purpose of further improving the conductivity. Metal fine particles (B ′) having an average particle diameter of 0.001 to 0.1 μm as measured by a particle size distribution measuring apparatus using a normal dynamic light scattering method. When metal fine particles (B ′) having an average particle diameter exceeding 0.1 μm are used, not only the conductivity is lowered, but also the stability of the ink and the fluidity imparting action to the ink are lowered, and printing is performed by screen printing or the like. It becomes difficult. It is more preferable to use metal fine particles (B ′) having an average particle diameter of 0.001 to 0.05 μm from the viewpoint of conductivity, ink stability, and fluidity.

  As the metal fine particles (B ′) having an average particle diameter of 0.001 to 0.1 μm, for example, as described in JP-A No. 11-319538, metal ions in a solution are used in the presence of a polymer dispersant. Fine metal particles protected by a high molecular weight dispersing agent obtained by reduction with can be used. Further, as described in JP-A-2002-266002, the metal is obtained by evaporating a metal under a reduced inert gas atmosphere and mixing the metal vapor with the monomer vapor. Metal fine particles in which the monomer adhering to the surface of the fine particles is polymerized and the surface portion is coated with a polymer compound can be used. When the metal fine particles (B ′) protected by the former polymer dispersant are used, the polymer dispersant acting as a protective colloid of the metal fine particles also acts on the conductive particles (B). The fine particles (B ′) effectively act as a fluidity-imparting agent and improve the conductivity.

  The photosensitive conductive ink of the present invention preferably contains 60 to 95% by weight of conductive particles, more preferably 70 to 95% by weight, and 85 to 95% by weight in the total solid content of the ink. Is more preferable. If the conductive particles are less than 60% by weight, the conductivity is not sufficient, and if it exceeds 95% by weight, the epoxy resin is reduced, and the adhesion of the conductive ink to the substrate and the mechanical strength of the coating film may be reduced. There is no.

[Photoinitiator (C)]
The photopolymerization initiator (C) is added when the photosensitive compound is cured by active energy rays. The photopolymerization initiator is not particularly limited as long as it has a function capable of initiating vinyl polymerization by photoexcitation. For example, a monocarbonyl compound, dicarbonyl compound, acetophenone compound, benzoin ether compound, acylphosphine oxide compound, aminocarbonyl A compound etc. can be used.

  Specific examples of monocarbonyl compounds include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 4- (4-methylphenylthio) phenyl-enetanone. 3,3′-dimethyl-4-methoxybenzophenone, 4- (1,3-acryloyl-1,4,7,10,13-pentaoxotridecyl) benzophenone, 3,3′4,4′-tetra ( t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N, N-trimethylbenzenemethammonium chloride, 2-hydroxy-3- (4-benzoyl-phenoxy) -N, N, N-trimethyl-1-propanamine Hydrochloride, 4-benzoyl-N, N-dimethyl-n- [2 (1-Oxo-2-propenyloxyethyl)] metaammonium bromide, 2- / 4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone 2-hydroxy-3- (3,4-dimethyl-9-oxo-9Hthioxanthone-2-yloxy) -N, N, N-trimethyl-1-propanamine hydrochloride, benzoylmethylene-3-methylnaphtho (1, 2-d) thiazoline and the like.

  Examples of the dicarbonyl compound include 1,7,7-trimethyl-bicyclo [2.1.1] heptane-2,3-dione, benzyl, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzene. Examples include acetate and 4-phenylbenzyl.

  Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- ( 4-Isopropylphenyl) 2-hydroxy-di-2-methyl-1-phenylpropan-1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 2-hydroxy-2-methyl-1-styrylpropan-1-one polymerization , Diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,2-diethoxy-1,2-diphenylethane-1-one, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethyla No-1- (4-morpholino-phenyl) butan-1-one, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2- Morpholino-propanonyl) -9-butylcarbazole and the like.

  Examples of the benzoin ether compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzoin normal butyl ether.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di (2,6-dichlorobenzoyl) phosphine oxide.

Examples of aminocarbonyl compounds include methyl-4- (dimethylamino) benzoate, ethyl-4- (dimethylamino) benzoate, 2-nbutoxyethyl-4- (dimethylamino) benzoate, isoamyl-4- (dimethylamino) benzoate, 2- (dimethylamino) ethyl benzoate, 4,4′-bis-4-dimethylaminobenzophenone, 4,4′-bis-4-diethylaminobenzophenone, 2,5′-bis- (4-diethylaminobenzal) cyclopenta Non etc. are mentioned.
In particular, in the present invention, when 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and thioxanthones are used in combination, the photosensitivity is very low, though it is inexpensive. It is particularly preferred because of its superiority.
These are not limited to the above-mentioned compounds, and any compounds can be used as long as they have the ability to initiate polymerization by ultraviolet rays. These can be used alone or in combination, and the amount used is not limited, but is preferably added in the range of 1 to 20 parts by weight with respect to 100 parts by weight as the total dry weight of the photosensitive resin (A). . Moreover, a well-known organic amine can also be added as a sensitizer.

[Ethylenically unsaturated compound (E)]
The ethylenically unsaturated compound (E) contained in the photosensitive conductive ink of the present invention is a compound having one or more ethylenically unsaturated double bonds, and monomers and oligomers can be used.

For example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meta ) Monofunctional (meth) acrylates such as acrylate, β-carboxyethyl (meth) acrylate, or polyethylene glycol di (meth) acrylate;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol polyethylene glycol di (meth) acrylate, dipropylene glycol polyethylene glycol di ( (Meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate , Tripropylene glycol di (meth) acrylate, neopentyl glycol modified trimethylolpropane di (meth) acrylate, etc. Difunctional (meth) acrylates;
Trifunctional or more polyfunctional compounds such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or dipentaerythritol penta (meth) acrylate Functional (meth) acrylates; or
(Meth) acrylic acid adduct of 1,6-hexanediol diglycidyl ether, (meth) acrylic acid adduct of neopentyl glycol diglycidyl ether, (meth) acrylic acid adduct of glycerol diglycidyl ether, bisphenol A diglycidyl Examples include (meth) acrylic acid adducts of ether, (meth) acrylic acid adducts of bisphenol F type epoxy, and (meth) acrylic acid adducts of novolac type epoxy.

  Moreover, what modified | denatured the (meth) acrylate mentioned above further by (poly) alkylene oxide, (poly) caprolactone, etc. can also be used.

  Other examples include tris [2- (meth) acryloyloxyethyl)] isocyanurate or a reaction product of isocyanurate of diisocyanates and hydroxyalkyl (meth) acrylate.

In addition, vinyl ethers such as hydroxyethyl vinyl ether, ethylene glycol divinyl ether, or pentaerythritol trivinyl ether;
Unit cost monomers such as (meth) acrylic acid, styrene, or vinyl acetate; or
A monofunctional monomer having a nitrogen element such as (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, or acrylonitrile can also be used.

  Furthermore, what modified | denatured oligomers, such as a polyurethane, polyester, a methylol melamine resin, polydimethylsiloxane, or rosin, with the (meth) acryloyl group can also be used.

  Other examples include (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.

  The ethylenically unsaturated compounds (E) listed above are not necessarily limited to these. It can be used alone or in combination of two or more.

  The ethylenically unsaturated compound (E) can be used in an amount of preferably 5 to 30% by weight based on the total solid content weight of the photosensitive conductive ink (100% by weight). When the content of the ethylenically unsaturated compound (E) is more than 30% by weight, the curing proceeds near the exposed surface and the internal curing does not proceed, so that there is a tendency that a pattern with sufficient coating strength cannot be formed. Yes, if it is less than 5% by weight, the effect of improving the sensitivity due to the addition of the ethylenically unsaturated compound cannot be sufficiently obtained.

[Heat-crosslinking compound (F)]
In the photosensitive conductive ink of the present invention, a heat-crosslinkable compound (F) can be further used for the purpose of further improving heat resistance, moist heat resistance and the like. As the heat-crosslinkable compound (F), various commonly used heat-crosslinkable compounds can be used, and particularly preferably, an epoxy group-containing compound, an isocyanate group-containing compound, a blocked isocyanate group-containing compound, and β At least one selected from the group consisting of -hydroxyalkylamide group-containing compounds can be used.

  Examples of the epoxy group-containing compound used as the thermally crosslinkable compound (F) in the present invention include the epoxy compound (a) having at least two epoxy groups in one molecule, and the epoxy group in the molecule. There is no particular limitation as long as it is a compound containing s.

  As a compound which has one epoxy group in a molecule | numerator, compounds, such as N-glycidyl phthalimide, glycidol, glycidyl (meth) acrylate, are mentioned, for example. Moreover, the epoxy group-containing compound described here may or may not have an ethylenically unsaturated group.

  When an epoxy group-containing compound used as the thermally crosslinkable compound (F) is an isocyanurate ring-containing epoxy compound such as trishydroxyethyl isocyanurate triglycidyl ether or triglycidyl isocyanurate, it adheres to a substrate such as polyimide. There is a tendency for the strength to improve, which is highly preferred in the present invention. In addition, “Epicoat 1031S”, “Epicoat 1032H60”, “Epicoat 604”, and “Epicoat 630” manufactured by Mitsubishi Chemical Corporation are preferred in the present invention because they are multifunctional and have excellent heat resistance. Type epoxy compounds and epoxy compounds described in JP-A Nos. 2004-156024, 2004-315595, and 2004-323777 are excellent in flexibility of a cured coating film and hardly adhere to ITO or the like. This is preferable because it improves adhesion to the substrate. In addition, the dicyclopentadiene type epoxy compound, the phenol novolak type epoxy resin, the cresol novolak type epoxy resin, the biphenol / epichlorohydrin type epoxy resin, etc. described in JP-A No. 2001-240654 are thermally cured in the present invention. It is excellent in terms of durability of a cured coating film including properties, hygroscopicity and heat resistance, and is preferable.

The isocyanate group-containing compound used as the thermally crosslinkable compound (F) in the present invention is not particularly limited as long as it is a compound having an isocyanate group in the molecule. Specific examples of the isocyanate group-containing compound having one isocyanate group in one molecule include n-butyl isocyanate, isopropyl isocyanate, phenyl isocyanate, benzyl isocyanate, (meth) acryloyloxyethyl isocyanate, 1,1-bis [ (Meth) acryloyloxymethyl] ethyl isocyanate, vinyl isocyanate, allyl isocyanate, (meth) acryloyl isocyanate, isopropenyl-α, α-dimethylbenzyl isocyanate and the like.
In addition, 1,6-diisocyanatohexane, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, xylylene diisocyanate, tolylene 2,4-diisocyanate, toluene diisocyanate, 2,4-diisocyanic acid Toluene, hexamethylene diisocyanate, 4-methyl-m-phenylene diisocyanate, naphthylene diisocyanate, paraphenylene diisocyanate, tetramethylxylylene diisocyanate, cyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl diisocyanate, tolidine diisocyanate, 2,2 , 4-Trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate Nitrate, m-tetramethylxylylene diisocyanate, p-tetramethylxylylene diisocyanate, diisocyanate ester compounds such as dimer acid diisocyanate and hydroxyl group, carboxyl group, and amide group-containing vinyl monomers are reacted in equimolar amounts. It can be used as an ester compound.

  Specific examples of the isocyanate group-containing compound having two isocyanate groups in one molecule include aromatic diisocyanates having 4 to 50 carbon atoms, aliphatic diisocyanates, araliphatic diisocyanates, and alicyclic diisocyanates. it can.

  Examples of the aromatic diisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6- Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 ', 4 "-Triphenylmethane triisocyanate etc. can be mentioned.

  Examples of the aliphatic diisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2 4,4-trimethylhexamethylene diisocyanate and the like.

  Examples of the araliphatic diisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1 , 4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.

  Examples of the alicyclic diisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate [also known as isophorone diisocyanate], 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, and 1,4-cyclohexane diisocyanate. , Methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanate methyl) A cyclohexane etc. can be mentioned.

  Specific examples of the isocyanate group-containing compound having three isocyanate groups in one molecule include aliphatic polyisocyanates such as aromatic polyisocyanates and lysine triisocyanates, araliphatic polyisocyanates, and alicyclic polyisocyanates. And the like, and the trimethylolpropane adduct of diisocyanate described above, a burette reacted with water, and a trimer having an isocyanurate ring.

  The blocked isocyanate group-containing compound used as the thermally crosslinkable compound (F) in the present invention may be a blocked isocyanate group-containing compound in which the isocyanate group in the isocyanate group-containing compound is protected with ε-caprolactam, MEK oxime, or the like. There is no particular limitation. Specific examples include those obtained by blocking the isocyanate group of the isocyanate group-containing compound with ε-caprolactam, MEK oxime, cyclohexanone oxime, pyrazole, phenol and the like. In particular, hexamethylene diisocyanate trimer having an isocyanurate ring and blocked with MEK oxime or pyrazole is excellent in heat resistance and moist heat resistance as well as storage stability when used in the present invention. Is preferable.

  The β-hydroxyalkylamide group-containing compound used as the thermally crosslinkable compound (F) in the present invention is not particularly limited as long as it is a compound containing a β-hydroxyalkylamide group in the molecule. When a β-hydroxyalkylamide group-containing compound is used as a curing agent for the photosensitive resin (A), the by-product during the reaction is only water, and has little effect on the cured product. There is a merit that there is no influence.

  As the β-hydroxyalkylamide group-containing compound, for example, a compound represented by the following general formula (4) can be used, and N, N, N ′, N′-tetrakis (hydroxyethyl) adipamide (emschemy) Examples include various compounds including Primid XL-552).

General formula (4)

In General Formula (4), X is an n-valent group composed of carbon, hydrogen, oxygen, nitrogen, sulfur, or halogen, and n is an integer of 2-6. Specific examples of X include an n-valent aliphatic hydrocarbon group having 2 or more carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group having a hetero atom.

  Examples of the halogen include fluorine, chlorine, bromine and iodine, and fluorine is preferable from the viewpoint of transparency. From the viewpoint of imparting flame retardancy, chlorine and bromine are preferred.

  An n-valent group is a group obtained by removing n hydrogen atoms from a compound. Hereinafter, this is referred to as an n-valent group derived from the compound.

  Examples of the n-valent aliphatic hydrocarbon group include n-valent groups derived from alkanes, alkenes, and alkynes.

  Alkanes include ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, heptadecane, hexadecane, octadecane, nonadecane, icosane, heicossan, docosane, isobutane, isopentane, Neopentane, methylpentane, dimethylpentane, ethylmethylpentane, diethylpentane, methylhexane, tetramethylheptane, and the like. As the n-valent group derived from alkane, for example, 1,6-hexyl group, 1,7-heptyl group, 1,8-octyl group, 1,9-nonyl group, 1,10-decyl group, 1,11 -Undecyl group, 1,12-dodecyl group, 1,13-tridecyl group, 1,14-tetradecyl group, 1,15-pentadecyl group, 1,16-hexadecyl group, 1,17-heptadecyl group, 1,18- Octadecyl group, 1,19-nonadecyl group, 1,3,6-hexyl group, 1,4,7-heptyl group, 1,2,8-octyl group, 1,3,9-nonyl group, 1,3, Examples include 4,6-hexyl group, 1,4,6,7-heptyl group, 1,4,5,6,7-heptyl group and 1,2,3,4,5,6-hexyl group.

  Alkenes include ethylene, propylene, butylene, pentene, hexene, heptene, octene, nonene, decene, undecene, docene, tridecene, tetracene, pentadecene, heptadecene, hexadecene, octadecene, nonadecene, icosene, heicocene, dococene, methylpentene, etc. Is mentioned. Examples of the n-valent group derived from an alkene include a 1,6- (2-hexenyl) group, a 1,7- (2-heptenyl) group, a 1,8- (2-octenyl) group, and a 1,9- (2-nonenyl) group, 1,10- (2-decenyl) group, 1,11- (2-undecenyl) group, 1,12- (2-dodecenyl) group, 1,13- (2-tridecenyl) group 1,14- (2-tetradecenyl) group, 1,15- (2-pentadecenyl) group, 1,16- (2-hexadecenyl) group, 1,17- (2-heptadecenyl) group, 1,18- ( 2-octadecenyl) group, 1,19- (2-nonadecenyl) group, 1,3,6- (2-hexenyl) group, 1,4,7- (3-heptenyl) group, 1,2,8- ( 4-octenyl) group, 1,3,9- (5-nonenyl) group, 1,3,4,6- (2-hex) ) Group, 1,4,6,7- (3-Hepuseniru) group, 1,4,5,6,7- (3- Hepuseniru) group.

  Examples of alkynes include ethyne, propyne, butyne, pentyne, hexyne, peptin, octyne, nonin, decyne, undecine, dodecin, tridecine, icosin, heicosin, docosin, and the like. Examples of the n-valent group derived from alkyne include 1,6- (2-hexynyl) group, 1,7- (2-hepsinyl) group, 1,8- (2-oxynyl) group, 1,9- (2-nonyl) group, 1,10- (2-decynyl) group, 1,11- (2-undecynyl) group, 1,12- (2-dodecynyl) group, 1,13- (2-tridecynyl) group 1,14- (2-tetradecynyl) group, 1,15- (2-pentadecynyl) group, 1,16- (2-hexadecynyl) group, 1,17- (2-heptadecynyl) group, 1,18- ( 2-octadecynyl) group, 1,19- (2-nonadecynyl) group, 1,3,6- (2-hexynyl) group, 1,4,7- (3-hepsinyl) group, 1,2,8- ( 4-octynyl) group, 1,3,9- (5-nonyl) group, 1,3,4,6- (2-hexini) ) Group, 1,4,6,7- (3-Hepushiniru) group, and 1,4,5,6,7- (3- Hepushiniru) group.

  Examples of the n-valent alicyclic hydrocarbon group include cyclopropane, cyclobutane, cyclopentane, methylcyclopentane, dimethylcyclopentane, trimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cyclohexene, methylcyclohexene, norbornane, norbornene, and bicyclo And n-valent groups derived from octene, decahydronaphthalene, adamantane, dimethyladamantane, and the like. For example, 1,1-cyclohexyl group, 1,2-cyclohexyl group, 1,3-cyclohexyl group, 1,4-cyclohexyl group, 1,2,4-cyclohexyl group, 1,3,5-cyclohexyl group, 1, Examples include 2,4,5-cyclohexyl group, 1,2,3,4,5,6-cyclohexyl group, 2,6-decahydronaphthyl group, 1,3-adamantyl group, 1,3,5-adamantyl group. .

  Examples of n-valent aromatic hydrocarbon groups include n-valent aromatic hydrocarbon groups derived from benzene, naphthalene, biphenyl, anthracene, toluene, xylene, ethylbenzene, tert-butylbenzene, diphenylethane, diphenylacetylene, 9,9-diphenylfluorene, and the like. Groups. For example, examples of the group in which an aromatic ring contains a carbon atom bonded to a carbonyl group include a phenylene group and a tolylene group. Examples of the group in which the carbon atom bonded to the carbonyl group is not contained in the aromatic ring include toluene-α, α-diyl group, ethylbenzene-α, β-diyl group, ethylbenzene-β, β-diyl group, 1,2-diphenyl. And ethane-1,2-diyl group.

  N-valent groups having heteroatoms (oxygen, sulfur, nitrogen, halogen atoms) include ethanol, ethylene glycol, ethylene diacetate, ethylene dipivalate, ethylene dibenzoate, ethylene bis (methyl benzoate), ethylene bis (methoxy Benzoate), propanol, isopropanol, ethyl acetate, erythritol, ethylene oxide, acetaldehyde, acetone, dipropyl ketone, γ-pentadecanolactone, 1,2-cyclohexane, γ-butyrolactone, ethylamine, ethylmethylamine, propylamine, N- Propylacetamide, ethanethiol, ethanedithiol, tetrafluoroethane, dibromoethane, hexafluoropropane, octofluorobutane, dodecafluorohexane, hexadecaf Fluorooctane, 1,2,3,4,7,7-hexachloronorbornene, anisole, fluorobenzene, tetrafluorobenzene, trifluoromethylbenzene, chlorobenzene, dichlorobenzene, tetrafluorobenzene, bromobenzene, tetrabromobenzene, nitrobenzene, phenol Aniline, benzenesulfonic acid, anthraquinone, butanephosphonic acid, triethyltriazine, tripropyltriazine, triethylisocyanurate, tripropylisocyanurate, benzophenone, thiophene, diethylsulfide, diphenylsulfone, 2,2-diphenyl-1,1,1 , 3,3,3-hexafluoropropane, diphenyl ether, and the like.

  Among these, as X, from the viewpoint of reactivity, it is preferable that the atom in X that is directly bonded to the carbonyl group is a carbon atom that is not included in the aromatic ring. Further, a linear aliphatic hydrocarbon group having 6 to 18 carbon atoms or an alicyclic hydrocarbon group is preferable, and more preferably a linear aliphatic hydrocarbon group having 6 to 12 carbon atoms, or It is an alicyclic hydrocarbon group, More preferably, it is a C6-C12 linear aliphatic hydrocarbon group.

In the formula, each of R ¹ and R ² independently represents a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a group represented by the general formula (5), or a general formula In the group represented by (6), at least one of one or more R ¹ and R ² bonded to one or more nitrogen atoms is a group represented by the general formula (5).

General formula (5)

General formula (6)

  Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group.

  As the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, decyl group , Dodecyl group, pentadecyl group, and octadecyl group.

  Examples of the alkenyl group include vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-octenyl group, 1-decenyl group and 1-octadecenyl group. Groups.

  Examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-octynyl group, 1-decynyl group and 1-octadecynyl group. .

  The alicyclic hydrocarbon group includes cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group, 2-indeno group, decahydronaphthyl group, adamantyl group, dicyclopenta And a cycloalkyl group such as a nyl group.

Examples of the aromatic hydrocarbon group include a single ring, a condensed ring, and a ring assembly aromatic hydrocarbon group.
The monocyclic aromatic hydrocarbon group includes monocyclic aromatic groups such as phenyl group, benzyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, p-cumenyl group and mesityl group. Group hydrocarbon group.
As the condensed ring aromatic hydrocarbon group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 5-anthryl group, 1-phenanthryl group, 9-phenanthryl group, 1-acenaphthyl group, Examples thereof include condensed ring aromatic hydrocarbon groups such as 2-azurenyl group, 1-pyrenyl group and 2-triphenylyl group.
Examples of the ring-assembled aromatic hydrocarbon group include ring-assembled aromatic hydrocarbon groups such as o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group.

Among them, R ¹ and R ² other than those represented by formulas (5) and (6) are preferably aliphatic hydrocarbon groups, alicyclic hydrocarbons, or monocyclic aromatic hydrocarbon groups, and more preferably An aliphatic hydrocarbon group and an alicyclic hydrocarbon, and more preferably an aliphatic hydrocarbon group having 4 or more carbon atoms.

R ^{3 to} R ^{6 in the} groups represented by the formulas (5) and (6) each independently represent a hydrogen atom, a hydrocarbon group, or a hydrocarbon group partially substituted with a hydroxyl group, and R ⁷ represents a hydroxyl group It represents a residue of a compound having a functional group capable of reacting with a group.

The hydrocarbon group is the same as that described above for R ¹ and R ² . Examples of the hydrocarbon group substituted with a hydroxyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxyphenyl group, a hydroxycyclohexyl group, and the like.

  The compound having a functional group capable of reacting with a hydroxyl group is not particularly limited, but isocyanate, carboxylic acid, carboxylic acid halide, carboxylic acid anhydride, carboxylic acid ester, silanol, alkoxysilane, silanol ester, amino resin, epoxy The compound etc. which have these are mentioned, An isocyanate, carboxylic acid, a carboxylic acid halide, and a carboxylic anhydride are preferable, More preferably, it is monofunctional isocyanate or monofunctional carboxylic acid.

Among these, from the viewpoint of easy production, it is more preferable that R ⁷ in the general formula (6) is a β-hydroxyalkylamide represented by the following general formula (7).
General formula (7)

here,
R ¹⁶ comprises a single bond, a (m ¹ +1) valent hydrocarbon group, or at least one of a urethane bond, a urea bond, an allophanate bond, a biuret bond, and an isocyanurate ring, and a carbon atom or a hydrogen atom (m ¹ +1) represents a valent group,
A ¹ represents a single bond, a urethane bond or a urea bond,
R ¹⁷ represents a divalent hydrocarbon group,
A ² represents an ether bond or an ester bond,
R ¹⁸ represents a monovalent hydrocarbon group,
m ¹ represents an integer of ¹ to 5,
p ¹ represents an integer of 0 to 100.

From the viewpoint of easy preparation, it is more preferable to obtain β-hydroxyalkylamide in which R ⁷ in the general formula (6) is represented by the following general formula (8).

General formula (8)
Here, R ¹⁹ represents a single bond, a (m ² +1) valent hydrocarbon group, or a (m ² +1) valent group consisting of a carbon atom, a hydrogen atom, and an oxygen atom,
A ³ represents a single bond, an ester bond or an amide bond,
R ²⁰ represents a divalent hydrocarbon group,
A ⁴ represents an ether bond or an ester bond,
R ²¹ represents a monovalent hydrocarbon group,
m ² represents an integer of 1 to 5,
p ² is an integer of 0 to 100.

  When these β-hydroxyalkylamide group-containing compounds are used, it becomes possible to further improve the storage stability, the coating film resistance after heat curing, and the adhesion to difficult-to-adhere substrates by improving the flexibility of the coating film. . Moreover, heat resistance and heat-and-moisture resistance can be improved more, and it is preferably used in the photosensitive conductive ink composition of the present invention.

  In the present invention, the thermally crosslinkable compound (F) may be used alone or in combination. The amount of the thermally crosslinkable compound (F) used may be determined in consideration of the use of the photosensitive conductive ink of the present invention, and is not particularly limited, but is 100 parts by weight of the photosensitive resin (A). The amount is preferably 0.5 to 100 parts by weight, more preferably 1 to 80 parts by weight. By using the thermally crosslinkable compound (F), the crosslinking density of the photosensitive conductive ink of the present invention can be adjusted to an appropriate value, so that various physical properties of the cured coating film can be further improved. Can do.

  In the present description, a thermosetting aid can be used as long as the physical properties of the photosensitive conductive ink are not impaired. The thermosetting aid here is a compound that directly contributes to the curing reaction or a compound that contributes catalytically when the thermally crosslinkable compound (F) and the photosensitive resin (A) are subjected to a curing reaction. .

  The compound that directly contributes to the curing reaction as a heat curing aid represents a compound having a functional group that can react with a hydroxyl group, an amino group, an epoxy group, a carboxyl group or the like alone by heat. Those belonging to F) are excluded and are preferably used in the photosensitive conductive ink of the present invention.

Examples of the compound that directly contributes to the curing reaction during thermosetting include amino resins, phenol resins, polyfunctional polycarboxylic acid anhydrides, polyfunctional vinyl ether compounds, high molecular weight polycarbodiimides, and aziridine compounds.
Examples of amino resins and phenol resins include addition compounds of urea, melamine, benzoguanamine, phenol, cresols, bisphenols, and the like with formaldehyde, or partial condensates thereof.
The polyfunctional polycarboxylic acid anhydride is a compound having two or more carboxylic acid anhydride groups and is not particularly limited, but tetracarboxylic dianhydride, hexacarboxylic dianhydride, hexacarboxylic dianhydride And polyvalent carboxylic acid anhydrides such as maleic anhydride copolymer resins. In addition, polycarboxylic acid, polycarboxylic acid ester, polycarboxylic acid half ester, and the like that can be converted into an anhydride via a dehydration reaction during the reaction are included.

  Examples of maleic anhydride copolymer resins include SMA resin series manufactured by Sartomer, GSM series manufactured by Gifu Shellac Co., Ltd., styrene-maleic anhydride copolymer resins, p-phenylstyrene-maleic anhydride copolymer resins, polyethylene- Α-olefin-maleic anhydride copolymer resin such as maleic anhydride, “VEMA” (copolymer of methyl vinyl ether and maleic anhydride) manufactured by Daicel Chemical Industries, Ltd., and acrylic anhydride modified maleic anhydride (“Aurolen series”) ": Nippon Paper Chemical Co., Ltd.), maleic anhydride copolymer acrylic resin, and the like.

  Specific examples of the polyfunctional vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, and tripropylene glycol. Divinyl ether, neopentyl glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, glycerin divinyl ether, trimethylolpropane divinyl ether, 1,4-dihydroxylcyclohexane divinyl ether, 1,4 -Dihydroxymethylcyclohexanedivinyl ether, Hyde Quinone divinyl ether, ethylene oxide modified hydroquinone divinyl ether, ethylene oxide modified resorcin divinyl ether, ethylene oxide modified bisphenol A divinyl ether, ethylene oxide modified bisphenol S divinyl ether, glycerin trivinyl ether, sorbitol tetravinyl ether, trimethylolpropane trivinyl ether, pentaerythritol Examples include trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol hexavinyl ether, dipentaerythritol polyvinyl ether, ditrimethylolpropane tetravinyl ether, and ditrimethylolpropane polyvinyl ether.

Examples of the high molecular weight polycarbodiimides include Nisshinbo's Carbodilite series. Among these, Carbodilite V-01, 03, 05, 07, and 09 are preferable because of excellent compatibility with organic solvents.
Examples of the aziridine compound include 2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], 4,4′-bis (ethyleneiminocarbonylamino) diphenylmethane, and the like.
Other compounds that directly contribute to the curing reaction during thermal curing include benzoxazine compounds, benzocyclobutene compounds, maleimide compounds, nadiimide compounds, allyl nadiimide compounds, melamine compounds, guanamine compounds, and the like that are cured by heating. Any of them can be used effectively. These photopolymerizable groups, functional groups capable of reacting with carboxyl groups, and compounds having functional groups capable of reacting with hydroxyl groups can improve the heat resistance of the coating film after curing, and are therefore used more effectively. be able to.

  Examples of the compound that contributes to the curing reaction as a heat curing aid include tertiary amines and salts thereof, dicyandiamide, carboxylic acid hydrazide, imidazoles, diazabicyclo compounds, phosphines, and phosphonium salts. When used, it is preferable because the thermosetting reaction proceeds more efficiently and the coating film has excellent resistance.

Specifically, tertiary amines such as triethylamine, tributylamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N-methylpiperazine, and salts thereof;
2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2,4-dicyano-6- [2-methylimidazolyl-1] Imidazoles such as ethyl-S-triazine, 2-ethyl-4-methylimidazole tetraphenylborate, and salts thereof;
1,5-diazabicyclo [5,4,0] -7-undecane, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,4-diabicyclo [2,2,2,] octane, , 8-diazabicyclo [5.4.0] undecene-7-tetraphenylborate and the like diazabicyclo compounds;
Phosphines such as tributylphosphine, triphenylphosphine, tris (dimethoxyphenyl) phosphine, tris (hydroxypropyl) phosphine, tris (cyanoethyl) phosphine;
Phosphonium salts such as tetraphenylphosphonium tetraphenylborate, methyltributylphosphonium tetraphenylborate, methyltricyanoethylphosphonium tetraphenylborate;
In addition, dicyandiamide, carboxylic acid hydrazide, and the like can be cited as compounds that are catalytic and that directly contribute to the curing reaction. Examples of the carboxylic acid hydrazide include succinic acid hydrazide and adipic acid hydrazide.

  Only one type of these thermosetting aids may be used, or two or more types may be used in combination. The amount of the thermosetting aid used may be determined in consideration of the intended use of the photosensitive conductive ink, and is not particularly limited. A range of 01 to 50 parts by weight is more preferable, and a range of 0.1 to 30 parts by weight is even more preferable. Thereby, since the crosslinking density of the photosensitive conductive ink can be adjusted to an appropriate value, various physical properties of the photosensitive conductive ink can be further improved. When the amount of the thermosetting aid used is more than 0.01 parts by weight, the cross-linking density of the coating film after heat curing can be increased, so that cohesive force and durability can be imparted. When the amount used is less than 50 parts by weight, the crosslink density after heat-curing is not excessively increased, and adhesion can be maintained.

[Other additives]
In addition, the photosensitive conductive ink of the present invention includes, as optional components, as long as the purpose is not impaired, and further includes solvents, dyes, pigments, flame retardants, antioxidants, polymerization inhibitors, chain transfer agents, leveling agents, and humectants. Viscosity modifiers, preservatives, antibacterial agents, antiblocking agents, ultraviolet absorbers, infrared absorbers, fillers, and the like can be added.

  Since the photosensitive conductive ink and the cured product thereof according to the present invention are characterized by excellent alkali developability, they can be suitably used for applications in which a film forming process including photocuring, alkali development, and post-cure is used. . Furthermore, since it has excellent conductivity, adhesion, etc., it provides a photosensitive conductive ink, its cured product, and a laminate, which are used for the formation of fine electrical circuits by photolithographic process, especially after creating a pattern by screen printing. I was able to do that. The photosensitive conductive ink of the present invention is suitably used as a photosensitive conductive ink for the formation of a fine conductive circuit formed on the frame of a touch screen panel or a fine metal mesh sheet having both transparency and low surface resistance. Can be used.

  The photosensitive conductive ink of the present invention can be applied to a metal, ceramics, glass, plastic, wood, slate or the like as a substrate, and is not particularly limited. Specific types of plastic include polyester, polyolefin, polycarbonate, polystyrene, polymethyl methacrylate, triacetyl cellulose resin, ABS resin, AS resin, polyamide, epoxy resin, melamine resin, and the like. Examples of the shape of the substrate include a film sheet, a plate-like panel, a lens shape, a disk shape, and a fiber shape, but are not particularly limited.

The conductive ink of the present invention can be suitably applied particularly to screen printing, but may be applied to various conventionally known printing methods. In the screen printing method, it is preferable to use a fine mesh screen, particularly preferably a fine mesh screen of about 400 to 650 mesh, in order to cope with high definition of the conductive circuit pattern. At this time, the open area of the screen is preferably about 20 to 50%. The screen wire diameter is preferably about 10 to 70 μm.
Examples of the screen plate include polyester screens, combination screens, metal screens, and nylon screens. Moreover, when printing the thing of a highly viscous paste state, a high tension stainless steel screen can be used.
The screen printing squeegee may be round, rectangular or square, and an abrasive squeegee can be used to reduce the attack angle (angle between printing plate and squeegee). Other printing conditions and the like may be appropriately designed according to conventionally known conditions.

  The photosensitive conductive ink of the present invention can be cured by a known radiation curing method to obtain a cured product, and as active energy rays, electron beams, ultraviolet rays, and visible light of 400 to 500 nm can be used. A thermionic emission gun, a field emission gun, or the like can be used as the electron beam source to be irradiated. For example, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, or the like can be used as a source (light source) for ultraviolet light and visible light of 400 to 500 nm. Specifically, an ultra-high pressure mercury lamp, a xenon mercury lamp, or a metal halide lamp is often used because of the point light source and the stability of luminance. The active energy dose to be irradiated can be set in a timely manner within a range of 5 to 2000 mJ / cm <2>, but is preferably within a range of 50 to 1000 mJ / cm <2> that can be easily managed in the process. Further, these active energy rays can be used in combination with heat by infrared rays, far infrared rays, hot air, high-frequency heating or the like.

  In order to increase exposure sensitivity by active energy rays, after applying and drying photosensitive conductive ink, water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to prevent polymerization inhibition by oxygen. After the film is formed, active energy rays can be irradiated from the composition application surface side.

  Furthermore, the photosensitive conductive ink of the present invention is irradiated with an active energy ray from the composition coated surface side through a photomask and immersed in a solvent or an alkaline developer, or sprayed with a developer by spraying or the like. It can be formed by removing the irradiated portion, that is, the uncured portion and developing. As the alkali developer, an aqueous solution such as sodium carbonate or sodium hydroxide is used, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. An antifoaming agent or a surfactant can also be added to the developer.

  Furthermore, the photosensitive conductive ink of this invention forms the coating film which is excellent in various durability and electroconductivity by heat-drying as a post-cure after pattern formation by radiation hardening / development. The post cure is preferably 30 to 2 hours at 100 to 200 ° C. Further, in order to further improve the resistance of the coating film, an active energy ray can be irradiated as necessary after post-curing. By irradiating active energy rays after post-cure, various durability, conductivity, etc. can be further improved.

The laminate with a conductive pattern according to the present invention can be suitably used particularly when a wiring structure is formed on a transparent electrode of a touch screen panel.
Here, an example in which the conductive ink of the present invention is applied to a resistive film type touch screen panel will be described with reference to FIGS. 1 and 2 are simple conceptual diagrams of the resistive touch screen panel, and the number of wirings, the wiring width, and the interval between the wirings are represented as conceptual diagrams. In FIG. 2, the laminated state of each substrate side is schematically shown with the viewpoint placed in the middle of the three layers, the position of the adhesive material 5, with the lower substrate 1 side looking down and the upper substrate 2 side looking up. .

The touch screen panel includes a lower substrate 1 and an upper substrate 2 made of a base material of glass or plastic film (polyethylene terephthalate film, polyethylene naphthalate film, acrylic resin film, polycarbonate film, or the like). Transparent electrodes 6 and 7 such as ITO are partially formed on the lower substrate 1 and the upper substrate 2, respectively. As a result, the lower substrate 1 and the upper substrate 2 and the transparent electrodes 6 and 7 are exposed.
Lower drive electrodes 13 and 14 made of the conductive ink pattern layer 3 are formed on both ends of the transparent electrode 6 on the lower substrate 1, respectively. The conductive ink layer 3 is covered with an insulating layer 4. As shown in FIG. 1, the conductive ink pattern layer 3 is in contact with the substrate 1, the transparent electrode 6 such as ITO, and the insulating layer 4.
Similarly, upper drive electrodes 9 and 10 made of the conductive ink layer 3 are formed on both ends of the transparent conductor 7 on the upper substrate 2.

  Specifically, the conductive ink of the present invention is used for the end of the transparent electrode 7 on the upper substrate 2 side, screen-printed, preliminary drying, exposure, development, and drying steps are performed in this order, and the low-resistance conductive ink. The pattern layer 3 is formed. Next, an insulating resist (not shown) is printed on the conductive ink layer 3 and the upper substrate 2 in the vicinity of the conductive ink pattern layer 3 and the end of the transparent electrode 7 by screen printing or the like. Then, it dries and hardens | cures, forms an insulating layer, and forms the laminated body with an insulating resist of this invention. The same applies to the lower substrate 1 side.

In order to prevent the transparent electrodes 6 and 7 from coming into contact with the transparent electrodes 6 and 7 at an appropriate place on the transparent electrode 6 provided on the lower substrate 1 except when the input is the original purpose, as shown in FIG. Small dot spacers 8 are provided at regular intervals at appropriate positions above.
Then, a certain interval (for example, an interval of 10 to 150 μm) is opened (see FIG. 1) so that the transparent electrodes 6 and 7 are not in contact with each other except at the time of input, which is the original purpose, and insulation on the lower substrate 1 side is performed. The layer 4 and the upper substrate 2, the lower substrate 1 and the upper substrate 2, and the lower substrate 1 and the insulating layer 4 on the upper substrate 2 side are respectively bonded and laminated by the adhesive material 5. The adhesive material 5 can be arranged in a frame shape. In addition, as shown in FIG. 2, the drive electrodes 13 and 14 on the lower substrate 1 side and the upper drive electrodes 9 and 10 on the upper substrate 2 side may be formed to be orthogonal to each other in plan view. Furthermore, connection electrodes 11 and 12 are connected to the drive electrodes 9 and 10 on the upper substrate 2 side by a conductive adhesive, respectively. Similarly, the drive electrodes 13 and 14 on the lower substrate 1 side are connected to the connection electrodes 15 and 16 with a conductive adhesive, respectively.

  The touch screen panel in which the conductive ink pattern layer 3 is formed using the conductive ink of the present invention on each of the lower substrate 1 side and the upper substrate 2 side has good resistance value stability and can be used for various electronic devices over a long period of time. It can be used stably as a component for switching the functions of the above, and has excellent electrical characteristics.

  EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight”.

The measurement conditions for GPC are as follows.
<Measurement of weight average molecular weight (Mw)>
For measurement of Mw, GPC (gel permeation chromatography) “HPC-8020” manufactured by Tosoh Corporation was used. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent (THF; tetrahydrofuran) based on the difference in molecular size. In the measurement of the present invention, two columns of “LF-604” (manufactured by Showa Denko KK: GPC column for rapid analysis: 6 mm ID × 150 mm size) are connected in series and the flow rate is 0.6 ml / min. The column temperature was 40 ° C., and the weight average molecular weight (Mw) was determined in terms of polystyrene.
<Molecular weight distribution (Mw / Mn)>
The degree of dispersion of the molecular weight is expressed. In the present invention, the weight average molecular weight (Mw) / number average molecular weight (Mn) was obtained from the measurement result of the molecular weight.

The acid value and hydroxyl value were measured according to IS K0070.
<Measurement of acid value>
About 1 g of a sample is accurately weighed in a stoppered Erlenmeyer flask, and 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution is added and dissolved. To this is added phenolphthalein reagent as an indicator and held for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red. The acid value was determined by the following formula (unit: mgKOH / g).
Acid value (mgKOH / g) = (5.611 × a × F) / S
However,
S: Sample collection amount (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution

<Measurement of hydroxyl value>
About 1 g of a sample is accurately weighed in a stoppered Erlenmeyer flask, and 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution is added and dissolved. Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for about 1 hour. To this, phenolphthalein reagent is added as an indicator and lasts for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red.
The hydroxyl value was determined by the following formula (unit: mgKOH / g).
Hydroxyl value (mgKOH / g) = [{(ba) × F × 28.05} / S] + D
However,
S: Sample collection amount (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption of 0.1N alcoholic potassium hydroxide solution in the empty experiment (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution D: Acid value (mgKOH / g)

In the present invention, the hydroxyl value of the side chain hydroxyl group-containing resin (c) is determined so that the amount of hydroxyl group contained in 1 g is neutralized with acetic acid bonded to the hydroxyl group when the hydroxyl group is acetylated. This is expressed in terms of the amount (mg) of potassium hydroxide required.
On the other hand, the hydroxyl value of a resin having both a carboxyl group and a hydroxyl group such as the photosensitive resin (A) is calculated by subtracting the amount of potassium hydroxide required for neutralization of the photosensitive resin (A) before acetylation. It is what you did.

<Calculation of ethylenically unsaturated group equivalent>
In this invention, the ethylenically unsaturated group equivalent of the photosensitive resin (A) was calculated | required by following Formula. (Unit: g / mol)
Ethylenically unsaturated group equivalent (g / mol) = total solid content of raw material (g) / number of moles of compound (f) charged (mol)

<Synthesis of carboxyl group-containing photosensitive resin (A-1-1)>
[Production Example 1]
Process 1
YD8125 (manufactured by Nippon Steel Chemical Co., Ltd., bisphenol A) as an epoxy compound (a) having two or more epoxy groups in a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet pipe, inlet pipe and thermometer Type epoxy compound, epoxy equivalent 173 g / eq) 57.1 parts, EX861 (manufactured by Nagase ChemteX Corporation: polyethylene glycol diglycidyl ether, epoxy equivalent 575 g / eq) 128.1 parts, two or more phenolic OH groups Bisphenol A 64.8 parts as a phenolic compound (b), 1.25 parts triphenylphosphine as a catalyst, 1.25 parts N, N-dimethylbenzylamine as a catalyst, 250 parts diethylene glycol monoethyl ether acetate as a solvent, and under nitrogen stream , Raised to 110 ° C. with stirring for 8 hours It is response, to obtain a hydroxyl group-containing resin having a hydroxyl value of 124mgKOH / g.

Process 2
Next, 54.6 parts of SA (succinic anhydride) (an amount corresponding to 98 mol% of the hydroxyl group) was added as the polybasic acid anhydride (d), and the reaction was allowed to proceed at 110 ° C. for 4 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. The acid value was 103 mgKOH / g.

Process 3
Next, in this flask, nitrogen from the nitrogen introduction tube is stopped, and switching to introduction of dry air is performed. While stirring, GMA (glycidyl methacrylate) is added as a compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group. ) 55.2 parts (an amount corresponding to 70 mol% of the carboxyl group derived from the succinic anhydride) and 0.18 part of hydroquinone as a polymerization inhibitor were added and reacted at 80 ° C. for 8 hours. After completion of the reaction, diethylene glycol monoethyl ether acetate was added to this solution to adjust the solid content to 50.0%.
The ethylenically unsaturated group equivalent of the carboxyl group-containing photosensitive resin (A-1-1) is 925 g / eq, the weight average molecular weight in terms of polystyrene is 25100, and the acid value of the resin solid content is 26 mgKOH / g.

[Production Examples 2 to 10]
Using the raw materials shown in Table 1, the same operations as in Production Example 1 were performed to obtain carboxyl group-containing photosensitive resins (A-1-2) to (A-1-10) of Production Examples 2 to 10. .

<Synthesis of carboxyl group-containing photosensitive resin (A-2-1)>
[Production Example 11]
Process 1
YD8125 (manufactured by Nippon Steel Chemical Co., Ltd., bisphenol A) as an epoxy compound (a) having two or more epoxy groups in a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet pipe, inlet pipe and thermometer Type epoxy compound, epoxy equivalent 173 g / eq) 19.4 parts, EX861 (manufactured by Nagase ChemteX Corporation: polyethylene glycol diglycidyl ether, epoxy equivalent 575 g / eq) 177.2 parts, 2 or more phenolic OH groups A phenol compound (b) having 53.4 parts of bisphenol A, 1.25 parts of triphenylphosphine, 1.47 parts of N, N-dimethylbenzylamine as a catalyst, 250 parts of diethylene glycol monoethyl ether acetate as a solvent, and under a nitrogen stream The temperature was raised to 110 ° C. with stirring for 8 hours. It is response, to obtain a hydroxyl group-containing resin having a hydroxyl value 95.7mgKOH / g.

Process 2
Next, 20.1 parts of SA (succinic anhydride) (an amount corresponding to 98 mol% of the hydroxyl group) was added as the polybasic acid anhydride (d), and the reaction was allowed to proceed at 110 ° C. for 4 hours. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature. The acid value was 102 mgKOH / g.

Process 3
Next, in this flask, nitrogen from the nitrogen introduction tube is stopped, and switching to introduction of dry air is performed. While stirring, GMA (glycidyl methacrylate) is added as a compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group. 41.1 parts (amount corresponding to 50 mol% of the carboxyl group derived from the succinic anhydride) and 0.17 part of hydroquinone as a polymerization inhibitor were added and reacted at 80 ° C. for 8 hours. The hydroxyl value of the product was 38 mgKOH / g, and the acid value was 40 mgKOH / g. The hydroxyl value depends on the hydroxyl group left in step 2 and the hydroxyl group newly generated in step 3.

Process 4
After completion of the reaction, 26.0 parts of SA (succinic anhydride) (an amount corresponding to 90 mol% of the hydroxyl group) was added as a polybasic acid anhydride (g) to a flask in which dry air was introduced, The reaction was continued for 4 hours at 80 ° C. After confirming that the absorption of the acid anhydride group disappeared by FT-IR measurement, it was cooled to room temperature.
Diethylene glycol monoethyl ether acetate was added to this solution to adjust the solid content to 50.0%.
The ethylenically unsaturated group equivalent of the carboxyl group-containing photosensitive resin (A-2-1) is 1547 g / eq, the polystyrene-equivalent weight average molecular weight is 23005, and the acid value is 68.9 mgKOH / g.

[Production Examples 12 to 36]
Using the raw materials shown in Table 1-1 to Table 1-4, the same operations as in Production Example 11 were performed, whereby carboxyl group-containing photosensitive resins (A-2-2) to (A-) in Production Examples 12-35. 2-36) was obtained.
The weight average molecular weight, the ethylenically unsaturated group equivalent, the hydroxyl value, the acid value, etc. of the photosensitive resins obtained in Production Examples 1 to 36 are shown in Tables 1-1 to 1-6.

<Epoxy compound having two or more epoxy groups (a)>
YD8125: manufactured by Nippon Steel Chemical Co., Ltd., bisphenol A type epoxy compound, epoxy equivalent of 171 g / eq)
EX861: manufactured by Nagase ChemteX Corporation, polyethylene glycol diglycidyl ether (epoxy equivalent 575 g / eq)
EX830: manufactured by Nagase ChemteX Corporation, polyethylene glycol diglycidyl ether (epoxy equivalent 267 g / eq)
EX931: manufactured by Nagase ChemteX Corporation, polypropylene glycol diglycidyl ether (epoxy equivalent 493 g / eq)
SR-PTMG: Sakamoto Pharmaceutical Co., Ltd., polytetraethylene glycol diglycidyl ether (epoxy equivalent 413 g / eq)
SR-16HL: Sakamoto Pharmaceutical Co., Ltd., 1,6-hexanediol diglycidyl ether (epoxy equivalent 125 g / eq)
PG100: manufactured by Osaka Gas Chemical Co., Ltd., fluorene diglycidyl ether (epoxy equivalent 214 g / eq)
EG250: manufactured by Osaka Gas Chemical Co., Ltd., fluorene diglycidyl ether (epoxy equivalent 417 g / eq)
YX4000: manufactured by Mitsubishi Chemical Corporation, biphenyl type epoxy resin (epoxy equivalent 177 g / eq)
YL7410: Mitsubishi Chemical Corporation, rubber-modified epoxy resin (epoxy equivalent 219 g / eq)

<Phenol compound (b) having two or more phenolic OH groups>
BisA: Bisphenol A: 4,4 ′-(Dimethylmethylene) diphenol BisF: Bisphenol F: 4,4′-methylenediphenol Biphenol: 2,2′-biphenol BS-PN: Konishi Chemical Co., Ltd. Bisphenol S: 4,4′-sulfonyldiphenol TDP: manufactured by Sumitomo Seika Co., Ltd., bis (4-hydroxyphenyl) sulfide / HMPS: manufactured by Sumitomo Seika Co., Ltd., bis (4-hydroxy-3-methyl) Phenyl) sulfide CP001: Fluorene bisphenol compound, manufactured by Osaka Gas Chemical Co., Ltd.

<Polybasic acid anhydrides (d), (g)>
SA: Shin Nippon Rika Co., Ltd., succinic anhydride. TH: Shin Nippon Rika Co., Ltd., tetrahydrophthalic anhydride <compound having epoxy group or oxetane group and ethylenically unsaturated group (f)>
GMA: glycidyl methacrylate 4HBAGE: 4-hydroxybutyl acrylate glycidyl ether OXMA: oxetanyl methacrylate <others>
-TPP: Triphenylphosphine-DMBA: N, N-dimethylbenzylamine

[Production Example 37]
A dropping funnel was placed in a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet pipe, inlet pipe, and thermometer, and 400 parts of diethylene glycol monoethyl ether acetate was charged into the flask while stirring under a nitrogen atmosphere. The temperature was raised to ° C.
In a separate container, 15 parts of methacrylic acid, 30 parts of methyl methacrylate, 30 parts of butyl methacrylate, 25 parts of benzyl methacrylate, 20 parts of azobisisobutyronitrile as a polymerization initiator and 100 parts of diethylene glycol monoethyl ether acetate are stirred and stirred. And evenly dissolved. The monomer solution was charged into a dropping funnel installed in the flask, and the monomer solution in the dropping funnel was dropped into the flask over 2 hours while stirring the flask at 90 ° C. in a nitrogen atmosphere. Stirring was continued at 90 ° C. even after completion of the dropping, and 0.5 part of azobisisobutyronitrile was charged into the flask after 2 hours from the end of the dropping. After 1 hour, 0.5 part of azobisisobutyronitrile was again added to the flask, and stirring was continued for another 2 hours. Thereafter, the flask was cooled to stop the reaction. A small amount of sampling was performed to obtain a carboxyl group-containing acrylic prepolymer having a polystyrene-equivalent weight average molecular weight of 18700, a molecular weight distribution of 2.58, and an acid value of resin solid content of 98 mgKOH / g.

  Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, and 111 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. , Reacted at 90 ° C. for 8 hours. After completion of the reaction, a small amount of sampling was performed to obtain a hydroxyl group-containing acrylic prepolymer having a polystyrene-equivalent weight average molecular weight of 19,900, a molecular weight distribution of 2.72, and an actually measured acid value of resin solids of 5 mgKOH / g.

Next, 63 parts of succinic anhydride was added to the flask and reacted for 6 hours with stirring at 90 ° C. in a dry air atmosphere. After confirming that absorption of the acid anhydride group disappeared by FT-IR measurement, the mixture was cooled to room temperature to obtain a carboxyl group-containing photosensitive resin whose main skeleton was an acrylic resin.
Next, diethylene glycol monoethyl ether acetate was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content by this design was 863 g / eq, the weight average molecular weight in terms of polystyrene was 22000, the molecular weight distribution was 2.81, and the acid value of the resin solid content was 70 mgKOH / g.

[Production Example 38]
A four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet pipe, inlet pipe, thermometer, bisphenol A type epoxy having an epoxy equivalent of 650, a softening point of 81.1 ° C., and a melt viscosity (150 ° C.) of 12.5 poise 371 parts of resin, 925 parts of epichlorohydrin, and 463 parts of dimethyl sulfoxide were added and dissolved uniformly, and then 52.8 parts of 98.5% aqueous sodium hydroxide solution was added at 70 ° C. over 100 minutes with stirring. After the addition, the reaction was further carried out at 70 ° C. for 3 hours.
Subsequently, most of the excess unreacted epichlorohydrin and dimethyl sulfoxide are distilled off under reduced pressure, and the reaction product containing the by-product salt and dimethyl sulfoxide is dissolved in 750 parts of diethylene glycol monoethyl ether acetate, and further 30% aqueous sodium hydroxide solution 10 parts were added and reacted at 70 ° C. for 1 hour. After completion of the reaction, washing was performed twice with 200 parts of water.
After separation of oil and water, diethylene glycol monoethyl ether acetate was recovered by distillation from the oil layer, epoxy equivalent 287, hydrolyzable chlorine content 0.07%, softening point 64.2 ° C, melt viscosity (150 ° C) 7.1 poise. 340 parts of epoxy resin were obtained.

287 parts of this epoxy resin was put into a four-necked flask equipped with another stirrer, reflux condenser, nitrogen inlet pipe, inlet pipe and thermometer, and further 72 parts of acrylic acid, 0.3 part of methylhydroquinone, diethylene glycol mono 194 parts of ethyl ether acetate was charged and heated to 90 ° C. and stirred to dissolve the raw materials.
Subsequently, the raw material solution was cooled to 60 ° C., 1.7 parts of triphenylphosphine was charged, and the reaction was performed at 100 ° C. for about 32 hours in the presence of oxygen to obtain a reaction product having an acid value of 1 mgKOH / g.
Next, 78 parts of succinic anhydride and 42 parts of diethylene glycol monoethyl ether acetate were added to this, and reacted at 95 ° C. for about 6 hours. A photosensitive resin having was obtained.
Next, diethylene glycol monoethyl ether acetate was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content was 450 eq / g, the polystyrene equivalent weight average molecular weight was 7400, the molecular weight distribution was 2.23, and the actually measured acid value of the resin solid content was 100 mgKOH / g.

[Production Example 39]
A cresol novolak type epoxy resin having an epoxy equivalent of 218 g / eq (manufactured by Toto Kasei Co., Ltd .: YDCN-702, epoxy equivalent of 203 g) was added to a four-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube and thermometer. / Eq) 330 parts were charged, heated and melted at 90 to 100 ° C., and stirred. Next, 120 parts of acrylic acid, 0.6 part of hydroquinone, and 5 parts of dimethylbenzylamine were added, and the mixture was heated to 115 ° C. with stirring in the presence of oxygen and reacted for 12 hours.
Next, 400 parts of diethylene glycol monoethyl ether acetate was put into this flask and dissolved by heating to 70 ° C. Next, 81 parts of succinic anhydride was added, and the temperature was raised to 95 ° C., followed by stirring and reaction for 8 hours. After confirming that the absorption of the acid anhydride group has disappeared by FT-IR measurement, it is cooled to room temperature, the main skeleton is a cresol novolak skeleton, and has a carboxyl group and an ethylenically unsaturated bond in the side chain A photosensitive resin was obtained.
Next, diethylene glycol monoethyl ether acetate was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content was 319 g / eq, the weight average molecular weight in terms of polystyrene was 11000, the molecular weight distribution was 2.90, and the acid value of the resin solid content measured was 85 mgKOH / g.

[Production Example 40]
In a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, thermometer, 212 parts of PTG850 (Hodogaya Chemical Co., Ltd .: polytetramethylene glycol, hydroxyl value = 129 mgKOH / g), ethylene glycol 75 Part, pyromellitic anhydride (manufactured by Daicel Chemical Industries, Ltd.) 159 parts, dimethylbenzylamine 2 parts, diethylene glycol monoethyl ether acetate 375 parts as a solvent, stirred at 100 ° C. for 10 hours with stirring under a nitrogen stream, Half-esterification reaction was performed. Subsequently, 54 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a polyester polyurethane prepolymer having a carboxyl group with a side chain of a polystyrene-equivalent weight average molecular weight of 15200, a molecular weight distribution of 2.87, and an acid value of 170 mgKOH / g of resin solids.

Next, the nitrogen from the nitrogen introduction tube was stopped in this flask, switched to introduction of dry air, 110 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine, and 0.3 part of hydroquinone as a polymerization inhibitor were added while stirring. The reaction was continued for 8 hours at 90 ° C. After cooling, a small amount of sampling was performed to obtain a photosensitive urethane resin having a main skeleton of polyester polyurethane and having a carboxyl group and an ethylenically unsaturated bond in the side chain.
Next, diethylene glycol monoethyl ether acetate was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content was 896 g / eq, the polystyrene-equivalent weight average molecular weight was 18,800, the molecular weight distribution was 3.12, and the acid value of the resin solid content was 72 mgKOH / g as measured.

[Production Example 41]
In a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, inlet tube, and thermometer, 218 parts of PTG850 (Hodogaya Chemical Co., Ltd .: polytetramethylene glycol, hydroxyl value = 129 mgKOH / g), ethylene glycol 47 Parts, 125 parts of pyromellitic anhydride (manufactured by Daicel Chemical Industries, Ltd.), 2 parts of dimethylbenzylamine, and 375 parts of diethylene glycol monoethyl ether acetate as a solvent, and stirred at 100 ° C. for 10 hours with stirring under a nitrogen stream, Half-esterification reaction was performed. Subsequently, 111 parts of isophorone diisocyanate was added to the flask and stirred at 90 ° C. for 8 hours to carry out a urethanization reaction. After completion of the reaction, a small amount of sampling was performed to obtain a polyester polyurethane prepolymer having a carboxyl group with a side chain of a weight-average molecular weight in terms of polystyrene of 17000, a molecular weight distribution of 2.60, and an acid value of 110 mg KOH / g of resin solid content by actual measurement. .

  Next, the nitrogen from the nitrogen introduction tube was stopped in this flask and switched to introduction of dry air. While stirring, 131 parts of glycidyl methacrylate, 6 parts of dimethylbenzylamine, and 0.3 part of hydroquinone as a polymerization inhibitor were added. The reaction was continued for 8 hours at 90 ° C. After completion of the reaction, a small amount of sampling was performed to obtain a polyester polyurethane prepolymer having a hydroxyl group with a weight average molecular weight of 19200 in terms of polystyrene, a molecular weight distribution of 3.00, and an acid value of 4 mgKOH / g of resin solids in the side chain.

Next, 74 parts of succinic anhydride was added to the flask, and the mixture was further reacted for 6 hours at 90 ° C. in a dry air atmosphere. After confirming that absorption of the acid anhydride group has disappeared by FT-IR measurement, it is cooled to room temperature, the main skeleton is a polyester polyurethane resin, and has a carboxyl group and an ethylenically unsaturated bond in the side chain. A photosensitive urethane resin was obtained.
Next, diethylene glycol monoethyl ether acetate was added to this solution to adjust the solid content to 50.0%. The ethylenically unsaturated group equivalent of the resin solid content was 765 g / eq, the weight average molecular weight in terms of polystyrene was 21400, the molecular weight distribution was 3.20, and the acid value of the resin solid content measured was 67 mgKOH / g.

[Examples 1-32, 83-86], [Comparative Examples 1-5] <Preparation of photosensitive conductive ink>
Photosensitive resins obtained in Production Examples 1 to 36 and Production Examples 37 to 41: 17 parts by weight of a resin solution containing 8.5 parts by weight; Silver powder A described later as conductive particles: 87 parts by weight; 5 parts by weight of a γ-butyrolactone solution of a photopolymerization initiator in which 1.5 parts by weight of “TPO” (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) is dissolved as an agent, and Toagosei Co., Ltd. as a monomer A “Aronix M400” manufactured by the manufacturer was mixed with a disper and dispersed with three rolls to prepare a photosensitive conductive ink.
The characteristic of the obtained photosensitive conductive ink was measured by the following method. The results are shown in Tables 3-1 to 3-5.

[Examples 33 to 40] <Preparation of photosensitive conductive ink>
Instead of 87 parts by weight of silver powder A used in Example 9, 87 parts by weight of silver powders B to G described later are used in Examples 33 to 38, respectively, and 82.6 parts by weight of silver powder A and silver powder H are used in Example 39. In Example 40, the photosensitive conductive ink was used in the same manner as in Example 9, except that 4.4 parts by weight of silver powder A: 82.6 parts by weight and silver powder I: 4.4 parts by weight were used. Obtained and evaluated in the same manner. The results are shown in Table 3-6.

[Examples 41 to 47] <Preparation of photosensitive conductive ink>
Instead of 1.5 parts by weight of the photopolymerization initiator “TPO” used in Example 9, each of Examples 41 to 45 used 1.5 parts by weight of photopolymerization initiators B to F described later. Initiator B: 1.2 parts by weight and initiator G: 0.3 parts by weight were used. In Example 47, initiator B: 1.2 parts by weight and initiator H: 0.3 parts by weight were used. Except for the above, a photosensitive conductive ink was obtained in the same manner as in Example 9 and evaluated in the same manner. The results are shown in Table 3-7.

[Examples 48 to 51] <Preparation of photosensitive conductive ink>
Monomer A used in Example 9: Instead of 3 parts by weight, in Examples 48 to 51, a photosensitive conductive ink was prepared in the same manner as in Example 9 except that 3 parts by weight of monomers B to E described later were used. Obtained and evaluated in the same manner. The results are shown in Table 3-8.

[Examples 52 to 53] <Preparation of photosensitive conductive ink>
The photosensitive resin (A-2-1) used in Example 9 was 7.5 parts by weight (15 parts by weight as a resin solution), epoxy resins A and B described later were each 1 part by weight, and diethylene glycol monoethyl. A photosensitive conductive ink was obtained in the same manner as in Example 9 except that 1 part by weight of ether acetate was added, and was similarly evaluated. The results are shown in Table 3-9.

[Examples 54 to 55] <Preparation of photosensitive conductive ink>
The photosensitive resin (A-2-1) used in Example 9 was 7.5 parts by weight (15 parts by weight as the resin solution), 1 part by weight of each of blocked isocyanates A and B described below, and diethylene glycol mono A photosensitive conductive ink was obtained and evaluated in the same manner as in Example 9 except that 1 part by weight of ethyl ether acetate was added. The results are shown in Table 3-9.

[Examples 56 to 59] <Preparation of photosensitive conductive ink>
The photosensitive resin (A-2-1) used in Example 9 was 7.5 parts by weight (15 parts by weight as a resin solution), primids A to D described later were each 1 part by weight, and diethylene glycol monoethyl ether acetate. A photosensitive conductive ink was obtained and evaluated in the same manner as in Example 9 except that 1 part by weight and 1 part by weight of methyl ethyl ketone were added. The results are shown in Table 3-9.

[Example 60] <Preparation of photosensitive conductive ink>
7.5 parts by weight of photosensitive resin (A-2-1) used in Example 9 (15 parts by weight as a resin solution), 6 parts by weight of diethylene glycol monoethyl ether acetate without using γ-butyrolactone, A photosensitive conductive ink was obtained in the same manner as in Example 9 except that the amount of the photopolymerization initiator was 1.5 parts by weight, and was similarly evaluated. The results are shown in Table 3-10.

[Example 61] <Preparation of photosensitive conductive ink>
7.5 parts by weight of the photosensitive resin (A-2-1) used in Example 9 (15 parts by weight as the resin solution), 1 part by weight of diethylene glycol monobutyl ether acetate, 5 parts by weight of γ-butyrolactone, A photosensitive conductive ink was obtained in the same manner as in Example 9 except that the amount of the photopolymerization initiator was 1.5 parts by weight, and was similarly evaluated. The results are shown in Table 3-10.

[Example 62] <Preparation of photosensitive conductive ink>
The photosensitive resin (A-2-1) used in Example 9 was 7.5 parts by weight (15 parts by weight as the resin solution), 6 parts by weight of diethylene glycol monobutyl ether acetate, and 1.5% of the photopolymerization initiator. A photosensitive conductive ink was obtained in the same manner as in Example 9 except that the parts were by weight, and evaluated in the same manner. The results are shown in Table 3-10.

[Examples 63 to 65] <Preparation of photosensitive conductive ink>
The photosensitive resin (A-2-1) used in Example 9 was 8 parts by weight (16 parts by weight as the resin solution), and 0.5 parts by weight of Al chelate, Ti chelate and Zr chelate described later and diethylene glycol were used respectively. A photosensitive conductive ink was obtained and evaluated in the same manner as in Example 9 except that 0.5 part by weight of monoethyl ether acetate was added. The results are shown in Table 3-11.

[Examples 66 to 67] <Preparation of photosensitive conductive ink>
The photosensitive resin (A-2-1) used in Example 9 was 8 parts by weight (16 parts by weight as the resin solution), 0.5 parts by weight of diethylene glycol monoethyl ether acetate, and an ultraviolet absorber (described later) A photosensitive conductive ink was obtained and evaluated in the same manner as in Example 9 except that 0.5 parts by weight of inorganic and dye-based ultraviolet absorbers were added as I). The results are shown in Table 3-11.

[Examples 68 to 82] <Preparation of photosensitive conductive ink>
Photosensitive resin (A-2-1) obtained in Production Example 9, the main skeleton obtained in Production Example 39 is a cresol novolac skeleton, and a photosensitive resin having a carboxyl group and an ethylenically unsaturated bond in the side chain; Using the silver powder A, the initiator A, and the monomer A, a photosensitive conductive ink was obtained in the same manner as in Example 1 according to the formulations shown in Tables 3-12 to 3-13, and similarly evaluated. The results are shown in Table 3-12 to Table 3-13.

[Comparative Examples 6 to 8] <Preparation of photosensitive conductive ink>
As shown in Table 3-14, no photosensitive resin was used (Comparative Examples 6 and 8) or no photopolymerization initiator was used (Comparative Example 7) to obtain a photosensitive conductive ink. Evaluation was performed in the same manner as in the examples. The results are shown in Table 3-14.

[Conductive particles (B)]
Silver powder A: Spherical silver powder (D50 particle diameter 2.8 μm, specific surface area 0.36 m 2 / g)
Silver powder B: D spherical silver powder (D50 particle diameter 0.9 μm, specific surface area 0.93 m 2 / g)
Silver powder C: Flake silver powder (D50 particle diameter 0.4 μm, specific surface area 1.90 m 2 / g)
Silver powder D: Flake silver powder (D50 particle diameter 2.5 μm, specific surface area 1.76 m 2 / g)
Silver powder E: Flake silver powder (D50 particle diameter 4.2 μm, specific surface area 0.41 m 2 / g)
Silver powder F: Flake silver powder (D50 particle size 6.3 μm, specific surface area 0.31 m 2 / g)
Silver powder G: Aggregated silver powder (D50 particle diameter 1.2 μm, specific surface area 1.50 m 2 / g)
Silver powder H: Silver fine particles (Nippon Paint Co., Ltd. Finesphere SVE102, D50 particle size 0.01 μm)

Silver powder I: Silver fine particles A separable four-necked flask was equipped with a cooling tube, a thermometer, a nitrogen gas introduction tube, and a stirrer, and charged with 200 parts of toluene and 22.3 parts of silver hexanoate while stirring at room temperature in a nitrogen atmosphere. After preparing a 0.5 M solution, 2.3 parts of diethylaminoethanol (0.2 mol times with respect to 1 mol of metal) and 2.8 parts of oleic acid (0.1 mol times with respect to 1 mol of metal) are added and dissolved as a dispersant. It was. Thereafter, when 73.1 parts of a 20% SUDH aqueous solution (2 mol times of hydrazide group with respect to 1 mol of metal) was dropped, the liquid color changed from light yellow to dark brown. In order to further promote the reaction, the temperature was raised to 40 ° C. to advance the reaction. After standing and separating, excess reducing agent and impurities were removed by taking out the aqueous phase, and distilled water was added several times to the toluene layer, washing and separation were repeated, and dried to obtain silver fine particles. . The average particle size of the silver fine particles was 0.005 μm.

[Photoinitiator (C)]
Initiator A: LUSFIRIN TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by BASF
Initiator B: IRGACURE 907 (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one) manufactured by BASF
Initiator C: IRGACURE 379 (2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1) manufactured by BASF
-Initiator D: IRGACURE 754 (oxyphenyl acetate ester) manufactured by BASF
Initiator E: IRGACURE OXE01 manufactured by BASF (1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)])
Initiator F: IRGACURE OXE02 manufactured by BASF (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime))
Initiator G: Kayacure DETX-S (2,4-diethylthioxanthone)
Initiator H: EAB-F (4,4′-bisdiethylaminobenzophenone) manufactured by Hodogaya Kogyo Co., Ltd.

[Ethylenically unsaturated compound (E)]
Monomer A: Aronix M400 manufactured by Toagosei Co., Ltd. (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
Monomer B: Nippon Kayaku Co., Ltd. DPCA60 (caprolactone modified product of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
Monomer C: Aronix M313 manufactured by Toagosei Co., Ltd. (mixture of isocyanuric acid EO-modified diacrylate and triacrylate)
Monomer D: Aronix M211B (bisphenol A EO-modified diacrylate) manufactured by Toagosei Co., Ltd.
Monomer E: Aronix M408 (ditrimethylolpropane tetraacrylate) manufactured by Toagosei Co., Ltd.

[Heat-crosslinking compound (F)]
Epoxy A: 1031s (multifunctional glycidyl ether type epoxy compound) manufactured by Mitsubishi Chemical Corporation
-Epoxy B: Mitsubishi Chemical Corporation 828 (bisphenol A type epoxy compound)
Block isocyan A: BL3175 (HDI isocyanurate type blocked isocyanate) manufactured by Sumika Bayer Urethane Co., Ltd.
Block isocyan B: BL4265SN (IPDI isocyanurate type blocked isocyanate) manufactured by Sumika Bayer Urethane Co., Ltd.

<Primid A: β-hydroxyalkylamide compound>
In a reaction vessel equipped with a stirrer, thermometer, dropping device, Dean-Stark tube, reflux condenser, and gas introduction tube, 210 parts of diethanolamine and 10 parts of potassium hydroxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 174 parts of dimethyl adipates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 144 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all the toluene was distilled off. To 447 parts of this liquid product, a mixture of 141 parts of 2-acryloyloxyethyl isocyanate (Karenz AOI manufactured by Showa Denko KK) and 0.3 part of methoquinone was dropped from a dropping device over 1 hour. It stirred at 100 degreeC after dripping for 1 hour. 1H-NMR measurement and IR measurement were performed to confirm that the target product was produced. After cooling to 50 ° C., methyl ethyl ketone was added to adjust to NV = 50%, and a β-hydroxyalkylamide solution (primid A) containing a photopolymerizable functional group was taken out.

<Primid B: β-hydroxyalkylamide compound>
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube, N, N, N ′, N′-tetrakis (hydroxyethyl) adipamide (Primid XL-552 manufactured by Emschemy) ) 320 parts were added and heated to 150 ° C. with stirring to melt. In this, 144 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, and water produced by azeotroping with toluene was removed. The refluxed toluene was returned to the reaction vessel. After sufficiently removing water, all of toluene was removed, and 1H-NMR measurement and IR measurement were performed to confirm that the target product was produced. After cooling to 50 ° C., methyl ethyl ketone was added to adjust to NV = 50%, and a β-hydroxyalkylamide solution (primid B) containing no photopolymerizable functional group was taken out.

<Primid C: β-hydroxyalkylamide compound>
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube, dimethyl sebacate 256 parts, diethanolamine 234 parts, potassium hydroxide 10 parts, toluene 300 parts, and Dean Stark The tube was filled with toluene and heated to reflux while blowing nitrogen to remove water produced by azeotropy. After 4 hours, all the toluene was removed, and 1H-NMR measurement and IR measurement were performed to confirm that the target product was produced. After cooling to 50 ° C., methyl ethyl ketone was added to adjust to NV = 50%, and a β-hydroxyalkylamide solution (primid C) containing no photopolymerizable functional group was taken out.

<Primid D: β-hydroxyalkylamide compound>
In a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a Dean-Stark tube, a reflux condenser, and a gas introduction tube, 210 parts of diethanolamine and 10 parts of sodium methoxide were placed and heated to 100 ° C. while blowing nitrogen. In this, 230 parts of dimethyl sebacates were dripped over 4 hours from the dripping apparatus. After completion of the dropwise addition, the reaction vessel was heated while being depressurized to 205 mmHg to remove the generated methanol. The slurry-like product produced in the container was taken out and vacuum dried. 320 parts of this product was again put into the reaction vessel and melted by heating and stirring at 150 ° C. In this, 144 parts of 2-ethylhexanoic acid was dripped from the dripping apparatus over 1 hour. After dropping, the mixture was stirred at 150 ° C. for 1 hour, 100 parts of toluene was added, the Dean-Stark tube was filled with toluene, heated to reflux while blowing nitrogen, and water produced by azeotropy was removed. After 4 hours, all the toluene was removed, and 1H-NMR measurement and IR measurement were performed to confirm that the target product was produced. After cooling to 50 ° C., methyl ethyl ketone was added to adjust to NV = 50%, and a β-hydroxyalkylamide solution (primid D) containing no photopolymerizable functional group was taken out.

[Solvent (G)]
EGDAc: diethylene glycol monoethyl ether acetate BuCBAc: diethylene glycol monobutyl ether acetate γ-BL: gamma butyl lactone MEK: methyl ethyl ketone

[Metal chelating agent (H)]
・ Al chelate: ALCH manufactured by Kawaken Fine Chemical Co., Ltd.
Ti chelate: Olga Chicks TC-100 manufactured by Matsumoto Fine Chemical Co., Ltd.
Zr chelate: Olga Chicks ZC-540 manufactured by Matsumoto Fine Chemical Co., Ltd.

[Ultraviolet absorber (I)]
・ Inorganic: TYPEKE FT-2000 manufactured by Ishihara Sangyo Co., Ltd.
-Dye system: Sumisorb200 manufactured by Sumika Chemtex

[Create test piece (1)]
Screen printing was performed on the 75-μm thick corona-treated polyethylene terephthalate film (hereinafter referred to as PET) with the conductive inks of Examples 1 to 88 and Comparative Examples 1 to 8 in a pattern shape of 15 mm × 30 mm. Thereafter, it was pre-dried at 70 ° C. for 15 minutes, exposed to 200 (mJ / cm ² ) ultraviolet rays using an ultrahigh pressure mercury lamp, and then applied to a spin developer using a 0.5% aqueous sodium carbonate solution. After developing with a spray pressure of 0.2 MPa and a development time of 30 seconds, ion-exchanged water was spray-washed with a pressure of 0.05 MPa for 15 seconds. Finally, it was dried in a 135 ° C. oven for 30 minutes, and a test piece (1) was prepared so that the film thickness after drying was 8 to 10 μm.

<Measurement of surface resistance value>
The surface resistance value of the test piece (1) printed matter was measured using a Loresta APMCP-T400 measuring instrument manufactured by Mitsubishi Chemical Corporation in an environment of 25 ° C. and 50% humidity.

<Calculation of volume resistivity>
The volume resistivity was calculated from the surface resistance value measured by the above method and the film thickness.
Volume resistivity (Ω · cm) = (Surface resistivity: Ω / □) x (Film thickness: cm)
The film thickness of the test piece (1) printed matter was measured using an MH-15M measuring instrument manufactured by Sendai Nikon Corporation.

[Create test piece (2)]
An ITO laminated film (manufactured by Nitto Denko Corporation, V270L-TEMP, 75 μm thick, having a portion where ITO is removed by etching and a portion where ITO remains) of Examples 1 to 88 and Comparative Examples 1 to 8 The photosensitive conductive ink is subjected to the same printing, preliminary drying, exposure, development, and drying steps as in the test piece (1) creation process, and the test piece (2) so that the film thickness after drying is 8 to 10 μm. It was created. Evaluation methods and evaluation criteria are as follows.

<Tape adhesion test>: A tape adhesion test was performed in accordance with JIS K5600.
Put a total of 100 squares of 10 squares x 10 squares at intervals of 1 mm in the conductive ink layer on each of the remaining ITO part and ITO etched part, and paste Nichiban cellophane tape (25 mm wide) on the printed surface. The evaluation was performed in the state of the cells that were peeled off rapidly and remained.
○: No peeling (good adhesion level)
Δ: Slightly chipped edges of the mass (adhesion is slightly poor, but practically usable level)
X: Peeling over 1 square is observed (adhesion failure level)

[Photolithographic characteristics (sensitivity)]
After coating the photosensitive conductive ink on the glass substrate by screen printing, a coating film having a dry film thickness of 8 to 10 μm was prepared by drying at 70 ° C. for 15 minutes, and the film thickness was measured. Thereafter, using an ultrahigh pressure mercury lamp, ultraviolet rays were irradiated through a photomask having a mask pattern of L / S (line / space) = 40 μm / 40 μm while changing the exposure amount (mJ / cm ² ). After developing with a 0.5% sodium carbonate aqueous solution in a spin developing machine with a spray pressure of 0.2 MPa and a development time of 30 seconds, ion-exchanged water is sprayed with a pressure of 0.05 MPa for 15 seconds, Removed. The film thickness of the exposed part after development and washing with water was measured, and the minimum exposure amount (mJ / cm ² ) at which a film thickness of 95% or more with respect to the film thickness before development was obtained was defined as sensitivity.

[Photolithographic characteristics (development speed)]
After coating photosensitive conductive ink on a glass substrate by screen printing, a coating film having a dry film thickness of 8 to 10 μm was prepared by drying at 70 ° C. for 15 minutes, and the film thickness was measured. A 0.5% aqueous sodium carbonate solution was sprayed on the dried coating film, and the time for the dried coating film of the photosensitive conductive ink to disappear was measured. The measurement time was divided by the measured film thickness, and the time per unit film thickness (seconds / μm) was taken as the development speed. If the development speed is 50 seconds / μm or less, the level is practically acceptable.

[Photolithographic characteristics (resolution)]
After coating photosensitive conductive ink on a glass substrate by screen printing, a coating film having a dry film thickness of 8 to 10 μm was prepared by drying at 70 ° C. for 15 minutes, and the film thickness was measured. Thereafter, using an ultrahigh pressure mercury lamp, ultraviolet rays were irradiated through a photomask having mask patterns of L / S = 20 μm / 20 μm, 30 μm / 30 μm, and 40 μm / 40 μm while changing the exposure dose (mJ / cm ² ). After developing with a 0.5% sodium carbonate aqueous solution in a spin developer with a spray pressure of 0.2 MPa and a development time of 30 seconds, ion-exchanged water was spray-washed with a pressure of 0.05 MPa for 15 seconds, and the unexposed portion was removed. Removed. The stripe pattern of each width | variety of the exposure part after image development and water washing was confirmed visually, and resolution was evaluated.
A: A stripe pattern of L / S = 20/20 μm can be formed.
A: A stripe pattern of L / S = 30/30 μm can be formed.
Δ: A stripe pattern of L / S = 40/40 μm can be formed.
X: A stripe pattern of L / S = 40/40 μm cannot be formed.

[Resistance stability evaluation]
A movable electrode substrate made of a transparent conductive film and a fixed electrode substrate made of a glass electrode substrate were bonded together with a double-sided adhesive layer made of double-sided tape to produce a resistive touch panel having the configuration shown in FIGS. .
The drive electrode, the handling circuit, and the connection electrode in FIG. Preliminary drying, exposure, development, and drying steps were performed in order.
Next, an insulating resist (manufactured by Toyochem Co., Ltd., Rio Resist NSP-11) was printed on the drive electrode and the handling circuit by screen printing and dried at 120 ° C. for 30 minutes. The completed upper and lower electrode substrates were bonded with a double-sided tape to produce a resistive touch screen panel. Note that an insulating resist layer was not provided in order for the terminal portion of the extraction circuit to be terminals A and B (not shown).

About the obtained resistive film type touch screen panel, the resistance value between terminals A and B in FIG. 2 was measured in an environment of 25 ° C. and 50% humidity. Next, the resistance value between terminals after storage for 120 hours in an environment of 85 ° C. and 85% was measured in an environment of 25 ° C. and humidity of 50%, and the increase rate of the resistance value between terminals after the environmental storage test was as follows. Evaluation based on the criteria. The results are shown in Tables 1 and 2. In addition, the resistance value between terminals was measured using the Sanwa Denki Keiki PC500 type | mold tester.
○: Increase rate of resistance value between terminals after environmental preservation test is less than 10% △: Increase rate of resistance value between terminals after environment preservation test is 10% or more and less than 20% ×: Resistance value between terminals after environmental preservation test An increase rate of 20% or more The increase rate of the resistance value between terminals after the environmental preservation test is 20% or less, which is a practically acceptable level for a standard touch screen panel.

<Evaluation results>
The evaluation results of Examples 1 to 88 and Comparative Examples 1 to 8 are shown in Tables 3-1 to 3-14.
In addition, Examples 83, 84, 85, and 86 using the photosensitive resins obtained in Production Examples 9, 10, 18, and 19 are reference examples.

  From the evaluation results, it was found that the prior art (Comparative Examples 1 to 8) is not an ink having both physical properties such as adhesion, photolithographic characteristics, and resistance value change after heat and humidity resistance. On the other hand, it was found that the resin compositions (Examples 1 to 88) of the present invention were excellent in balance among the physical properties of adhesion, photolithographic properties, and resistance value change after heat and humidity resistance.

1: Lower substrate 2: Upper substrate 3: Conductive ink pattern layer 4: Insulating layer 5: Adhesive material (bonding)
6: Transparent electrode on the lower substrate 7: Transparent electrode on the upper substrate 8: Dot spacer 9, 10: Upper drive electrode 11, 12: Upper connection electrode 13, 14: Lower drive electrode 15, 16: Lower connection electrode 17: Handling circuit

Claims (11)

A photosensitive conductive ink containing a photosensitive resin (A), conductive particles (B) and a photopolymerization initiator (C),
The photosensitive resin (A) is
Epoxy compound having at least two epoxy groups in a molecule formed by a combination of a bisphenol type epoxy resin and polyethylene glycol diglycidyl ether and (a), a phenol compound having at least two phenolic hydroxyl groups in the molecule (B) is reacted to produce a resin (c) having a hydroxyl group in the side chain;
Reacting at least a part of the hydroxyl groups in the resin (c) having hydroxyl in the side chain with the polybasic acid anhydride (d) to produce a resin (e) having a carboxyl group in the side chain;
A part of the carboxyl group in the resin (e) having a carboxyl group in the side chain is reacted with the epoxy group or oxetane group in the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group. A photosensitive resin (A-1) having a carboxyl group and an ethylenically unsaturated group in the side chain,
A photosensitive conductive ink. A photosensitive conductive ink containing a photosensitive resin (A), conductive particles (B) and a photopolymerization initiator (C),
The photosensitive resin (A) is
Epoxy compound having at least two epoxy groups in a molecule formed by a combination of a bisphenol type epoxy resin and polyethylene glycol diglycidyl ether and (a), a phenol compound having at least two phenolic hydroxyl groups in the molecule (B) is reacted to produce a resin (c) having a hydroxyl group in the side chain;
Reacting at least part of the hydroxyl groups in the resin (c) having a hydroxyl group in the side chain with a polybasic acid anhydride (d) to produce a resin (e) having a carboxyl group in the side chain;
At least part of the carboxyl group in the resin (e) having a carboxyl group in the side chain; and the epoxy group or oxetane group in the compound (f) having an epoxy group or oxetane group and an ethylenically unsaturated group; To produce a resin (AA-1) having a hydroxyl group and an ethylenically unsaturated group in the side chain,
Further, at least a part of the hydroxyl group in the resin (AA-1) having a hydroxyl group and an ethylenically unsaturated group in the side chain is reacted with the acid anhydride group in the polybasic acid anhydride (g). It is a photosensitive resin (A-2) having a carboxyl group and an ethylenically unsaturated group in the side chain formed.
A photosensitive conductive ink.   The photosensitive conductive ink according to claim 1 or 2, wherein the acid value of the photosensitive resin (A) is 10 to 200 mgKOH / g.   The photosensitive conductive ink according to any one of claims 1 to 3, wherein the photosensitive resin (A) has an ethylenically unsaturated group equivalent of 200 to 5000 g / eq.   The photosensitive conductive ink according to any one of claims 1 to 4, wherein the photosensitive resin (A) has a weight average molecular weight of 1,000 to 100,000. Hardened | cured material formed by hardening | curing the photosensitive conductive ink in any one of Claims 1-5 . The laminated body with a conductive pattern which comprises a base material and the conductive pattern formed on the said base material, and the said conductive pattern is formed with the conductive ink of any one of Claims 1-5. . The laminated body with a conductive pattern according to claim 7 , further comprising an insulating layer laminated so as to cover the conductive pattern. The conductive pattern according to claim 7 , wherein another conductive film having a predetermined pattern electrically connected to the conductive pattern is further formed on the base material on a lower layer side of the conductive pattern. Laminated body. The laminated body with a conductive pattern according to claim 9 , wherein the other conductive film is a transparent conductive film mainly composed of indium oxide doped with tin. The laminated body with a conductive pattern of any one of Claims 7-10 used for a touch screen panel use.