JP6951312B2 - Composition for forming a layer to be plated, a substrate with a precursor layer to be plated, a substrate with a layer to be plated, a conductive film, a touch panel sensor, a touch panel - Google Patents

Description

The present invention relates to a composition for forming a layer to be plated, a substrate with a layer to be plated, a substrate with a layer to be plated, a conductive film, a touch panel sensor, and a touch panel.

A conductive film in which a metal layer (preferably a patterned metal layer) is arranged on a substrate is used for various purposes. For example, in recent years, as the mounting rate of touch panels on mobile phones or mobile game devices has increased, the demand for conductive films for capacitive touch sensors capable of detecting multiple points has rapidly increased.

Various methods for producing a conductive film have been proposed, and for example, a method using a plating treatment has been proposed. More specifically, in Patent Document 1, a resin obtained by curing a resin composition layer containing a polymerizable group, a resin having a functional group that interacts with a plating catalyst or a precursor thereof, and a polymerization initiator. A method is disclosed in which a layer (corresponding to the second resin layer of Patent Document 1) is used as a layer to be plated, and a metal layer is formed on the layer to be plated by a plating treatment.

Japanese Unexamined Patent Publication No. 2012-97296

On the other hand, recently, a conductive film having a three-dimensional shape is required.
For example, in order to further improve operability, a touch panel having a three-dimensional shape such as a curved surface is required, and a conductive film having a three-dimensional shape is used for the touch panel sensor included in such a touch panel.

The present inventor forms a resin layer (corresponding to the second resin layer of Patent Document 1) formed by curing the resin composition layer described in Patent Document 1, and deforms this resin layer into a three-dimensional shape. After that, a plating process was carried out to form a conductive film having a three-dimensional shape. However, the stretchability of the resin layer to be plated is not sufficient, and it is difficult to deform the resin layer into a desired shape.

In view of the above circumstances, it is an object of the present invention to provide a composition for forming a layer to be plated, which is excellent in stretchability and can form a layer to be plated on which a metal layer can be formed by a plating treatment.
Another object of the present invention is to provide a substrate with a precursor layer to be plated, a substrate with a layer to be plated, a conductive film, a touch panel sensor, and a touch panel.

As a result of diligent studies on the above problems, the present inventor has found that the above problems can be solved by using a composition having a predetermined formulation.
That is, the present inventor has found that the above problem can be solved by the following configuration.

[1] With at least one of the oxime ester-based polymerization initiator and the acylphosphine oxide-based polymerization initiator.
A polymer containing a double bond in the main chain and a functional group that interacts with the plating catalyst or its precursor.
A composition for forming a layer to be plated, which comprises a polyfunctional radically polymerizable monomer.
[2] The composition for forming a layer to be plated according to [1], wherein the functional group that interacts with the plating catalyst or its precursor is a carboxylic acid group.
[3] The composition for forming a layer to be plated according to [1] or [2], wherein the polymer contains a repeating unit derived from a conjugated diene compound and a repeating unit derived from an unsaturated carboxylic acid or a derivative thereof.
[4] The composition for forming a layer to be plated according to any one of [1] to [3], wherein the polyfunctional radically polymerizable monomer is a bifunctional acrylamide compound or a bifunctional methacrylamide compound.
[5] The composition for forming a layer to be plated according to any one of [1] to [4], wherein the polyfunctional radically polymerizable monomer is a compound represented by the formula (1) described later.
[6] A layer to be plated having a substrate and a layer to be plated, a precursor layer, which is arranged on the substrate and is formed from the composition for forming a layer to be plated according to any one of [1] to [5]. Substrate with precursor layer.
[7] A substrate with a layer to be plated, which is obtained by curing the precursor layer to be plated in the substrate with a layer to be plated according to [6], and has a substrate and a layer to be plated.
[8] The substrate with a layer to be plated according to [7], wherein the layers to be plated are arranged in a pattern.
[9] A conductive film comprising the substrate with a layer to be plated according to [7] or [8] and a metal layer arranged on the layer to be plated in the substrate with a layer to be plated.
[10] A touch panel sensor including the conductive film according to [9].
[11] A touch panel including the touch panel sensor according to [10].

According to the present invention, it is possible to provide a composition for forming a layer to be plated, which can form a metal layer on the metal layer by a plating treatment and has excellent stretchability.
Further, according to the present invention, it is possible to provide a substrate with a layer to be plated, a substrate with a layer to be plated, a conductive film, a touch panel sensor, and a touch panel.

It is a top view of the substrate which has a mesh-like layer to be plated. It is a perspective view of one Embodiment of the substrate with a layer to be plated which has a three-dimensional shape.

The present invention will be described in detail below.
The numerical range represented by using "~" in the present specification means a range including the numerical values before and after "~" as the lower limit value and the upper limit value. Further, the diagram in the present invention is a schematic diagram for facilitating the understanding of the invention, and the relationship between the thickness and the positional relationship of each layer does not necessarily match the actual one.

[Composition for forming a layer to be plated]
The composition for forming a layer to be plated of the present invention is
A functional group that contains at least one of the oxime ester-based polymerization initiator and the acylphosphine oxide-based polymerization initiator and has a double bond in the main chain and interacts with the plating catalyst or its precursor (hereinafter, "interactive group"). ”(Also also referred to as“ interacting polymer ”), and a polyfunctional radically polymerizable monomer.
With the above configuration, the layer to be plated formed from the composition for forming a layer to be plated of the present invention can form a metal layer on it by a plating treatment and is excellent in stretchability.
This is not clear in detail, but the present inventor speculates as follows.
The oxime ester-based polymerization initiator and the acylphosphine oxide-based polymerization initiator are relatively hydrophobic polymerization initiators. On the other hand, since the interacting group in the interacting polymer is relatively hydrophilic, the above-mentioned polymerization initiator is in the vicinity of the interacting group of the interacting polymer in the composition for forming the layer to be plated. It is presumed that it is unevenly distributed in the vicinity of the relatively hydrophobic double bond, avoiding.
Due to the above factors, in the composition for forming a layer to be plated, a polymerization reaction between an interactive polymer and a polyfunctional radical polymerizable monomer is likely to occur during polymerization, and further, interaction between interacting groups is likely to occur. Since the aggregation of the interacting polymer caused by the above is also suppressed, the glass transition temperature is unlikely to rise. As a result, it is considered that the layer to be plated formed from the composition for forming the layer to be plated of the present invention has a relatively low glass transition temperature (non-rigidity) and is excellent in stretchability.

[Polymerization initiator]
The composition for forming a layer to be plated contains at least one polymerization initiator of an oxime ester-based polymerization initiator and an acylphosphine oxide-based polymerization initiator. An oxime ester-based polymerization initiator is preferable because it is superior in sensitivity at the time of exposure. The oxime ester-based polymerization initiator and the acylphosphine oxide-based polymerization initiator will be described below.

<Oxime ester polymerization initiator>
The oxime ester-based polymerization initiator is intended to be a compound having an oxime ester structure in the molecule. The oxime ester-based polymerization initiator is not particularly limited, and a known oxime ester-based polymerization initiator can be used.
As a specific example of the oxime ester-based polymerization initiator, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-80068, or the compound described in JP-A-2006-342166 can be used.
Examples of the oxime ester-based polymerization initiator include 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) and 1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazole-3-yl] Etanone 1- (O-acetyloxime), 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxy Iminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-( 4-Toluenesulfonyloxy) iminobutane-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like can also be used.
Commercially available oxime ester-based polymerization initiators include IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), IRGACURE-OXE04 (manufactured by BASF), TR- PBG-304 (manufactured by Changshu Powerful Electronics New Materials Co., Ltd.), ADEKA Arkuru's NCI-831, ADEKA Arkuru's NCI-930 (manufactured by ADEKA), and N-1919 (Carbazole / oxime ester skeleton-containing photoinitiator (ADEKA)) , Etc., among which IRGACURE-OXE01 (manufactured by BASF) or IRGACURE-OXE02 (manufactured by BASF) is preferable.
The specific structures of IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are shown below in this order.

<Acylphosphine oxide-based polymerization initiator>
The acylphosphine oxide-based polymerization initiator is intended to be a compound having an acylphosphine oxide structure in the molecule, and also includes a bisacylosphineoxide compound. The acylphosphine oxide-based polymerization initiator is not particularly limited, and a known acylphosphine oxide-based polymerization initiator can be used.
Examples of the acylphosphine oxide-based compound include compounds described in JP-A-63-40799, JP-A-5-29234, JP-A-10-95788, JP-A-10-29997, and Patent No. 4225898. Can be mentioned.
Commercially available acylphosphine oxide-based polymerization initiators include Omnirad 819 (manufactured by IGM Resins VV; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide) and Omnirad TPO H (IGM Resins B.V.). V. made; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide).

As the polymerization initiator, a polymerization initiator having a ClogP of 5.00 or more is preferable, and a polymerization initiator having a ClogP of 6.00 or more is more preferable, in that the stretchability of the layer to be plated is more excellent. The upper limit is not particularly limited, and is, for example, 12.00 or less, preferably 9.00 or less.
ClogP of the above-mentioned polymerization initiator is described in ChemBio Drow Ultra ver. Of PerkinElmer. Represents a calculated value calculated using Chemproperty of 13.0. The larger the ClogP value, the higher the hydrophobicity.

Only one type of polymerization initiator may be used, or two or more types may be combined.
The content of the polymerization initiator in the composition for forming a layer to be plated (the total content thereof when a plurality of types are contained) is not particularly limited, but radical polymerization with the interactive polymer in the composition for forming a layer to be plated and polyfunctional radical polymerization. It is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on the total amount of the sex monomers.

[Polymer containing a double bond in the main chain and a functional group that interacts with the plating catalyst or its precursor (interactive polymer)]
The composition for forming a layer to be plated contains a polymer (interactive polymer) containing a double bond in the main chain and containing a functional group (interactive group) that interacts with the plating catalyst or a precursor thereof.

The form in which the interacting polymer contains a double bond in the main chain is not particularly limited, and examples thereof include a form containing a repeating unit derived from a conjugated diene compound.

The conjugated diene compound is not particularly limited as long as it is a compound having a molecular structure having two carbon-carbon double bonds separated by one single bond.
Examples of the conjugated diene compound include isoprene, 1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 1,3-hexadiene, 1,3-heptadiene, 2,4-heptadiene, and 1,3-. Octadien, 2,4-octadien, 3,5-octadien, 1,3-nonadien, 2,4-nonadien, 3,5-nonadien, 1,3-decadien, 2,4-decadien, 3,5-decadien, 2,3-Dimethyl-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-phenyl-1,3-butadiene, 2- Phenyl-1,3-pentadiene, 3-phenyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2-hexyl-1,3-butadiene, Examples thereof include 3-methyl-1,3-hexadiene, 2-benzyl-1,3-butadiene, 2-p-tolyl-1,3-butadiene and the like.

Among them, the repeating unit derived from the conjugated diene compound is a repeating unit derived from a compound having a butadiene skeleton represented by the formula (X1) because it is easy to synthesize an interactive polymer and the characteristics of the layer to be plated are more excellent. Is preferable.

Wherein (X1), _{R a} each independently represent a hydrogen atom, a halogen atom, or a hydrocarbon group. Examples of the hydrocarbon group include an aliphatic hydrocarbon group (for example, an alkyl group and an alkenyl group, preferably having 1 to 12 carbon atoms), and an aromatic hydrocarbon group (for example, a phenyl group and a naphthyl group). Etc.). A plurality of _Ras may be the same or different.

Examples of the compound having a butadiene skeleton represented by the formula (X1) (monomer having a butadiene structure) include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, and 2-n-propyl. -1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1-phenyl-1,3-butadiene, 1-α-naphthyl-1,3-butadiene, 1-β-naphthyl-1,3 -Butadiene, 2-chloro-1,3-butadiene, 1-brom-1,3-butadiene, 1-chlorobutadiene, 2-fluoro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, Examples thereof include 1,1,2-trichloro-1,3-butadiene, 2-cyano-1,3-butadiene and the like.

The content of the repeating unit derived from the conjugated diene compound in the interacting polymer is not particularly limited, but 1 to 90 mol% with respect to all the repeating units in terms of the balance between the stretchability and the plating precipitation property of the layer to be plated. Is preferable, and 10 to 90 mol% is more preferable.

The interacting group is intended to be a functional group capable of interacting with the plating catalyst or its precursor applied to the layer to be plated, and for example, a functional group capable of forming an electrostatic interaction with the plating catalyst or its precursor. Further, a nitrogen-containing functional group, a sulfur-containing functional group, and an oxygen-containing functional group capable of coordinating with the plating catalyst or its precursor can be mentioned.
Examples of the interacting group include an amino group, an amide group, an imide group, a urea group, a tertiary amino group, an ammonium group, an amidino group, a triazine group, a triazole group, a benzotriazole group, an imidazole group, and a benzimidazole group. Includes quinoline group, pyridine group, pyrimidine group, pyrazine group, quinazoline group, quinoxalin group, purine group, triazine group, piperidine group, piperazine group, pyrrolidine group, pyrazole group, aniline group, group containing alkylamine structure, isocyanul structure. Nitrogen-containing functional groups such as groups, nitro groups, nitroso groups, azo groups, diazo groups, azido groups, cyano groups, and cyanate groups; ether groups, hydroxyl groups, phenolic hydroxyl groups, carboxylic acid groups, carbonate groups, carbonyl groups, esters Oxygen-containing functional groups such as groups, groups containing N-oxide structure, groups containing S-oxide structure, and groups containing N-hydroxy structure; thiophene group, thiol group, thiourea group, thiocyanuric acid group, benzthiazole group, Includes mercaptotriazine group, thioether group, thioxy group, sulfoxide group, sulfone group, sulfite group, group containing sulfoxyimine structure, group containing sulfoxynium salt structure, sulfonic acid group, group containing sulfonic acid ester structure, etc. Sulfur functional group; phosphorus-containing functional group such as phosphate group, phosphoramide group, phosphine group, and group containing phosphoric acid ester structure; group containing halogen atom such as chlorine atom and bromine atom, and salt structure. These salts can also be used in functional groups capable of taking.
Among them, an ionic polar group such as a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a boronic acid group, or a cyano group is used because of its high polarity and high adsorption ability to a plating catalyst or its precursor. Preferably, a carboxylic acid group or a cyano group is more preferable, and a carboxylic acid group is further preferable in that it is more excellent in plating precipitation property.
The interacting polymer may have two or more interacting groups.

It is preferable that the interacting polymer contains a repeating unit having an interacting group.
One preferred embodiment of the repeating unit having an interacting group is a repeating unit represented by the formula (Y1).

In formula (Y1), R _b represents a hydrogen atom or an alkyl group (for example, a methyl group and an ethyl group).
L _a represents a single bond or a divalent linking group.
The type of the divalent linking group is not particularly limited, and may be, for example, a divalent hydrocarbon group (a divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group). The saturated hydrocarbon group of No. may be linear, branched, or cyclic, and preferably has 1 to 20 carbon atoms, and examples thereof include an alkylene group and a divalent aromatic hydrocarbon. The group preferably has 5 to 20 carbon atoms, and examples thereof include a phenylene group. In addition, an alkenylene group or an alkynylene group may be used.) Divalent heterocyclic group, -O-, -S. −, −SO ₂ −, −NR ₁₀ −, −CO− (−C (= O) −), −COO− (−C (= O) O−), −NR ₁₀ −CO−, −CO−NR _{Examples thereof include 10} −, −SO ₃₋ , −SO ₂ NR ₁₀ −, and groups in which two or more of these are combined. Here, R ₁₀ represents a hydrogen atom or an alkyl group (preferably having 1 to 10 carbon atoms).
The hydrogen atom in the divalent linking group may be substituted with another substituent such as a halogen atom.

X represents an interacting group. The definition of the interacting group is as described above.

Another preferred embodiment of the repeating unit having an interacting group is a repeating unit derived from an unsaturated carboxylic acid or a derivative thereof.
The unsaturated carboxylic acid is an unsaturated compound having a carboxylic acid group (-COOH group). Examples of the unsaturated carboxylic acid derivative include an anhydride of the unsaturated carboxylic acid, a salt of the unsaturated carboxylic acid, and a monoester of the unsaturated carboxylic acid.
Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid.

The content of the repeating unit having an interacting group in the interacting polymer is not particularly limited, but 1 to 90 mol with respect to all the repeating units in terms of the balance between the stretchability of the layer to be plated and the plating precipitation property. %, More preferably 10 to 90 mol%.

The weight average molecular weight of the interacting polymer is not particularly limited, but is preferably 1,000 to 700,000, more preferably 2,000 to 200,000 in terms of better handleability.

Preferable embodiments of the interactive polymer are a repeating unit derived from a conjugated diene compound and an unsaturated carboxylic acid or a derivative thereof, in that a layer to be plated is easily formed with a small amount of energy applied (for example, an exposure amount). Polymer X having a repeating unit can be mentioned.
The description of the repeating unit derived from the conjugated diene compound is as described above.
Further, the description of the repeating unit derived from the unsaturated carboxylic acid or its derivative is as described above.

The content of the repeating unit derived from the conjugated diene compound in the polymer X is preferably 25 to 75 mol% with respect to all the repeating units.
The content of the repeating unit derived from the unsaturated carboxylic acid or its derivative in the polymer X is preferably 25 to 75 mol% with respect to all the repeating units.

Only one type of interacting polymer may be used, or two or more types may be combined.
The content of the interacting polymer in the composition for forming the layer to be plated (the total content when a plurality of types are contained) is not particularly limited, and is often 10 to 90% by mass with respect to the total solid content. From the point that the tackiness of the precursor layer to be plated, which will be described later, is further suppressed, 15 to 85% by mass is preferable with respect to the total solid content, and the balance between the stretchability of the layer to be plated and the plating precipitation property is more excellent. In terms of points, 25 to 80% by mass is more preferable, and 35 to 80% by mass is further preferable.
In the present specification, the solid content is intended to be a component constituting the layer to be plated, and does not include a solvent. As long as it is a component constituting the layer to be plated, it is included in the solid content even if the property is liquid.

The ratio of the mass of the interacting polymer to the mass of the polyfunctional radically polymerizable monomer described later (mass of the interacting polymer / mass of the polyfunctional radically polymerizable monomer) is not particularly limited and is 0.1 to 10 However, in that the tackiness of the precursor layer to be polymerized is more suppressed, more than 0.25 is preferable, more than 0.25 is more preferable, and the stretchability and plating precipitation property of the layer to be polymerized are more preferable. 0.3 to 4 is more preferable in that the balance with the above is more excellent.

[Polyfunctional radically polymerizable monomer]
The composition for forming a layer to be plated contains a polyfunctional radically polymerizable monomer.
The polyfunctional radically polymerizable monomer is intended to be a compound having two or more radically polymerizable groups.
The number of radically polymerizable groups in the polyfunctional radically polymerizable monomer is not particularly limited, but is preferably 2 to 10, more preferably 2 to 5, and even more preferably 2.

The radically polymerizable group is not particularly limited, and examples thereof include an acryloyloxy group, a methacryloyloxy group, an acrylamide group, a methacrylicamide group, a vinyl group, and a styryl group, and examples thereof include an acryloyloxy group, a methacryloyloxy group, and an acrylamide group. Alternatively, a methacrylicamide group is preferable, and an acrylamide group or a methacrylicamide group is more preferable in that it is more excellent in alkali developability.
Here, the acryloyloxy group is a group represented by the following formula (A), the methacryloyloxy group is a group represented by the following formula (B), and the acrylamide group is a group represented by the following formula (C). The methacrylamide group is a group represented by the following formula (D).
In formulas (A) to (D), * represents a coupling position.
In formulas (C) and (D), R represents a hydrogen atom or a substituent. The type of the substituent is not particularly limited, and a known substituent (for example, an aliphatic hydrocarbon group (for example, an alkyl group) which may contain a heteroatom), an aromatic hydrocarbon group (for example, an aryl group, etc.) and the like can be used. Can be mentioned.) Can be mentioned. As R, a hydrogen atom is preferable.

The polyfunctional radically polymerizable monomer preferably has a polyoxyalkylene group.
The polyoxyalkylene group is a group having an oxyalkylene group as a repeating unit. As the polyoxyalkylene group, the group represented by the formula (E) is preferable.
Equation (E)-(A-O) _m-
A represents an alkylene group. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 4 is preferable, and 2 to 3 is more preferable. For example, when A is an alkylene group having 1 carbon atom, − (A—O) − is an oxymethylene group (−CH ₂ O−), and when A is an alkylene group having 2 carbon atoms, − (A—O). -Is an oxyethylene group (-CH ₂ CH ₂ O-), and when A is an alkylene group having 3 carbon atoms,-(A-O)-is an oxypropylene group (-CH ₂ CH (CH ₃ ) O-, -CH (CH ₃ ) CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-) is shown. The alkylene group may be linear or branched.

m represents the number of repetitions of the oxyalkylene group and represents an integer of 2 or more. The number of repetitions is not particularly limited, but among them, 2 to 10 is preferable, and 2 to 6 is more preferable.
The carbon number of the alkylene group in the plurality of oxyalkylene groups may be the same or different. For example, in the formula (E), a plurality of repeating units represented by − (A—O) − are included, and the number of carbon atoms in the alkylene group in each repeating unit is the same but different. May be good. For example, at − (A—O) _m −, an oxymethylene group and an oxypropylene group may be contained.
When a plurality of types of oxyalkylene groups are contained, the bonding order thereof is not particularly limited, and may be a random type or a block type.

Among them, a bifunctional acrylamide compound or a bifunctional methacrylamide compound is preferable as the polyfunctional radically polymerizable monomer in that the stretchability of the layer to be plated is more excellent, and the compound represented by the formula (1) is preferable. More preferred.

In formula (1), R ₁ and R ₂ independently represent a hydrogen atom or a methyl group, respectively.
The definitions of A and m are the same as the definitions of A and m in the above formula (E).

R ₃ and R ₄ represent a hydrogen atom or a substituent.
The types of substituents represented by R ₃ and R ₄ are synonymous with the substituents represented by R in the above-mentioned formulas (C) and (D), and the preferred embodiments are also the same.
Of these, hydrogen atoms are preferable as _{R 3} and R _4.

L ₁ and L ₂ each independently represent a single bond or a divalent linking group.
The divalent types of linking groups represented by L ₁ and L _2, has the same meaning as the divalent linking group represented by L _a in the above-mentioned formula (Y1), preferred embodiments are also the same.

Various commercially available products can be used as the above-mentioned polyfunctional radically polymerizable monomer, and the polyfunctional radical-polymerizable monomer can be synthesized by the method described in Japanese Patent Application Laid-Open No. 2013-502654. Examples of commercially available products of the compound represented by the above formula (1) include FAM-201 (manufactured by FUJIFILM Corporation) and the like.

Only one type of the polyfunctional radically polymerizable monomer may be used, or two or more types may be combined.
The content of the polyfunctional radically polymerizable monomer in the composition for forming the layer to be plated (the total content when a plurality of types are contained) is not particularly limited, and may be 10 to 90% by mass with respect to the total solid content. Although there are many, 15 to 85 mass is preferable with respect to the total solid content in that the tackiness of the precursor layer to be plated, which will be described later, is more suppressed, and the balance between the stretchability of the layer to be plated and the plating precipitation property is balanced. In terms of superiority, 15 to 75% by mass is more preferable, and 15 to 65% by mass is further preferable.

[Arbitrary component]
The composition for forming a layer to be plated may contain components other than the above-mentioned polymerization initiator, interacting polymer, and polyfunctional radical polymerizable monomer. Hereinafter, the optional components will be described in detail.

<Surfactant>
The composition for forming a layer to be plated may contain a surfactant.
The type of the surfactant is not particularly limited, and examples thereof include a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant. Among them, a fluorine-based surfactant or a silicone-based surfactant is preferable, and a fluorine-based surfactant is more preferable, in that the tackiness of the precursor layer to be plated is further suppressed.
Only one type of surfactant may be used, or two or more types may be combined.

Examples of the fluorine-based surfactant include W-AHE, W-AHI (manufactured by FUJIFILM Corporation), Megafuck F171, F172, F173, F176, F177, F141, and F142. F143, F144, R30, F437, F475, F479, F482, F554, F569, F780, F781F (all manufactured by DIC Co., Ltd.), Florard FC430, FC431, FC171. (Above, manufactured by Sumitomo 3M Co., Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, SC Examples thereof include S393, KH-40 (manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA) and the like.

The content of the surfactant in the composition for forming the layer to be plated (the total content thereof when a plurality of types are contained) is not particularly limited, but is 0.005 to 100% by mass based on 100% by mass of the composition for forming the layer to be plated. 0.5% by mass is preferable, 0.01 to 0.2% by mass is more preferable, and 0.01 to 0.1% by mass is further preferable.

<Solvent>
The composition for forming the layer to be plated may contain a solvent.
The type of solvent is not particularly limited, and examples thereof include water and organic solvents. Examples of the organic solvent include known organic solvents (for example, alcohol-based solvent, ester-based solvent, ketone-based solvent, halogen-based solvent, hydrocarbon-based solvent, etc.).

The composition for forming a layer to be plated may contain other components (for example, a sensitizer, a curing agent, a polymerization inhibitor, an antioxidant, an antioxidant, a filler, a flame retardant, a lubricant, a plasticizer, or a plasticizer, if necessary. It may contain a plating catalyst or a precursor thereof).

The method for producing the composition for forming the layer to be plated is not particularly limited, and known methods can be mentioned. For example, a method of mixing each of the above-mentioned components at once, a method of mixing each component step by step, and the like can be mentioned.

[Layer to be plated and its manufacturing method]
The layer to be plated can be formed by using the composition for forming the layer to be plated described above. The layer to be plated is a layer to which a plating treatment described later is performed, and a metal layer is formed on the surface of the layer by the plating treatment.
As a method for producing the layer to be plated, a method having the following steps is preferable.
Step 1: The substrate and the composition for forming the layer to be plated are brought into contact with each other to form the precursor layer of the layer to be plated on the substrate. Step 2: The precursor layer of the layer to be plated is cured to form the layer to be plated. Steps for Forming The above steps 1 and 2 will be described in detail below.

Step 1 is a step of bringing the substrate into contact with the composition for forming a layer to be plated to form a layer to be plated precursor layer on the substrate.
The layer to be plated is a layer in an uncured state before being cured.
The type of substrate used is not particularly limited, and examples thereof include known substrates (for example, resin substrates, glass substrates, ceramic substrates, and the like). Of these, a resin substrate is preferable because it has excellent stretchability.

The thickness of the substrate is not particularly limited, but is preferably 0.05 to 2 mm, more preferably 0.1 to 1 mm, from the viewpoint of balance between handleability and thinning.
Further, it is preferable that the substrate appropriately transmits light. Specifically, the total light transmittance of the substrate is preferably 85 to 100%.

Further, the substrate may have a multi-layer structure, and for example, a functional film may be included as one layer thereof. The substrate itself may be a functional film. Although not particularly limited, examples of functional films include polarizing plates, retardation films, cover plastics, hard coat films, barrier films, adhesive films, electromagnetic wave shielding films, heat generating films, antenna films, and wiring for devices other than touch panels. Examples include films.

If necessary, a primer layer for improving the adhesion between the layer to be plated and the substrate may be arranged on the substrate. The film-forming component forming the primer layer is not particularly limited, but a urethane-based resin is preferable.

The method of contacting the substrate with the composition for forming the layer to be plated is not particularly limited, and for example, a method of applying the composition for forming the layer to be plated onto the substrate and a method of applying the substrate to the composition for forming the layer to be plated A method of dipping can be mentioned.
After the substrate is brought into contact with the composition for forming the layer to be plated, a drying treatment may be carried out in order to remove the solvent from the precursor layer of the layer to be plated, if necessary.

By the above method, the layer to be plated precursor layer formed from the composition for forming the layer to be plated is arranged on the substrate. That is, a substrate with a layer to be plated precursor layer having a substrate and a layer to be plated precursor layer arranged on the substrate can be obtained.

The average thickness of the precursor layer to be plated is not particularly limited, but 50 nm or more is preferable, and 100 nm or more is more preferable, because it is easy to support the plating catalyst or its precursor in a more sufficient amount. On the other hand, the upper limit is preferably 2 μm or less, more preferably 1.5 μm or less, in that the patterning property is more excellent and plating abnormalities due to excessive activity can be further suppressed.
The average thickness is an average value obtained by observing the vertical cross section of the precursor layer to be plated with an electron microscope (for example, a scanning electron microscope), measuring the thickness of any 10 points, and arithmetically averaging them. be.

Step 2 is a step of applying a curing treatment to the precursor layer of the layer to be plated to form the layer to be plated.
The curing treatment method is not particularly limited, and examples thereof include heat treatment and exposure treatment (light irradiation treatment). Of these, the exposure treatment is preferable because the treatment can be completed in a short time. The curing treatment activates the polymerizable group contained in the compound in the precursor layer of the layer to be plated, causes cross-linking between the compounds, and the curing of the layer proceeds.
When the above-mentioned curing treatment (particularly, exposure treatment) is carried out, the curing treatment may be performed in a pattern so as to obtain a desired patterned layer to be plated. For example, it is preferable to perform the exposure treatment using a mask having an opening having a predetermined shape. A patterned layer to be plated is formed by subjecting the precursor layer to be plated, which has been cured in a pattern, to a developing treatment.
The method of development processing is not particularly limited, and optimum development processing is carried out according to the type of material used. Examples of the developing solution include an organic solvent, pure water, and an alkaline aqueous solution.

By the above method, the layer to be plated obtained by curing the composition for forming the layer to be plated is arranged on the substrate. That is, a substrate with a layer to be plated having a substrate and a layer to be plated arranged on the substrate can be obtained.

The average thickness of the layer to be plated is not particularly limited, but is preferably 50 nm or more, more preferably 100 nm or more, in that a plating catalyst or a precursor thereof can be easily supported in a more sufficient amount. On the other hand, the upper limit is preferably 2 μm or less, more preferably 1.5 μm or less, in that the patterning property is more excellent and plating abnormalities due to excessive activity can be further suppressed.
The average thickness is an average value obtained by observing the vertical cross section of the precursor layer to be plated with an electron microscope (for example, a scanning electron microscope), measuring the thickness of any 10 points, and arithmetically averaging them. be.

The layer to be plated may be formed in a pattern. For example, the layer to be plated may be formed in a mesh shape. In FIG. 1, a mesh-shaped layer to be plated 12 is arranged on the substrate 10.
The size of the line width W of the thin wire portion constituting the mesh of the layer to be plated 12 is not particularly limited, but is 30 μm or less in terms of the balance between the conductive characteristics of the metal layer formed on the layer to be plated and the difficulty of visibility. Is preferable, 15 μm or less is more preferable, 10 μm or less is further preferable, 5 μm or less is particularly preferable, 0.5 μm or more is preferable, and 1.0 μm or more is more preferable.

In FIG. 1, the opening 14 has a substantially rhombic shape, but is not limited to this shape, and may be another polygonal shape (for example, a triangle, a quadrangle, a hexagon, or a random polygon). Further, the shape of one side may be a linear shape, a curved shape, or an arc shape. In the case of arcuate shape, for example, the two opposing sides may have an arcuate shape that is convex outward, and the other two opposite sides may have an arcuate shape that is convex inward. Further, the shape of each side may be a wavy line shape in which an arc convex outward and an arc convex inward are continuous. Of course, the shape of each side may be a sine curve.

The length L of one side of the opening 14 is not particularly limited, but is preferably 1500 μm or less, more preferably 1300 μm or less, further preferably 1000 μm or less, more preferably 5 μm or more, more preferably 30 μm or more, still more preferably 80 μm or more. When the length of one side of the opening is within the above range, the transparency of the conductive film described later is more excellent.

The substrate with a layer to be plated may be deformed to obtain a substrate with a layer to be plated having a three-dimensional shape. That is, by deforming the above-mentioned substrate with a layer to be plated, a substrate having a three-dimensional shape and a layer to be plated (or a patterned layer to be plated) arranged on the substrate are attached. A substrate (a substrate with a layer to be plated having a three-dimensional shape) can be obtained.
As described above, the layer to be plated obtained by curing the composition for forming the layer to be plated has excellent stretchability, and its shape can be changed by following the deformation of the substrate.
The method of deforming the substrate with the layer to be plated is not particularly limited, and examples thereof include known methods such as vacuum forming, blow molding, free blow molding, vacuum forming, vacuum-press air forming, and hot press forming.
For example, as shown in FIG. 2, a part of the substrate with a layer to be plated may be deformed into a hemispherical shape to obtain a substrate 20 with a layer to be plated having a hemispherical shape. In FIG. 2, the layer to be plated is not shown.
Although the mode of imparting the three-dimensional shape has been described above, the shape may be deformed by applying a stretching treatment such as uniaxial stretching or biaxial stretching to the substrate with the layer to be plated.

Although the mode of deforming the substrate with the layer to be plated has been described above, the present invention is not limited to this mode, and the above-mentioned step 2 is carried out after the above-mentioned substrate with the layer to be plated is deformed. A substrate with a layer to be plated having a three-dimensional shape may be obtained.
Further, although the embodiment in which the precursor layer to be plated is subjected to a pattern-like curing treatment to form a patterned layer to be plated has been described above, the present invention is not limited to this embodiment, and the pattern is formed on the substrate. A patterned layer to be plated can also be formed by arranging a precursor layer to be plated and subjecting the patterned layer to be plated to a curing treatment. Examples of the method of arranging the precursor layer of the layer to be plated in a pattern include a method of applying the composition for forming the layer to be plated to a predetermined position on the substrate by a screen printing method or an inkjet method.

[Conductive film and its manufacturing method]
A metal layer can be formed on the layer to be plated by subjecting the layer to be plated in the substrate with the layer to be plated described above to a plating treatment. In particular, when the layers to be plated are arranged in a pattern on the substrate, a metal layer (patterned metal layer) is formed along the pattern.
The method for forming the metal layer is not particularly limited, and for example, the step 3 of applying the plating catalyst or its precursor to the layer to be plated and the plating treatment on the layer to be plated to which the plating catalyst or its precursor is applied are performed. It is preferable to carry out the step 4.
Hereinafter, the procedures of steps 3 and 4 will be described in detail.

Step 3 is a step of applying a plating catalyst or a precursor thereof to the layer to be plated. Since the layer to be plated contains the above-mentioned interacting group, the interacting group adheres (adsorbs) the applied plating catalyst or its precursor according to its function.
The plating catalyst or its precursor functions as a catalyst or electrode for the plating process. Therefore, the type of plating catalyst or precursor thereof to be used is appropriately determined depending on the type of plating treatment.

The plating catalyst or its precursor is preferably an electroless plating catalyst or a precursor thereof.
The electroless plating catalyst is not particularly limited as long as it is an active nucleus during electroless plating, and is known as, for example, a metal having a catalytic ability for a self-catalytic reduction reaction (a metal capable of electroless plating having a lower ionization tendency than Ni). What can be done). Specific examples thereof include Pd, Ag, Cu, Pt, Au, and Co.
A metal colloid may be used as the electroless plating catalyst.
The electroless plating catalyst precursor is not particularly limited as long as it becomes an electroless plating catalyst by a chemical reaction, and examples thereof include metal ions mentioned as the electroless plating catalyst.

As a method of applying the plating catalyst or its precursor to the layer to be plated, for example, a method of preparing a solution in which the plating catalyst or its precursor is dispersed or dissolved in a solvent and applying the solution on the layer to be plated. Alternatively, a method of immersing the substrate with the layer to be plated in the solution can be mentioned.
Examples of the solvent include water and an organic solvent.

Step 4 is a step of performing a plating treatment on the layer to be plated to which the plating catalyst or a precursor thereof is applied.
The method of plating treatment is not particularly limited, and examples thereof include electroless plating treatment and electrolytic plating treatment (electroplating treatment). In this step, the electroless plating treatment may be carried out alone, or the electroless plating treatment may be carried out and then the electrolytic plating treatment may be further carried out.
Hereinafter, the procedure of the electroless plating treatment and the electrolytic plating treatment will be described in detail.

The electroless plating treatment is a treatment for precipitating a metal by a chemical reaction using a solution in which a metal ion to be precipitated as plating is dissolved.
As a procedure for the electroless plating treatment, for example, it is preferable to wash the substrate with the layer to be plated to which the electroless plating catalyst is applied with water to remove excess electroless plating catalyst, and then immerse the substrate in the electroless plating bath. .. As the electroless plating bath used, a known electroless plating bath can be used.
In addition to the solvent (for example, water), the general electroless plating bath mainly contains a metal ion for plating, a reducing agent, and an additive (stabilizer) for improving the stability of the metal ion. Is done.

When the plating catalyst or its precursor applied to the layer to be plated has a function as an electrode, the electroplating treatment can be applied to the layer to be plated to which the catalyst or its precursor is applied.
As described above, after the electroless plating treatment, if necessary, an electrolytic plating treatment can be performed. In such a form, the thickness of the formed metal layer can be adjusted as appropriate.

Although the embodiment in which the step 3 is carried out has been described above, the step 3 may not be carried out when the plating catalyst or a precursor thereof is contained in the layer to be plated.

By carrying out the above treatment, a metal layer is formed on the layer to be plated. That is, a conductive film including a substrate with a layer to be plated and a metal layer arranged on the layer to be plated in the substrate with a layer to be plated can be obtained.
By arranging the patterned metal layer to be plated on the substrate according to the shape of the patterned metal layer to be formed, a conductive film having the patterned metal layer having a desired shape can be obtained. For example, when it is desired to obtain a mesh-shaped metal layer, a mesh-shaped layer to be plated may be formed.
Further, when the steps 3 and 4 are carried out using a substrate with a layer to be plated having a three-dimensional shape, a conductive film having a three-dimensional shape can be obtained.

The conductive film obtained by the above procedure (particularly, the conductive film having a three-dimensional shape) can be applied to various uses. For example, it can be applied to various applications such as touch panel sensors, semiconductor chips, FPCs (Flexible printed circuits), COFs (Chips on Film), TABs (Tape Automated Bonding), antennas, multilayer wiring boards, and motherboards. Above all, it is preferable to use it for a touch panel sensor (particularly, a capacitive touch panel sensor). When the conductive film is applied to the touch panel sensor, the patterned metal layer functions as a detection electrode or a lead-out wiring in the touch panel sensor. Such a touch panel sensor can be suitably applied to a touch panel.
The conductive film can also be used as a heating element. For example, by passing an electric current through the patterned metal layer, the temperature of the patterned metal layer rises, and the patterned metal layer functions as a thermal electric wire.

The wiring pattern of the three-dimensional shape portion of the conductive film having the three-dimensional shape is deformed as compared with that before molding, and the substrate is thin. As a result, when a conductive film having a patterned metal layer on both sides and having a three-dimensional shape is used as the touch panel sensor, the ΔCm value of the portion where the area of the patterned metal layer, which is the wiring pattern, is expanded is small. Therefore, the ΔCm value increases where the substrate becomes thinner.
Therefore, in the present invention, the above problems can be dealt with by individually setting the range of ΔCm for each address.
In addition to the above-mentioned corresponding methods, for example, in consideration of the degree of deformation of the patterned metal layer during molding, the pattern shape in the state before molding so that the ΔCm value after molding is substantially constant in the plane. Another method is to adjust the arrangement position of the metal layer.
Further, by changing the thickness of the cover film laminated on the patterned metal layer in the conductive film having a three-dimensional shape, the ΔCm value can be made substantially constant in the plane.
It should be noted that these methods can also be used in combination.

Insert molding may be used to enhance the self-supporting property of the conductive film having a three-dimensional shape. For example, a conductive film having a three-dimensional shape may be arranged in a mold, the resin may be filled in the mold, and a resin layer may be laminated on the conductive film. Further, after imparting a three-dimensional shape to the substrate with the layer to be plated before the plating treatment, the substrate with the layer to be plated having the three-dimensional shape is arranged in the mold and the resin is filled in the mold to obtain the result. A conductive film having excellent self-supporting property may be produced by subjecting the laminated body to a plating treatment.

When decorating a conductive film having a three-dimensional shape, for example, the decorative film may be molded and attached to the conductive film having a three-dimensional shape. Specifically, TOM (Three dimension Overlay Method) molding can be used.
Further, the conductive film having a three-dimensional shape may be directly coated and decorated.
Further, the decorative layer may be arranged on the front surface and / or the back surface of the substrate before forming the precursor layer to be plated. Further, when the layer to be plated precursor layer is arranged on one surface of the substrate, the decorative layer may be formed on the other surface of the substrate, or the decorative film may be bonded.
Further, the conductive film having a three-dimensional shape may be decorated by in-mold molding or insert molding using a decorative film.

Hereinafter, the present invention will be described in more detail based on Examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.

[Example 1]
[Preparation of composition for forming primer layer]
The following components were mixed to obtain a composition for forming a primer layer.
Z913-3 (manufactured by Aica Kogyo Co., Ltd.) 33% by mass
IPA (isopropanol) 67% by mass
[Preparation of Composition A for Forming Layer to be Plated]
The following components were mixed to obtain a composition A for forming a layer to be plated.
Isopropanol 38 parts by mass Polybutadiene maleic acid (butadiene-maleic acid alternating copolymer, repeating unit derived from butadiene: repeating unit derived from maleic acid = 1: 1 (molar ratio), manufactured by Polysciences)
4 parts by mass FAM-201 (manufactured by FUJIFILM Corporation, corresponds to a bifunctional acrylamide compound)
1 part by mass IRGACURE-OXE02 (manufactured by BASF, corresponding to oxime ester-based polymerization initiator, ClogP: 6.55) 0.05 part by mass

[Preparation of substrate with precursor layer to be plated]
A composition for forming a primer layer was bar-coated on one surface of a substrate (PC (polycarbonate) film manufactured by Teijin, Panlite PC, thickness: 250 μm) and dried at 80 ° C. for 3 minutes. Then, the formed composition layer for forming a primer layer was irradiated with UV (ultraviolet rays) at an irradiation amount of 1000 mJ to form a primer layer (thickness 0.8 μm).
Next, the composition A for forming the layer to be plated was bar-coated on the primer layer so as to have a film thickness of 0.2 μm and dried at 120 ° C. for 1 minute to obtain a substrate with a precursor layer to be plated. .. Then, immediately, a polypropylene film (protective film) having a thickness of 12 μm was attached to the surface of the precursor layer to be plated.

[Manufacturing a patterned substrate with a layer to be plated]
Next, with respect to the substrate with the precursor layer to be plated with the protective film, through a mask having a mesh-like opening pattern in which the width of the thin line portion is 4 μm and the length of a piece of the opening is 150 μm. UV irradiation was performed ^{at 30 mJ / cm 2} with a high-pressure mercury lamp.
After UV irradiation, the protective film was peeled off from the substrate with the precursor layer to be plated. Next, the exposed substrate with the precursor layer to be plated is shower-washed with an aqueous sodium carbonate solution (1% by mass) and subjected to alkali development treatment after the protective film has been peeled off. To obtain a patterned substrate with a layer to be plated. The thickness of the layer to be plated was 0.2 μm. The patterned substrate with a layer to be plated (that is, the one before hemispherical molding) obtained here was used in the stretchability evaluation described later.

Next, the mold having the hemispherical recess was heated for 1 hour or more in an oven whose temperature was adjusted to 180 ° C. After the temperature of the mold was raised to 180 ° C., the mold was taken out of the oven, and a substrate with a patterned layer to be plated was attached to the mold using heat-resistant tape so as to cover the openings of the recesses. The mold was quickly returned to the oven, left for 30 seconds, and then vacuum sucked from the air hole at the bottom of the hemispherical recess for 5 seconds to obtain a substrate with a hemispherical shape and a layer to be plated. (See FIG. 2).

[Manufacturing of conductive film]
Next, the Pd catalyst-imparting liquid Omnishield 1573 Activator (Rome & Haas Electronic Materials Co., Ltd.) was diluted with pure water to 3.6% by volume, and the pH was adjusted to 4.0 with 0.1N HCl. The hemispherical substrate with the layer to be plated was immersed in the prepared aqueous solution at 45 ° C. for 5 minutes, and then washed twice with pure water. Next, the hemispherical substrate with a layer to be plated is immersed in a 0.8% by volume aqueous solution of a reducing agent Circuposit PB oxide converter 60C (manufactured by Rohm & Haas Electronic Materials Co., Ltd.) at 30 ° C. for 5 minutes. Then, it was washed twice with pure water. Then, the hemispherical substrate with the layer to be plated is mixed with 12% by volume of M agent, 6% by volume of A agent, and 10% by volume of B agent of Circuposit 4500 (manufactured by Rohm & Haas Electronic Materials Co., Ltd.). The electroless plating solution was immersed in a bath at 45 ° C. for 15 minutes and washed with pure water to form a patterned metal layer to obtain a conductive film having a hemispherical curved surface.

[Example 2]
Examples except that the type of polymerization initiator was changed from IRGACURE-OXE02 to IRGACURE-OXE01 (manufactured by BASF, which corresponds to an oxime ester-based polymerization initiator, ClogP: 8.50) and the exposure amount was 50 mJ / cm ^2. The conductive film of Example 2 was produced by the same method as in 1.

[Example 3]
The type of polymerization initiator was changed from IRGACURE-OXE02 to Omnirad 819 (manufactured by IGM Resins BV, corresponding to acylphosphine oxide-based polymerization initiator, ClogP: 6.69), and the exposure amount was 100 mJ / cm ² . The conductive film of Example 3 was produced by the same method as in Example 1 except for the above.

[Example 4]
Example 1 except that the type of the polyfunctional radically polymerizable monomer was changed from FAM-201 to light acrylate 9EG-A (corresponding to a bifunctional acrylate compound manufactured by Kyoeisha Chemical Co., Ltd.) and the exposure amount was 100 mJ / cm ^2. The conductive film of Example 4 was produced by the same method.

[Comparative Example 1]
The conductive film of Comparative Example 1 was produced by the same method as in Example 1 except that a polyfunctional radically polymerizable monomer was not used and the exposure amount was 1500 mJ / cm ^2.

[Comparative Example 2]
The conductivity of Comparative Example 2 was carried out by the same method as in Example 1 except that the interacting polymer was changed to polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight of about 25,000) and the exposure amount was 450 mJ / cm ^2. A film was made.

[Comparative Example 3]
A composition B for forming a layer to be plated having the following composition was prepared with reference to [Example 8] described in the Example column of JP2012-97296A.
[Composition B for forming a layer to be plated]
Pure water 4.628g
NaHCO ₃ 0.31g
Polymer having the following structure (corresponding to the specific polymer B of Example 8 of JP2012-97296A) 1.742 g
1-methoxy-2-propanol 18.51 g
IRGACURE-OXE02 0.174g

The conductive film of Comparative Example 3 was produced by the same method as in Example 1 except that the composition A for forming the layer to be plated was changed to the composition B for forming the layer to be plated and the exposure amount was 1000 mJ / cm ^2. ..

[Comparative Example 4]
The type of polymerization initiator was changed from IRGACURE-OXE02 to Omnirad-379 (manufactured by IGM Resins VV, corresponding to alkylphenone-based photopolymerization initiator, ClogP: 4.31), and the exposure amount was 1000 mJ / cm ² . The conductive film of Comparative Example 4 was produced by the same method as in Example 1 except for the above.

[Various evaluations]
The following various evaluations were carried out using the substrate with the precursor layer to be plated, the substrate with the patterned layer to be plated, and the conductive film obtained in the above Examples and Comparative Examples. The results are summarized in Table 1 described later.

[Stretchability]
Using a Tensilon universal material tester (manufactured by Shimadzu Corporation), the substrates with the patterned layer to be plated obtained in the above Examples and Comparative Examples were stretched. Specifically, a substrate with a patterned plated layer having a mesh-shaped plated layer having a width of a thin wire portion of 4 μm and a length of a piece of an opening of 150 μm under a heating environment of 160 ° C. Stretch at a magnification of 250% so that it is parallel to one of the two adjacent sides of the quadrangle formed by the fine lines of the mesh, and observe the range of 1 cm x 1 cm of the substrate with the patterned layer to be plated. It was confirmed whether or not the layer to be plated was broken inside.

[Patterning property (presence or absence of pattern collapse)]
With respect to the substrate with the layer to be plated precursor layer to which the protective film obtained in the above Examples and Comparative Examples is applied, the width of the thin wire portion is 4 μm and the length of one piece of the opening is 150 μm. UV irradiation was performed with a ^{high-pressure mercury lamp at an exposure amount of 100 mJ / cm 2} through a mask having an opening pattern.
After UV irradiation, the protective film was peeled off from the substrate with the precursor layer to be plated. Next, the exposed substrate with the precursor layer to be plated is shower-washed with an aqueous sodium carbonate solution (1% by mass) and subjected to alkali development treatment after the protective film has been peeled off. To obtain a patterned substrate with a layer to be plated.
The range of 1 cm × 1 cm of the obtained patterned substrate with a layer to be plated was observed, and the presence or absence of pattern collapse within that range was confirmed.

[Alkaline development suitability]
The unexposed portion of the conductive film obtained in the above Examples and Comparative Examples was observed to confirm the presence or absence of plating copper precipitation in the unexposed portion.
"A": No plating copper precipitation occurred "B": Plated copper precipitation occurred

[Water development suitability]
In the method for producing the conductive film obtained in the above Examples and Comparative Examples, the same method except that the alkali development treatment performed in [Preparation of a substrate with a patterned layer to be plated] is changed to the following water development treatment. Each conductive film was manufactured by.
Next, the unexposed portion of the patterned substrate with the layer to be plated obtained through the above water development treatment was observed to confirm the presence or absence of plating copper precipitation in the unexposed portion.
"A": No plating copper precipitation occurred "B": Plated copper precipitation occurred (water development treatment)
The exposed substrate with the precursor layer to be plated was shower-washed with water at room temperature and subjected to water development treatment after the protective film was peeled off.

Table 1 is shown below.
In Table 1, "-" in the "water development suitability" column and the "alkali development suitability" column in the comparative example column is either unmeasurable (comparative example 1) or not evaluated (comparative examples 2 to 4). ) Is intended.
The polymerization initiator ClogP is described in ChemBio Drow Ultra ver. Of PerkinElmer. It is a calculated value calculated using Chemproperty of 13.0.
In addition, it was confirmed that the metal layer can be formed on the layers to be plated formed in Examples 1 to 4 by the plating treatment.

As shown in Table 1, a desired effect was obtained by using a composition for forming a layer to be plated containing a predetermined component.
Further, from the comparison between Examples 1 and 4, it was confirmed that when the polyfunctional radically polymerizable monomer is a bifunctional acrylamide compound or a bifunctional methacrylamide compound, it is excellent in various development suitability.
Further, as shown in Table 1, the desired effect was not obtained with the composition for forming the layer to be plated of the comparative example.

10 Substrate 12 Mesh-shaped layer to be plated 14 Opening 20 Substrate with layer to be plated having a hemispherical shape

Claims (9)

With at least one of the oxime ester-based polymerization initiator and the acylphosphine oxide-based polymerization initiator,
A polymer containing a double bond in the main chain and a functional group that interacts with the plating catalyst or its precursor.
A composition for forming a layer to be plated, which comprises a polyfunctional radically polymerizable monomer .
The polymer contains a repeating unit derived from a conjugated diene compound and a repeating unit derived from an unsaturated carboxylic acid or a derivative thereof, and the content of the repeating unit derived from the conjugated diene compound is 25 to 25 to all the repeating units. A polymer in which the content of the repeating unit derived from the unsaturated carboxylic acid or its derivative is 75 mol% and the content of the repeating unit is 25 to 75 mol% with respect to all the repeating units.
The polyfunctional radically polymerizable monomer is a bifunctional acrylamide compound or a bifunctional methacrylamide compound.
A composition for forming a layer to be plated, wherein the ratio of the mass of the polymer to the mass of the polyfunctional radically polymerizable monomer is 0.3 to 4. With at least one of the oxime ester-based polymerization initiator and the acylphosphine oxide-based polymerization initiator,
A polymer containing a double bond in the main chain and a functional group that interacts with the plating catalyst or its precursor.
A composition for forming a layer to be plated, which comprises a polyfunctional radically polymerizable monomer.
The polymer contains a repeating unit derived from a conjugated diene compound and a repeating unit derived from an unsaturated carboxylic acid or a derivative thereof, and the content of the repeating unit derived from the conjugated diene compound is 25 to 25 to all the repeating units. A polymer in which the content of the repeating unit derived from the unsaturated carboxylic acid or its derivative is 75 mol% and the content of the repeating unit is 25 to 75 mol% with respect to all the repeating units.
The polyfunctional radically polymerizable monomer is a bifunctional acrylamide compound or a bifunctional methacrylamide compound.
The content of the polymer is 35 to 80% by mass with respect to the total solid content, and the content of the polyfunctional radically polymerizable monomer is 15 to 65% by mass with respect to the total solid content. Composition for forming a layer to be plated. The composition for forming a layer to be plated according to claim 1 or 2 , wherein the polyfunctional radically polymerizable monomer is a compound represented by the formula (1).

In formula (1), R ₁ and R ₂ independently represent a hydrogen atom or a methyl group, respectively. R ₃ and R ₄ independently represent a hydrogen atom or a substituent. L ₁ and L ₂ each independently represent a single bond or a divalent linking group. A represents an alkylene group. m represents an integer of 2 or more. A layer to be plated precursor layer having a substrate and a layer to be plated precursor layer formed from the composition for forming the layer to be plated according to any one of claims 1 to 3 arranged on the substrate. With board. A substrate with a layer to be plated, which is obtained by curing the precursor layer to be plated in the substrate with a layer to be plated according to claim 4, and has a substrate and a layer to be plated. The substrate with a layer to be plated according to claim 5 , wherein the layers to be plated are arranged in a pattern. A conductive film comprising the substrate with a layer to be plated according to claim 5 or 6 and a metal layer arranged on the layer to be plated in the substrate with a layer to be plated. A touch panel sensor including the conductive film according to claim 7. A touch panel including the touch panel sensor according to claim 8.

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