TW202041364A - Laminate, method for producing substrate with layer to be plated, metohd for producing conductive film - Google Patents

Abstract

The present invention provides: a laminate having a to-be-plated precursor layer; a method for manufacturing a substrate having a to-be-plated layer; and a method for manufacturing a conductive film, wherein a patterned to-be-plated layer formed from the to-be-plated precursor layer can be thinned, and cracking and peeling during the thermal deformation of the patterned to-be-plated layer can be suppressed. This laminate comprises: a transparent substrate; a to-be-plated precursor layer disposed on one surface-side of the transparent substrate and containing a photo polymerization initiator; and an anti-halation layer releasably disposed on the other surface-side of the transparent substrate, wherein the to-be-plated precursor layer has a functional group capable of interacting with a plating catalyst or a precursor thereof, and a polymerizable group.

Description

Laminate, method of manufacturing substrate with plated layer, method of manufacturing conductive film

The present invention relates to a method for manufacturing a laminate, a substrate with a plated layer, and a method for manufacturing a conductive film.

A conductive film (substrate with a metal layer) provided with a metal layer (preferably a patterned metal layer) on a substrate is used in various applications. For example, in recent years, with the increase in the mounting rate of touch panels for mobile phones, portable game consoles, etc., the demand for conductive films for capacitive touch panel sensors capable of multi-point detection is rapidly increasing.

For example, Patent Document 1 discloses a method of forming a patterned layer (the patterned layer to be plated) containing functional groups that interact with a plating catalyst or its precursor on a substrate, and then make the substrate After the deformation, electroplating is performed to form a patterned metal layer to obtain a conductive thin film.

[Patent Document 1] JP 2016-213435 A

In recent years, there has been a demand for further thinning of the patterned metal layer in the conductive film. The inventors of the present invention conducted research on the technique of Patent Document 1, and found that when the patterned layer is formed by light irradiating the plating precursor layer, halo is generated and it is difficult to thin the patterned layer. In addition, in order to obtain a conductive film having a predetermined three-dimensional shape, it is also expected that cracks and peeling do not occur in the patterned layer to be plated during thermal deformation.

In view of the above situation, the subject of the present invention is to provide a laminate having a precursor layer to be plated, which can thin the patterned plated layer formed by the plated precursor layer, and can suppress the patterned plated layer from being thermally deformed. Cracking and peeling. Moreover, the subject of the present invention is to provide a method of manufacturing a substrate with a plated layer and a method of manufacturing a conductive film.

As a result of intensive research on the above-mentioned problems, the inventors found that the above-mentioned problems can be solved by the following configuration.

(1) A laminated body having: a transparent substrate; a precursor layer to be plated, which is arranged on one surface side of the transparent substrate and contains a photopolymerization initiator; and an anti-halation layer, which is arranged in a peelable manner On the other surface side of the transparent substrate, the precursor layer to be plated has a functional group and a polymerizable group capable of interacting with the electroplating catalyst or its precursor. (2) (1) of the laminate, wherein the photopolymerization initiator is a maximum absorption wavelength in the wavelength range of 310 ~ 450nm is defined as the absorbance at λ _max, antihalation layer at λ _max tie 0.50 the above. (3) The laminate as described in (2), wherein the absorbance of the precursor layer to be plated at λ _max is 0.06 to 0.40. (4) The laminated body according to any one of (1) to (3), wherein the haze value of the anti-halation layer is 20% or less. (5) The layered product according to any one of (1) to (4), wherein the wavelength of the absorption end of the ultraviolet-visible absorption spectrum of the anti-halation layer on the long-wavelength side is greater than the wavelength of the ultraviolet-visible absorption spectrum of the coated precursor layer The long-wavelength side of the absorption end has a large wavelength. (6) The laminate according to any one of (1) to (5), wherein when the transparent substrate does not contain an ultraviolet absorber or the transparent substrate contains an ultraviolet absorber, the ultraviolet absorber is relative to the total mass of the transparent substrate The content is 0.01% by mass or less. (7) A method of manufacturing a substrate with a plated layer, comprising: Process 1, which is to perform exposure treatment and development treatment on the plated precursor layer of the laminate according to any one of (1) to (6) Forming a patterned layer to be plated; Process 2 is to peel off the anti-halation layer from the laminate obtained in Process 1 to obtain a layered laminate containing a transparent substrate and a patterned layer to be plated; and Process 3 is to include the layer to be plated The laminated body is thermally deformed to obtain a substrate with a coating having a three-dimensional shape. (8) A method for manufacturing a conductive thin film, which has: Process 4, which imparts an electroplating catalyst or its precursor to the patterned layer of the plated substrate manufactured by the manufacturing method described in (7); In process 5, electroplating is performed on the patterned layer to be plated with the electroplating catalyst or its precursor to form the electroplated layer. [Invention Effect]

According to the present invention, it is possible to provide a laminate having a plated precursor layer, which can thin the patterned plated layer formed by the plated precursor layer, and can suppress the cracking and peeling of the patterned plated layer during thermal deformation . Furthermore, according to the present invention, it is possible to provide a method of manufacturing a substrate with a plated layer and a method of manufacturing a conductive film.

Hereinafter, the present invention will be described in detail. In addition, the numerical range shown by "-" in this specification means the range which contains the numerical value described before and after "-" as the lower limit and the upper limit.

As a characteristic point of the laminated body of the present invention, an anti-halation layer arranged so as to be peelable is provided on the surface side of the transparent substrate. The inventors of the present invention conducted in-depth research on the problems of the prior art, and found that as shown in FIG. 1, when the layered body 100 having the transparent substrate 102 and the plated precursor layer 104 is processed from the side of the plated precursor layer 104 During exposure (open arrow), a halo (solid arrow) reflecting transmitted light is generated on the surface (surface 102A) of the transparent substrate 102 opposite to the precursor layer 104 to be plated. If this halo occurs, light is incident on the side of the precursor layer 104 to be plated again, and the resolution of the formed pattern decreases. As a method of suppressing the above-mentioned problems, there is a method of disposing the anti-halation layer 106 on the surface 102A side of the transparent substrate 102 as shown in FIG. 2. However, it has been found that if a patterned layer is formed from the precursor layer 104 to be plated using the laminated body 110 provided with the anti-halation layer 106 and then thermally deformed, the patterned layer will be generated due to the presence of the anti-halation layer 106 Cracking and peeling. It is presumed that this is caused by the difference in thermal expansion coefficients of the anti-halation layer 106, the transparent substrate 102, and the patterned layer to be plated. Therefore, in the present invention, the above-mentioned problem is solved by using an anti-halation layer arranged in a peelable manner. That is, after forming the patterned layer by using the anti-halation layer when forming the patterned layer to be plated, the anti-halation layer is peeled off before the thermal deformation, thereby suppressing the occurrence of cracks and peeling in the layer to be plated as described above.

Hereinafter, an embodiment of the laminate of the present invention will be described. Fig. 3 is a cross-sectional view of an embodiment of the laminate of the present invention. The laminate 10 includes a transparent substrate 12, a precursor layer 14 to be plated arranged on one surface side of the transparent substrate 12, and an anti-halation layer 16 arranged on the other surface side of the transparent substrate 12 in a peelable manner. In FIG. 1, the transparent substrate 12 and the plated precursor layer 14 are arranged in a manner of being connected, but as described later, other layers (for example, a primer layer) may also be arranged between the transparent substrate 12 and the plated precursor layer 14 ). That is, the plated precursor layer 14 may be disposed on one surface of the transparent substrate 12 in a direct contact manner, or may be disposed on one surface of the transparent substrate 12 through other layers. Hereinafter, each member constituting the laminate will be described in detail.

>Transparent substrate> The transparent substrate only needs to be a member that supports each member. The transparent substrate usually has two opposing surfaces (main surfaces). The transparent substrate refers to a substrate whose transmittance of visible light (wavelength 400-700 nm) is 60% or more. Preferably, the transmittance is 80% or more, and more preferably 90% or more. The upper limit is not particularly limited, but it is often less than 100%.

As a transparent substrate, a well-known transparent substrate (for example, a resin substrate, a glass substrate, a ceramic substrate, etc.) can be mentioned, a flexible substrate is preferable, and a resin substrate is more preferable. Examples of materials for the resin substrate include polycarbonate resins, polyacrylic resins, polymethacrylic resins, polyether-based resins, polyurethane-based resins, polyester-based resins, poly-based resins, and polyamides. Amine resin, polyarylate resin, polyolefin resin, cellulose resin, polyvinyl chloride resin, cycloolefin resin, etc. The thickness of the transparent substrate is not particularly limited. From the viewpoint of the balance between operability and thinning, 0.05 to 2 mm is preferable, and 0.1 to 1 mm is more preferable.

The transparent substrate may or may not contain an ultraviolet absorber. Among them, from the viewpoint of suppressing the bleeding of the ultraviolet absorber during thermal deformation, when the transparent substrate does not contain the ultraviolet absorber or the transparent substrate contains the ultraviolet absorber, the content of the ultraviolet absorber is 0.01% by mass or less relative to the total mass of the transparent substrate For better. In addition, when the transparent substrate contains an ultraviolet absorber, the lower limit of the content of the ultraviolet absorber is not particularly limited, and it is often 0.001% by mass or more.

When the maximum absorption wavelength of the light will later be plated layer precursor contained in the polymerization initiator in the range of 310 ~ 450nm wavelength λ _max is set, the absorbance at λ _max of the transparent substrate is not particularly limited, but as Considering that the transparency of the conductive film described later is more excellent, it is preferably less than 0.06, and more preferably 0.04 or less. The lower limit is not particularly limited, but it is more than 0 in many cases.

>Precursor layer to be plated> The layer precursor layer to be plated is a layer arranged on one surface side of the transparent substrate, and is a layer for forming the layer to be plated described later. That is, the plated layer precursor layer is a layer in an unhardened state before the hardening treatment is performed. The layer precursor layer to be plated is a photosensitive layer and contains a photopolymerization initiator. As the photopolymerization initiator, a known photopolymerization initiator can be mentioned. As the type of the photopolymerization initiator, for example, a photoradical polymerization initiator and a photocationic polymerization initiator are mentioned, and a photoradical polymerization initiator is preferred. As the photopolymerization initiator, benzophenones, acetophenones, α-aminoalkyl phenones, benzoin, ketones, thioxanthones, benzyls, benzyl ketones can be mentioned. Ketones, oxime esters, anthrones, tetramethylthiuram monosulfide, bis-acetoxyphosphine oxides, acetoxyphosphine oxides, anthraquinones and azos.

The content of the photopolymerization initiator in the precursor layer to be plated is not particularly limited, but from the perspective of enabling further thinning of the patterned layer to be plated, 0.1-15% by mass relative to the total mass of the precursor layer to be plated It is preferable, and 0.5-10 mass% is more preferable.

In addition, the position of the wavelength of the absorption end of the ultraviolet-visible absorption spectrum of the photopolymerization initiator is not particularly limited, but it is longer than the ultraviolet-visible absorption spectrum of the anti-halation layer in terms of being able to further thin the patterned layer. The wavelength of the absorption end on the wavelength side is preferably small. In addition, the absorption end of the ultraviolet-visible absorption spectrum of the photopolymerization initiator refers to preparing a solution with a concentration of the photopolymerization initiator of 0.01% by mass (using a solvent in which the polymerization initiator is dissolved, such as acetonitrile), and When measured with V-670 (JASCO Corporation), the absorbance was 0.01 or less on the longest wavelength side. The definition of the wavelength of the absorption end on the long wavelength side of the ultraviolet-visible absorption spectrum of the anti-halation layer will be described in detail later.

When the photopolymerization initiator in the wavelength range of 310 ~ 450nm in maximum absorption wavelength λ _max is set, the precursor coating layer on the above-described absorbance λ _max is not particularly limited, and 0.01 to 0.60 in the case of many, can be from In consideration of further thinning of the patterned layer, 0.06 to 0.40 is preferable. In addition, light with a wavelength of less than 310 nm is absorbed by the transparent substrate in many cases, so the effect on halo is less. In addition, a photopolymerization initiator having a λ _max at a wavelength greater than 450 nm has slightly poor operability, so it is preferable to use a photopolymerization initiator having a λ _max within the above range.

The precursor layer to be plated has a functional group capable of interacting with the plating catalyst or its precursor (hereinafter, also referred to as "interactive group") and a polymerizable group. The details of the interactive group and the polymerizable group will be described later.

The precursor layer to be plated may also contain other components besides the photopolymerization initiator. It is preferable that the precursor layer to be plated contains the following compound X or composition Y. Compound X: a compound with an interactive group and a polymerizable group Composition Y: A composition containing a compound with an interactive group and a compound with a polymerizable group

Compound X is a compound having an interactive group and a polymerizable group. The interactive group refers to a functional group that can interact with the electroplating catalyst or its precursor provided on the patterned layer, for example, functional groups that can form electrostatic interaction with the electroplating catalyst or its precursor and It can form coordinated nitrogen-containing functional groups, sulfur-containing functional groups and oxygen-containing functional groups with the electroplating catalyst or its precursors. As the interactive group, for example, an amino group, an amide group, an imine group, a ureido group, a tertiary amino group, an ammonium group, an amidino group, a tricyclic ring, a triazole ring, and a benzotriazole group , Imidazolyl, benzimidazolyl, quinolinyl, pyridinyl, pyrimidinyl, pyridinyl, oxazolinyl, quinoxinyl, purinyl, trisyl, piperidinyl, piperidine, pyrrolidine Group, pyrazolyl, aniline, alkylamine structure-containing group, isocyanuric acid structure-containing group, nitro group, nitroso group, azo group, diazo group, azide group, cyano group, cyano group Nitrogen-containing functional groups such as acid ester groups; ether groups, hydroxyl groups, phenolic hydroxyl groups, carboxyl groups, carbonate groups, carbonyl groups, ester groups, groups containing N-oxide structure, groups containing S-oxide structure, groups containing N- Oxygen-containing functional groups such as groups of hydroxyl structure; thienyl, thiol, thiourea, thiocyanurate, benzothiazolyl, mercapto trithiol, thioether, thioketone, oxylene Sulfur-containing functional groups such as sulfide, sulfite, sulfite, sulfimide structure, sulfonium salt structure, sulfonic acid group, sulfonate structure-containing group, etc.; phosphate ester group, phosphatidylamine group Phosphorus-containing functional groups such as phosphine groups, groups containing phosphate structures; groups containing halogen atoms such as chlorine atoms and bromine atoms, etc. Among the functional groups that can adopt salt structures, salts of these functional groups can also be used. Among them, due to the high polarity and high adsorption energy for electroplating catalysts or their precursors, ionic polar groups or cyano groups of carboxylic acid groups, sulfonic acid groups, phosphoric acid groups and boric acid groups are preferred. The base is better. The compound X may have two or more types of interactive groups.

The polymerizable group is a functional group capable of forming a chemical bond by applying energy, and examples thereof include a radical polymerizable group and a cationic polymerizable group. Among them, a radical polymerizable group is preferred from the viewpoint of being more excellent in reactivity. Examples of radical polymerizable groups include alkenyl groups (example: -C=-C), acrylate groups (acryloxy groups), methacrylate groups (methacryloxy groups), and itaconic acid Ester group, crotonate group, isocrotonic acid ester group, maleic acid ester group, styryl group, vinyl group, acrylamide group and methacrylamide group. Among them, alkenyl, methacryloxy, acryloxy, vinyl, styryl, acrylamido or methacrylamido are preferred, methacryloxy and acryloxy Or styryl is more preferable. The compound X may have two or more types of polymerizable groups. In addition, the number of polymerizable groups possessed by the compound X is not particularly limited, and it may be one or two or more.

The aforementioned compound X may be a low-molecular compound or a high-molecular compound. The low-molecular compound refers to a compound with a molecular weight of less than 1,000, and the high-molecular compound refers to a compound with a molecular weight of 1,000 or more.

When the above-mentioned compound X is a polymer, the weight average molecular weight of the polymer is not particularly limited. From the viewpoint of better handling properties such as solubility, 1,000 to 700,000 are preferable, and 2,000 to 200,000 are more preferable. The synthesis method of the polymer having a polymerizable group and an interactive group is not particularly limited, and a known synthesis method is used (refer to paragraphs [0097] to [0125] of JP 2009-280905 A).

The composition Y is a composition containing a compound having an interactive group and a compound having a polymerizable group. That is, the composition Y contains two kinds of compounds having an interactive group and a compound having a polymerizable group. The definitions of the interactive group and the polymerizable group are as described above. The compound having an interactive group may be a low-molecular compound or a high-molecular compound. In addition, the compound having an interactive group may contain a polymerizable group. As a preferable aspect of the compound having an interactive group, a polymer (for example, polyacrylic acid) containing a repeating unit having an interactive group can be mentioned. As a preferable aspect of the repeating unit having an interactive group, a repeating unit represented by formula (A) can be cited.

[化1]

In the formula (A), R ¹ represents a hydrogen atom or an alkyl group (for example, a methyl group, an ethyl group, etc.). L ¹ represents a single bond or a divalent linking group. The divalent linking group is not particularly limited. For example, a divalent hydrocarbon group (may be a divalent saturated hydrocarbon group or a divalent aromatic hydrocarbon group. The divalent saturated hydrocarbon group may be linear, branched or cyclic, The carbon number is preferably from 1 to 20, such as alkylene. In addition, the divalent aromatic hydrocarbon group has a carbon number of 5 to 20, for example, an aryl group. In addition, it may be an alkylene group. Alkenyl, alkynylene.), divalent heterocyclic group, -O-, -S-, -SO ₂ -, -NR-, -CO-(-C(=O)-), -COO-(- C(=O)O-), -CO-NR-, -SO ₃ -, -SO ₂ NR-, and groups formed by combining two or more of these. Among them, R represents a hydrogen atom or an alkyl group (preferably with 1 to 10 carbon atoms). Z represents an interactive group. The definition of the interactive group is as described above.

As another preferable aspect of the repeating unit having an interactive group, a repeating unit derived from an unsaturated carboxylic acid or a derivative thereof can be mentioned. The unsaturated carboxylic acid refers to an unsaturated compound having a carboxylic acid group (-COOH group). As for derivatives of unsaturated carboxylic acids, for example, anhydrides of unsaturated carboxylic acids, salts of unsaturated carboxylic acids, and monoesters of unsaturated carboxylic acids can be cited. 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 with the interactive group in the polymer containing the repeating unit with the interactive group is not particularly limited. From the standpoint of the balance of the electroplating precipitation property, it is 1-100 relative to the total repeating unit system. Mole% is preferable, and 10-100 mole% is more preferable.

As a preferable aspect of a polymer containing a repeating unit having an interactive group, from the viewpoint of easily forming the layer to be plated with a small amount of energy imparted (for example, exposure amount), it is possible to include Polymer X which is a repeating unit of a conjugated diene compound and a repeating unit derived from an unsaturated carboxylic acid or its derivative. The description of the repeating unit derived from the unsaturated carboxylic acid or its derivative is as described above.

The conjugated diene compound is not particularly limited as long as it is a compound separated by a single bond and containing a molecular structure having two carbon-carbon double bonds. Examples of conjugated diene compounds include isoprene, 1,3-butadiene, 1,3-pentadiene, 2,4-hexadiene, 1,3-hexadiene, 1, 3-heptadiene, 2,4-heptadiene, 1,3-octadiene, 2,4-octadiene, 3,5-octadiene, 1,3-nonadiene, 2,4- Nonadiene, 3,5-nonadiene, 1,3-decadiene, 2,4-decadiene, 3,5-decadiene, 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, 3-methyl-1,3-hexadiene, 2-benzyl-1,3-butadiene and 2-p-tolyl-1 ,3-Butadiene.

Among them, in terms of easy synthesis of polymer X and better properties of the layer to be plated, the repeating unit derived from the conjugated diene compound is the repeating unit derived from the compound having the butadiene skeleton represented by formula (2) For better.

[化2]

In formula (2), R ² each independently represents a hydrogen atom, a halogen atom, or a hydrocarbon group. As the hydrocarbon group, an aliphatic hydrocarbon group (for example, an alkyl group, an alkenyl group, etc.. The carbon number is preferably 1 to 12) and an aromatic hydrocarbon group (for example, a phenyl group, a naphthyl group, etc.). The plural R ² may be the same or different.

As a compound having a butadiene skeleton represented by formula (2) (monomer having a butadiene structure), for example, 1,3-butadiene, isoprene, 2-ethyl-1, 3-butadiene, 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-bromo-1,3-butadiene Diene, 1-chlorobutadiene, 2-fluoro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 1,1,2-trichloro-1,3- Butadiene, 2-cyano-1,3-butadiene.

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 the total 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% relative to the total repeating units.

The compound having a polymerizable group is a so-called monomer, and a polyfunctional monomer having two or more polymerizable groups is preferred from the viewpoint that the hardness of the formed patterned layer is more excellent. Specifically, a multifunctional monosystem monomer having 2 to 6 polymerizable groups is preferable. From the viewpoint of the fluidity of the molecules in the crosslinking reaction that affects the degree of reactivity, the molecular weight of the polyfunctional monomer used is preferably 150 to 1,000, and more preferably 200 to 800.

As the multifunctional monomer, an amide compound selected from the group including multifunctional acrylamide and multifunctional methacrylamide is preferred. The polyfunctional acrylamide contains two or more acrylamide groups. The number of acrylamide groups in the multifunctional acrylamide is not particularly limited, and 2 to 10 are preferred, 2 to 5 are more preferred, and 2 is even more preferred. The polyfunctional methacrylamide contains two or more methacrylamide groups. The number of methacrylamide groups in the multifunctional methacrylamide is not particularly limited, and 2-10 groups are preferable, and 2-5 groups are more preferable. In addition, the acrylamido group and the methacrylamido group are groups represented by the following formula (B) and formula (C), respectively. * Indicates the bonding position.

[化3]

R ³ represents a hydrogen atom or a substituent. The type of the substituent is not particularly limited, and known substituents (for example, an aliphatic hydrocarbon group and an aromatic hydrocarbon group that may contain a heteroatom. More specifically, an alkyl group, an aryl group, etc.) can be mentioned.

The polyfunctional acrylamide and the polyfunctional methacrylamide preferably have a polyoxyalkylene group. The polyoxyalkylene group refers to a group having an oxyalkylene group as a repeating unit. As the polyoxyalkylene group, a group represented by formula (D) is preferred. Formula (D)-(AO) _q -A represents an alkylene group. The number of carbon atoms in the alkylene group is not particularly limited, and 1 to 4 are preferred, and 2 to 3 are more preferred. For example, when A is an alkylene group with carbon number 1, -(AO)- represents an oxymethylene group (-CH ₂ O-), and when A is an alkylene group with carbon number 2, -(AO)- represents Oxyethylene (-CH ₂ CH ₂ O-), when A is an alkylene with carbon number 3, -(AO)- means oxyethylene (-CH ₂ CH(CH ₃ )O-, -CH (CH ₃ )CH ₂ O- or -CH ₂ CH ₂ CH ₂ O-). In addition, the alkylene group may be linear or branched.

q represents the repeating number of the oxyalkylene group, and represents an integer of 2 or more. The number of repetitions is not particularly limited, and among them, 2-10 is preferred, and 2-6 is more preferred. In addition, the number of carbon atoms in the alkylene group in the plurality of oxyalkylene groups may be the same or different. Moreover, when a plurality of types of oxyalkylene groups are contained, their bonding order is not particularly limited, and it may be a random type or a block type.

The content of the compound X (or composition Y) in the precursor layer to be plated is not particularly limited. With respect to the total mass of the precursor layer to be plated, 50% by mass or more is preferable, and 80% by mass or more is more preferable. As the upper limit, 100% by mass can be mentioned. When the precursor layer to be plated contains composition Y, the content of the compound having an interactive group in the precursor layer to be plated is not particularly limited, but is 10 to 90% by mass relative to the total mass of the precursor layer to be plated More preferably, 25 to 75% by mass is more preferable, and 35 to 65% by mass is still more preferable. In addition, the mass ratio of the compound having an interactive group to the compound having a polymerizable group (mass of the compound having an interactive group/mass of the compound having a polymerizable group) is not particularly limited, and it is formed from In consideration of the balance between the strength of the patterned layer and the plating suitability, 0.1-10 is preferable, and 0.5-2 is more preferable.

The precursor layer to be plated may contain other ingredients as needed (for example, sensitizers, hardeners, polymerization inhibitors, antioxidants, antistatic agents, fillers, flame retardants, lubricants, plasticizers or electroplating catalysts or their Precursor).

The method for forming the precursor layer to be plated is not particularly limited. For example, a composition containing a photopolymerization initiator and compound X or composition Y is brought into contact with a transparent substrate to form a precursor layer to be plated on the transparent substrate. method. The method of bringing the above composition into contact with the transparent substrate is not particularly limited. For example, a method of coating the composition on a transparent substrate or a method of immersing the transparent substrate in the composition can be mentioned. In addition, after the above-mentioned composition is brought into contact with the transparent substrate, a drying process may be performed in order to remove the solvent from the precursor layer to be plated as necessary.

The aforementioned composition may contain a solvent. The type of solvent is not particularly limited, and water and organic solvents can be mentioned. Examples of the organic solvent include well-known organic solvents (for example, alcohol solvents, ester solvents, ketone solvents, halogen solvents, hydrocarbon solvents, etc.).

>Anti-halation layer> The anti-halation layer is a layer that absorbs the light incident from the side of the coated precursor layer and transmitted through the transparent substrate. Due to the presence of the anti-halation layer, it is possible to prevent the light from being reflected on the surface of the transparent substrate on the side opposite to the side of the precursor layer to be plated and returning to the halo of the precursor layer to be plated again. The anti-halation layer is disposed on the transparent substrate in a peelable manner. That is, it means that when an external force for peeling off the anti-halation layer is applied to the layered product of the present invention, the layered product of the present invention will peel off between the anti-halation layer and the transparent substrate, and will not be separated from the precursor layer to be coated. The nature of peeling between transparent substrates. That is, in the laminate of the present invention, the peel strength between the precursor layer to be plated and the transparent substrate is greater than the peel strength between the anti-halation layer and the transparent substrate.

The absorption of the anti-halation layer under the above-mentioned λ _max is better, so as to effectively absorb the ultraviolet rays reacted by the photopolymerization initiator. More specifically, the absorbance of the anti-halation layer at the aforementioned λ _max is not particularly limited. It is often 0.30 or more. From the viewpoint that the patterned layer can be further thinned, 0.50 or more is preferable. The upper limit is not particularly limited, but it is often 3.00 or less.

The haze value of the anti-halation layer is not particularly limited, and it is often 30% or less. From the viewpoint that the patterned layer can be further thinned, 20% or less is preferable. The lower limit is not particularly limited, but it is often more than 1%. As long as the haze value of the anti-halation layer is within the above range, it is possible to further suppress the return of light to the precursor layer to be plated due to scattering in the anti-halation layer.

Considering that the patterned layer can be further thinned, the wavelength of the long-wavelength side of the ultraviolet-visible absorption spectrum of the anti-halation layer is larger than the wavelength of the long-wavelength side of the ultraviolet-visible absorption spectrum of the coated precursor layer For better. In addition, the absorption end on the long wavelength side of the ultraviolet-visible absorption spectrum of the anti-halation layer refers to the longest wavelength at which the absorbance becomes below 0.05 when the ultraviolet-visible absorption spectrum of the anti-halation layer is measured by V-670 (JASCO Corporation) The wavelength of the side. In addition, the absorption end on the long-wavelength side of the ultraviolet-visible absorption spectrum of the precursor layer to be plated means that when the ultraviolet-visible absorption spectrum of the precursor layer to be plated is measured by V-670 (JASCO Corporation), the absorbance becomes the longest of 0.05 or less The wavelength on the side of the wavelength.

It is preferable that the anti-halation layer can be easily peeled off from the transparent substrate. As peel strength, 0.5N/30mm or less is preferable. The lower limit is not particularly limited, but if peeling occurs accidentally, in order to avoid scratches caused by the friction between the transparent substrate and the anti-halation layer and the pattern resolution caused by the gap between the transparent substrate and the anti-halation layer The deterioration of the width is preferably 0.05 N/30 mm or more. The measuring method of the above-mentioned peel strength is as follows. The laminate was cut into 30 mm width×100 mm length, part of the anti-halation layer was peeled off and reinforced with Kempton tape, and the anti-halation layer was turned upward to fix the laminate on the sample stage. The peeling part was clamped to the device, and the anti-halation layer was pulled at a speed of 50 mm/min at 90° to measure the peel strength. In addition, AUTOGRAPH "AGS-X" (manufactured by Shimadzu Corporation) was used for the measurement.

The material of the anti-halation layer is not particularly limited, as long as it satisfies the above-mentioned characteristics. Regarding the anti-halation layer, a resin layer containing a resin is preferable from the viewpoint of handleability. Examples of the resin include known resins, such as polyolefin resins, polyacrylate resins, polymethacrylate resins, polyester resins, polyurethane resins, and polycarbonate resins. In addition, the anti-halation layer preferably contains a light absorber capable of absorbing light transmitted through the transparent substrate. The light absorber appropriately selects the best material according to the wavelength of the absorbed light, and examples thereof include ultraviolet absorbers and visible light absorbers. In particular, a light absorber having absorption at the wavelength of λ _max described above is preferable. In addition, the anti-halation layer may contain colorants such as dyes and pigments. The absorption wavelength range of the colorant is selected according to the type of the photopolymerization initiator used and the exposure wavelength.

The anti-halation layer may have a single-layer structure or a multiple-layer structure. When the anti-halation layer has a multiple-layer structure, it may include a support body and an adhesive layer disposed on the support body. When the anti-halation layer has a multiple-layer structure, at least one of the support and the adhesive layer may contain the above-mentioned light absorber (for example, an ultraviolet absorber, a visible light absorber, a colorant, etc.).

The method of forming the anti-halation layer is not particularly limited, and known methods can be mentioned. For example, a method of bonding an anti-halation layer to one surface of a transparent substrate can be cited. Specifically, a method of bonding the anti-halation layer to a transparent substrate using a laminator can be mentioned.

>Other layers> The laminate of the present invention may include other layers other than the transparent substrate, the precursor layer to be plated, and the anti-halation layer. For example, a primer layer can also be arranged between the transparent substrate and the precursor layer to be plated. As a primer layer, a well-known primer layer can be mentioned. In addition, a protective film may be disposed on the surface of the precursor layer to be plated on the side opposite to the transparent substrate side. As a protective film, a well-known resin film (for example, polypropylene film) is mentioned.

>Method of manufacturing substrate with plated layer> The above-mentioned laminated body can be used to manufacture a substrate with a coating layer having a three-dimensional shape. The manufacturing method of the substrate with a plated layer preferably has the following processes. Process 1 is to perform exposure treatment and development treatment on the plated precursor layer of the laminate of the present invention to form a patterned plated layer Process 2 is to peel off the anti-halation layer from the laminate obtained in Process 1 to obtain a laminate with a transparent substrate and a patterned layer to be plated Process 3 is to thermally deform the laminated body containing the plated layer to obtain a three-dimensional shape of the substrate with the plated layer Hereinafter, each manufacturing process will be described in detail.

(Process 1) Process 1 is a process of performing exposure treatment and development treatment on the precursor layer to be plated to form a patterned layer to be plated. In the exposure process, the precursor layer to be plated is irradiated with light in a pattern to obtain a desired pattern to be plated. The kind of light used is not particularly limited, and examples include ultraviolet light and visible light. When the light is irradiated in a pattern, it is preferable to irradiate the light with a mask having an opening of a predetermined shape. In the exposed portion of the precursor layer to be plated, the polymerizable group contained in the precursor layer to be plated is activated to generate crosslinks between compounds, and the layer is cured.

Next, a development process is performed on the plated precursor layer that has been hardened in a pattern, whereby the unexposed part is removed to form a patterned plated layer. The method of the development treatment is not particularly limited, and the best development treatment is performed according to the type of material used. Examples of the developing solution include organic solvents, pure water, and alkaline aqueous solutions.

The patterned layer to be plated formed by the above steps is a layer having functional groups that interact with the electroplating catalyst or its precursor, and is a layer arranged in a predetermined pattern. The patterned layer usually contains the above-mentioned compound having an interactive group. As the compound, polymers are preferred. That is, it is preferable that the patterned layer to be plated contains a polymer containing a repeating unit having an interactive group. When the patterned layer contains a polymer containing a repeating unit having an interactive group, the content of the polymer relative to the total mass of the patterned layer is preferably 10% by mass or more, and more preferably 30% by mass or more . The upper limit is not particularly limited, and may be 100% by mass.

The plating layer described later is arranged along the pattern of the patterned layer to be plated. Therefore, the patterned layer to be plated is arranged on the substrate corresponding to the shape of the plating layer to be formed, thereby forming the patterned layer to be plated in a desired shape. In addition, FIG. 4 shows a form in which the patterned layer 18 is arranged in a grid on the transparent substrate 12, but the present invention is not limited to this form, and the patterned layer may be arranged in other patterns (for example, Bar).

The thickness of the patterned layer to be plated is not particularly limited. In terms of being able to fully support the electroplating catalyst or its precursor and preventing abnormal electroplating, 0.05-2.0 μm is preferred, and 0.1-1.0 μm is more preferred.

When the patterned layer is grid-shaped, the line width W of the fine line portions constituting the grid is not particularly limited. From the viewpoint of the balance between the conductive properties of the plating layer and the difficulty of visual recognition, 30μm or less is preferred, and 15μm or less More preferably, 10 μm or less is more preferable, 5 μm or less is particularly preferable, 0.5 μm or more is preferable, and 1 μm or more is more preferable.

When the pattern-like plated layer is in a grid shape, the opening of the grid (the opening 20 in FIG. 4) preferably has a substantially diamond shape. However, in addition to this, it may also be polygonal (for example, triangle, quadrilateral, hexagon, and random polygon). In addition, the shape of one side may be linear, and the rest may be curved, or may be arc-shaped. In the case of an arc shape, for example, the two opposing sides may be arcs that protrude outward, and the other two opposing sides may be arcs that protrude inward. In addition, the shape of each side may be a wavy line in which an arc projecting outward and an arc projecting inward are continuous. Of course, the shape of each side can also be sinusoidal.

The length L of one side of the opening is not particularly limited. It is preferably 1500 μm or less, more preferably 1300 μm or less, more preferably 1000 μm or less, preferably 5 μm or more, more preferably 30 μm or more, and even more preferably 80 μm or more. When the length of the side of the opening is within the above-mentioned range, the transparency can be maintained well, and when the conductive film is mounted on the front of the display device, the display can be visually recognized without discomfort.

Furthermore, from the perspective of transmittance, the area where the patterned layer is formed is preferably 50 area% or less, more preferably 40 area% or less, and more preferably 30 area% or less relative to the entire surface area of the transparent substrate.

(Process 2) Process 2 is a process in which the anti-halation layer is peeled off from the laminate obtained in Process 1 to obtain a plated laminate containing a transparent substrate and a patterned layer. The anti-halation layer can be removed by implementing this process. The method of peeling off the anti-halation layer is not specifically limited, A well-known method can be mentioned. For example, a method of peeling off the anti-halation layer by setting a peeling trigger between the anti-halation layer and the transparent substrate can be cited.

(Process 3) Process 3 is a process for thermally deforming the laminated body containing the layer to be plated. By implementing this process, a substrate with a three-dimensional shape with a coating layer can be obtained. The three-dimensional shape is preferably a shape mainly having a curved surface. Specific examples of the three-dimensional shape include a semi-cylindrical shape, a wave shape, a convex-concave shape, and a cylindrical shape. The method of thermal deformation is not particularly limited, and known methods can be cited. Examples of the thermal deformation method include known methods such as thermal vacuum forming, blow molding, free blow molding, pressure forming, vacuum-pressure forming, and hot stamping.

>Method for manufacturing conductive film> The conductive thin film can be manufactured using the above-mentioned substrate with a plated layer. The formed conductive film has a three-dimensional shape and can be used in various applications. The manufacturing method of the conductive film preferably has the following processes. Process 4: The process of imparting electroplating catalyst or its precursor to the patterned layer of the substrate with the plated layer Process 5: It is a process of electroplating the patterned layer to be plated with electroplating catalyst or its precursor to form an electroplated layer Hereinafter, each manufacturing process will be described in detail.

(Process 4) Process 4 is a process of imparting electroplating catalyst or its precursor to the patterned layer of the plated substrate. The patterned layer to be plated has the above-mentioned interactive group, and therefore the interactive group adheres (adsorbs) to the provided electroplating catalyst or its precursor according to its function. The electroplating catalyst or its precursor functions as a electroplating catalyst or electrode. Therefore, the type of electroplating catalyst or its precursor used can be appropriately determined by the type of electroplating treatment.

The electroplating catalyst or its precursor is preferably an electroless plating catalyst or its precursor. There are no particular restrictions on the electroless plating catalyst as long as it becomes the active nucleus during electroless plating. For example, a metal having a catalytic ability for self-catalyst reduction reaction can be mentioned (as a catalyst which has a higher ionization tendency than Ni Low electroless plating metal and known). Specifically, Pd, Ag, Cu, Pt, Au, Co, etc. can be mentioned. As the electroless plating catalyst, a metal colloid can be used. 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 a plating catalyst or its precursor to the patterned layer, for example, a solution may be prepared by dispersing or dissolving the plating catalyst or its precursor in a solvent, and coating the solution on the patterned layer The method or the method of immersing the coated substrate in the solution. As said solvent, water or an organic solvent can be mentioned, for example.

(Process 5) Process 5 is a process of performing electroplating on the patterned layer to be plated with the electroplating catalyst or its precursor to form an electroplated layer (equivalent to a metal layer). The method of the electroplating treatment is not particularly limited, and examples include non-electrolytic plating treatment or electrolytic plating treatment (plating treatment). In this manufacturing process, the electroless plating treatment may be performed alone, or the electrolytic plating treatment may be performed after the non-electrolytic plating treatment is performed. The type of plating treatment is not particularly limited, and examples include copper plating treatment and silver plating treatment.

The electroplating layer is preferably arranged to cover the patterned layer to be plated. As described above, the plating layer is arranged along the pattern of the patterned layer to be plated. For example, when the patterned layer to be plated is grid-shaped, the formed electroplated layer also becomes grid-shaped.

When the electroplating layer is grid-like, the line width of the fine lines constituting the grid is not particularly limited. From the perspective of the balance between the conductive properties of the electroplated layer and the difficulty of visual recognition, 30μm or less is preferred, and 15μm or less is more preferred , 10 μm or less is more preferable, 5 μm or less is particularly preferable, 0.5 μm or more is preferable, and 1 μm or more is more preferable.

The thickness of the plating layer is not particularly limited. From the viewpoints of lower resistance and better adhesion, 0.1-5.0 μm is preferred, and 0.3-3.0 μm is more preferred.

>Use> The conductive film of the present invention can be used in various applications. For example, it can be applied to touch panel sensors, semiconductor chips, FPC (Flexible printed circuits), COF (Chip on Film), TAB (Tape Automated Bonding) ), antennas, multilayer wiring boards and motherboards for various purposes. Among them, it is better to use in touch panel sensors (especially, capacitive touch panel sensors). When the above-mentioned conductive film is applied to a touch panel sensor, the plating layer functions as a detection electrode or a lead wire in the touch panel sensor. This kind of touch panel sensor can be better applied to touch panels. In addition, the conductive film can be used as a heating element. For example, the temperature of the plating layer is increased by flowing current to the plating layer, so that the plating layer functions as a heating wire. [Example]

Hereinafter, the present invention will be described in further detail based on examples. The materials, usage amount, ratio, processing content, and processing steps shown in the following examples can be appropriately changed without departing from the scope of the present invention. Therefore, the scope of the present invention is limitedly interpreted by the examples shown below.

>Example 1> (Preparation of composition for forming primer layer) The following components were mixed to obtain a primer layer forming composition. ･Z913-3 (manufactured by Aica Kogyo Company, Limited): 33 parts by mass ･Isopropanol: 67 parts by mass

(Preparation of the composition for forming a precursor layer) The following components were mixed to obtain a composition for forming a precursor layer. In addition, Irgacure OXE02 has a maximum absorption wavelength λ _max of 340 nm at a wavelength of 310 to 450 nm. 38 parts by mass of isopropanol polybutadiene maleic acid (butadiene-maleic acid alternating copolymer, butadiene: maleic acid = 1:1 (molar ratio), Polysciences Inc . System) 4 parts by mass of FAM-201 (manufactured by FUJIFILM Corporation, the following structural formula) 1 part by mass of photopolymerization initiator (Irgacure OXE02 (manufactured by BASF)) 0.05 parts by mass

FAM-201 (equivalent to a bifunctional acrylamide compound, refer to the following structural formula)

[化4]

(Production of conductive film) The composition for forming a primer layer was coated on a resin substrate (PC (polycarbonate) film manufactured by Teijin Limited, PANLITE PC, thickness 250 μm) to form a coating film. Next, ultraviolet light was irradiated to the obtained coating film, and the coating film was cured to form a primer layer with a thickness of 0.8 μm. In addition, the transmittance of visible light (wavelength 400 to 700 nm) of the resin substrate is 60% or more. Next, the composition for forming a precursor layer was coated on the obtained primer layer, and dried at 120° C. for 1 minute to form a precursor layer to be plated with a thickness of 0.2 μm. then. A polypropylene film (thickness: 12μm) is attached to the precursor layer to be plated. Then, E-MASK-R100 (manufactured by Nitto Denko Corporation) was bonded to the surface of the resin substrate on the opposite side to the precursor layer to be plated as an anti-halation layer using a laminator.

Next, the precursor layer to be plated was exposed (100 mJ/cm ² ) through a photomask with a predetermined opening pattern. During exposure, a photomask is arranged by vacuum suction so that the photomask and the polypropylene film are closely attached. In addition, a high-pressure mercury lamp was used for exposure. After the exposure, the polypropylene film was peeled off, and the exposed precursor layer to be plated was developed with water at 40°C to remove the unhardened portion to obtain a patterned plated layer, thereby manufacturing a predetermined laminate.

(Evaluation: resolution width) When using the above-mentioned photomask for exposure, use a photo film with a pattern in which the line width of the line is 50μm, and the width of the spacing between the lines changes in the range of 1-50μm for exposure and development, and inspection The resolution of the resulting patterned coating. The smaller the value shown in Table 1, the thinner the line can be.

(Evaluation: cracking and peeling during deformation) After peeling the anti-halation layer from the laminate obtained above, the resulting laminate was vacuum-formed into a hemispherical shape using a vacuum forming machine Formech 508FS (manufactured by NIHON SEIZUKI KOGYO CO., LTD). Regarding the obtained hemispherical layered body, the presence or absence of abnormal parts such as cracks and peeling in the patterned layer to be plated was confirmed with the naked eye. Set the conditions without cracks and peeling to "None", and set the conditions with cracks and peeling to "Yes".

(Peeling evaluation) The layered body was cut into 30mm wide×100mm long, a part of the anti-halation layer was peeled off and reinforced with Kempton tape, and the layered body was fixed on the sample stage with the anti-halation layer facing upward. The peeling part was clamped to the device, and the anti-halation layer was pulled at a speed of 50 mm/min at 90° to measure the peel strength. The case where the peel strength is 0.5N/30mm or less is set as "Available", and the case where the peel strength is greater than 0.5N/30mm is set as "Not possible". In addition, AUTOGRAPH "AGS-X" (manufactured by Shimadzu Corporation) was used for the measurement.

>Example 2 to Example 13, Comparative Example 1 to Comparative Example 2> Except that the type of the anti-halation layer was changed as in Table 1, a laminate was produced in the same procedure as in Example 1, and predetermined evaluation was performed. In addition, regarding Examples 9 to 12, the content of the photopolymerization initiator was adjusted so as to have a predetermined λ _max absorbance. In addition, with regard to Comparative Example 1, in the above-mentioned evaluation (evaluation: cracking and peeling during deformation), the evaluation was carried out using a laminate including the anti-halation layer without peeling the anti-halation layer.

In Table 1, the "λ _max absorbance" column of the "Anti-halation layer" column indicates that the maximum absorption wavelength of the photopolymerization initiator measured by V-670 (JASCO Corporation) in the wavelength range of 310 to 450 nm is set as antihalation layer at λ _max absorbance at the λ _max. In Table 1, the "absorption end (nm)" column of the "anti-halation layer" column indicates the wavelength of the absorption end on the long wavelength side of the ultraviolet-visible absorption spectrum of the anti-halation layer measured by V-670 (JASCO Corporation). And the definition is as described above. In Table 1, the "λ _max absorbance" column of the "Precursor layer to be coated" column indicates that the maximum absorption wavelength of the photopolymerization initiator measured by V-670 (JASCO Corporation) in the wavelength range of 310 to 450 nm is set when the coating precursor layer for λ _max absorbance at the λ _max. [Lambda] _max of the coating layer precursor is obtained by subtracting the value of [lambda] _max of the transparent substrate from the value [lambda] _max of the laminate precursor was plated layer and the transparent substrate. In Table 1, the "absorption end (nm)" column of the "precursor layer to be plated" column indicates the absorption end of the long wavelength side of the ultraviolet-visible absorption spectrum of the precursor layer to be plated measured by V-670 (JASCO Corporation) The wavelength is defined as above. In addition, regarding Example 11 of Table 1, the resolution width was small and excellent, but it was confirmed that wiring was blurred. In addition, in Table 1, ">2700" means greater than 2700 nm. ">4" means less than 4nm. In addition, in Table 1, "-" means that evaluation was not performed.

The types "1" to "9" of the anti-halation layer in Table 1 indicate the following. In addition, as shown in Table 1 below, the anti-halation layer used is a layer that has absorption within a predetermined range. "1": E-MASK-R100 (manufactured by Nitto Denko Corporation) "2": Laminated body of Lumirror X30 (manufactured by Toray Industries Inc.) and an adhesive layer. "3": Colored polyethylene film "4": Colored polyethylene film "5": A laminate of polyethylene film and adhesive layer. In addition, the adhesive layer contains TINUVIN1600. "6": A laminate of polyethylene film and adhesive layer. In addition, the adhesive layer contains TINUVIN360. "7": Colored polyethylene film "8": Colored polyethylene film "9": A laminate of polyethylene film and adhesive layer. In addition, the adhesive layer contains TINUVIN360.

[Table 1] Anti-halation layer Precursor layer to be plated Evaluation species Peel evaluation λ _max absorbance Absorption end (nm) HAZE value λ _max absorbance Absorption end (nm) Cracking and peeling Resolution width (nm) Example 1 1 can 0.61 850 10% 0.10 400 no 8 Example 2 2 can 2.85 >2700 18% 0.10 400 no 6 Example 3 3 can 0.65 850 19% 0.10 400 no 10 Example 4 4 can 0.50 1150 12% 0.10 400 no 10 Example 5 1 can 0.59 850 10% 0.10 350 no 8 Example 6 5 can 0.50 380 10% 0.10 400 no 20 Example 7 6 can 0.50 420 10% 0.10 400 no 10 Example 8 7 can 0.52 850 twenty two% 0.10 400 no 20 Example 9 4 can 0.50 1150 12% 0.06 400 no 8 Example 10 4 can 0.50 1150 12% 0.40 400 no 15 Example 11 4 can 0.50 1150 12% 0.03 400 no >4 Example 12 4 can 0.50 1150 12% 0.50 400 no 20 Example 13 8 can 0.45 850 12% 0.10 400 no 20 Comparative example 1 9 No 3.90 420 10% 0.10 400 Have 5 Comparative example 2 no - - - - 0.10 400 - 30

As shown in Table 1, it was confirmed that the desired effect can be obtained as long as it is the laminate of the present invention. In addition, by comparing Example 6 with Example 7, it was confirmed that when the wavelength of the absorption end on the long-wavelength side of the ultraviolet-visible absorption spectrum of the anti-halation layer is greater than the wavelength of the long-wavelength side of the ultraviolet-visible absorption spectrum of the coated precursor layer The effect is more excellent when the wavelength of the absorption end. In addition, by comparing Example 8 with other examples, it was confirmed that the effect is more excellent when the haze value of the anti-halation layer is 20% or less. In addition, by comparison of Examples 9 to 12, it was confirmed that when the absorbance of the precursor layer to be plated at λ _max is 0.06 to 0.40, the effect is more excellent. In particular, as described above, in Example 11, the resolution width was small and excellent, but it was confirmed that the wiring was blurred. In addition, by comparing Example 13 with other examples, it was confirmed that when the absorbance of the anti-halation layer at λ _max is 0.50 or more, the effect is more excellent.

>Method for manufacturing conductive film> At 30°C, the three-dimensionally shaped substrate with plated layer obtained in each example after the above (evaluation: cracking and peeling during deformation) was applied to a Pd catalyst application solution (Omnishield 1573 activator, Rohm and After being immersed in Haas Electronic Materials for 5 minutes, the removed substrate with plated layer was washed with pure water. Next, after immersing the obtained plated substrate in a reducing solution (CIRCUPOSIT P13 oxide converter 60C, manufactured by Rohm and Haas Electronic Materials) for 5 minutes at 30°C, the removed plated substrate was washed with pure water . Next, after immersing the obtained substrate with a plated layer in an electroless plating solution (CIRCUPOSIT 4500, manufactured by Rohm and Haas Electronic Materials) for 15 minutes at 45°C, the removed substrate with a plated layer was washed with pure water to obtain Substrate with grid-like copper electroplating layer (substrate with copper electroplating layer).

10, 100, 110: laminated body 12.102: Transparent substrate 14, 104: Precursor layer to be plated 16, 106: anti-halation layer 18: Patterned layer 20: Opening

Figure 1 is a schematic diagram for explaining the problems of the prior art. Fig. 2 is a schematic diagram for explaining the problems of the prior art. Fig. 3 is a cross-sectional view of an embodiment of a laminate. Fig. 4 is a plan view showing one aspect of the patterned layer.

10: Laminated body

12: Transparent substrate

14: Precursor layer to be plated

16: Anti-halation layer

Claims (8)

A layered body, which has: Transparent substrate The precursor layer to be plated is arranged on one surface side of the aforementioned transparent substrate and contains a photopolymerization initiator; and The anti-halation layer is arranged on the other surface side of the aforementioned transparent substrate in a peelable manner, The aforementioned precursor layer to be plated has a functional group and a polymerizable group capable of interacting with the electroplating catalyst or its precursor. The laminate of one of the requests, wherein the photopolymerization initiator at a wavelength of 310nm ~ 450nm in the range of the maximum absorption wavelength of λ _max is set, the antihalation layer at the Department of absorbance λ _max 0.50 the above. The laminate according to claim 2, wherein the absorbance of the precursor layer to be plated at the λ _max is 0.06 to 0.40. The laminate according to any one of claims 1 to 3, wherein The haze value of the aforementioned anti-halation layer is 20% or less. The laminate according to any one of claims 1 to 3, wherein The wavelength of the absorption end on the long wavelength side of the ultraviolet-visible absorption spectrum of the antihalation layer is larger than the wavelength of the absorption end on the long wavelength side of the ultraviolet-visible absorption spectrum of the precursor layer to be coated. The laminate according to any one of claims 1 to 3, wherein When the aforementioned transparent substrate does not contain ultraviolet absorbers, or When the transparent substrate contains an ultraviolet absorber, the content of the ultraviolet absorber is 0.01% by mass or less relative to the total mass of the transparent substrate. A method for manufacturing a substrate with a plated layer, which has: Process 1, which is to perform exposure treatment and development treatment on the coating precursor layer of the laminate according to any one of claim 1 to claim 6 to form a patterned coating layer; In process 2, the anti-halation layer is peeled from the laminate obtained in the foregoing process 1 to obtain the plated layer-containing laminate having the transparent substrate and the patterned layer; and Process 3 is to thermally deform the aforementioned layer-containing laminate to obtain a substrate with a three-dimensional shape. A method for manufacturing a conductive film, which has: Process 4 is to apply a plating catalyst or its precursor to the patterned layer of the plated-coated substrate manufactured by the manufacturing method described in claim 7; and In process 5, electroplating is performed on the patterned layer to be plated with the electroplating catalyst or its precursor to form an electroplated layer.

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