JP2018183934A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate excellent in transparency of a base material layer, uniformity of a plating film, adhesion of a plating layer to a base material layer, and conductivity. SOLUTION: This is a laminate having an alicyclic structure-containing resin layer and a plating base layer adjacent to each other in order, and the plating base layer is (A) metal nanoparticles and (B) an organic π-conjugated system. A laminate, characterized in that it contains a compound. [Selection diagram] None

Description

  The present invention relates to a laminate.

  Conventionally, a method of forming a conductive layer or a wiring layer using nano-sized metal fine particles is known.

  For example, in Patent Document 1, an amine mixed solution containing an alkylamine having 6 or more carbon atoms and an alkylamine having 5 or less carbon atoms and a metal compound containing a metal atom are mixed, and the metal compound and A method for producing coated metal fine particles is described which includes a first step of producing a complex compound containing an amine and a second step of producing metal fine particles by decomposition of the complex compound by heating. . Patent Document 1 also describes that the metal fine particles obtained using the production method can be sintered smoothly even at a low temperature and can form a conductive layer or the like on a plastic substrate having poor heat resistance. Has been.

JP 2012-162767 A

  However, according to the study by the present inventors, the laminated film obtained using the coated metal fine particles described in Patent Document 1 is inferior to the transparency of the base material layer, on the metal layer containing the coated metal fine particles. It has been found that there are problems that the formed plating layer is inferior in uniformity, the adhesion of the plating layer to the base material layer is inferior, and the conductivity of the metal layer is inferior.

  Then, an object of this invention is to provide the laminated body excellent in transparency of a base material layer, the uniformity of a plating film, the adhesiveness of the plating layer with respect to a base material layer, and electroconductivity.

The laminate according to the present invention is
In order, adjacent to the alicyclic structure-containing resin layer,
A plating underlayer;
A laminate having
The plating base layer is
(A) metal nanoparticles,
(B) an organic π-conjugated compound;
It is a laminated body characterized by including. Thereby, it is possible to provide a laminate having excellent transparency of the base material layer, uniformity of the plating film, adhesion of the plating layer to the base material layer, and conductivity.

  In the laminate according to the present invention, it is preferable that the plating base layer further includes (C) a surfactant. Thereby, the uniformity of a plating film, the adhesiveness of the plating layer with respect to a base material layer, and electroconductivity improve.

  In the laminate according to the present invention, the (C) surfactant is preferably selected from the group consisting of a fluorine-based surfactant, an acetylene-based surfactant, a silicone-based surfactant, and a combination thereof.

In the laminate according to the present invention, the (B) organic π-conjugated compound has a phthalocyanine ring or a naphthalocyanine ring,
The (B) organic π-conjugated compound is an amino group, mercapto group, hydroxyl group, carboxyl group, phosphine group, phosphonic acid group, halogen group, selenol group, sulfo group, sulfide group, selenoether group and combinations thereof. It preferably has a substituent selected from the group consisting of

の１つ以上を有することが好ましい。 In the laminate according to the present invention, the (B) organic π-conjugated compound has the following structure:

It is preferred to have one or more of

  In the laminate according to the present invention, it is preferable that the plating base layer further contains (D) a binder. Thereby, the adhesiveness of the plating layer with respect to a base material layer improves.

The laminate according to the present invention is
In order, adjacent to the alicyclic structure-containing resin layer,
A plating underlayer;
Plating film,
It is a laminated body in any one of the above which has. Thereby, it is excellent in the transparency of a base material layer, the uniformity of a plating film, the adhesiveness of the plating layer with respect to a base material layer, and electroconductivity.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body excellent in transparency of a base material layer, the uniformity of a plating film, the adhesiveness of the plating layer with respect to a base material layer, and electroconductivity can be provided.

  Hereinafter, embodiments of the present invention will be described. These descriptions are intended to exemplify the present invention and do not limit the present invention in any way.

  In this specification, numerical ranges are intended to include the lower and upper limits of the range, unless otherwise specified. For example, 1 to 500 nm is intended to include a lower limit value of 1 nm and an upper limit value of 500 nm, and means 1 nm or more and 500 nm or less.

(Laminate)
The laminate according to the present invention is
In order, adjacent to the alicyclic structure-containing resin layer,
A plating underlayer;
A laminate having
The plating base layer is
(A) metal nanoparticles,
(B) an organic π-conjugated compound;
It is a laminated body characterized by including. Thereby, it is possible to provide a laminate having excellent transparency of the base material layer, uniformity of the plating film, adhesion of the plating layer to the base material layer, and conductivity.

<Alicyclic structure-containing resin layer>
The alicyclic structure-containing resin layer is a layer that functions as a base material layer of the laminate according to the present invention, and may also be referred to as a “base material layer” hereinafter.

  The alicyclic structure-containing resin layer is a layer containing an alicyclic structure-containing polymer as a resin component. The alicyclic structure-containing polymer is a polymer having an alicyclic structure in at least one of the main chain and the side chain. Especially, since it is excellent in mechanical strength, heat resistance, chemical resistance, low water absorption, etc., the alicyclic structure containing polymer which has alicyclic structure in a principal chain is preferable. An alicyclic structure containing polymer may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the alicyclic structure include a saturated cyclic hydrocarbon (cycloalkane) structure and an unsaturated cyclic hydrocarbon (cycloalkene) structure. Of these, a cycloalkane structure is preferred because it is excellent in mechanical strength, heat resistance, chemical resistance, low water absorption, and the like.

  The number of carbon atoms constituting the alicyclic structure is not particularly limited. For example, it is in the range of 4 to 30, preferably 5 to 20, more preferably 5 to 15. When the number of carbon atoms constituting the alicyclic structure is within these ranges, the properties of the base material layer such as mechanical strength, heat resistance, chemical resistance, and low water absorption are more highly balanced.

  What is necessary is just to adjust suitably the ratio of the repeating unit which has an alicyclic structure in an alicyclic structure containing polymer. The ratio of this repeating unit is, for example, 30% by weight or more, preferably 50% by weight or more, more preferably 70% by weight or more with respect to all repeating units. When the ratio is 30% by weight or more, it is excellent in mechanical strength, heat resistance, chemical resistance, low water absorption, and the like. The remainder other than the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer is not particularly limited and may be appropriately selected.

  The weight average molecular weight (Mw) of the alicyclic structure-containing polymer is not particularly limited, and may be adjusted as appropriate. For example, it is 5,000 to 500,000, preferably 8,000 to 200,000, more preferably 10,000 to 100,000. When the weight average molecular weight (Mw) of the alicyclic structure-containing polymer is in the range of 5,000 to 500,000, various properties such as the mechanical strength of the base material layer and the base material layer are produced. Workability is more highly balanced.

  The molecular weight distribution (Mw / Mn) of the alicyclic structure-containing polymer is not particularly limited, and may be adjusted as appropriate. For example, it is 1.0 to 4.0, preferably 1.0 to 3.0, and more preferably 1.0 to 2.5. The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the alicyclic structure-containing polymer are determined according to the method described in the examples.

  The glass transition temperature (Tg) of the alicyclic structure-containing polymer is not particularly limited, and may be adjusted as appropriate. For example, it is 50-200 degreeC, Preferably it is 80-170 degreeC. The heat resistance of a base material layer improves because the said Tg is 80 degreeC or more. Tg is determined according to the method described in the examples.

  Examples of the alicyclic structure-containing polymer include (1) a norbornene polymer, (2) a monocyclic olefin polymer, (3) a cyclic conjugated diene polymer, and (4) a vinyl alicyclic hydrocarbon. Examples thereof include a system polymer. Among these, norbornene-based polymers are preferable because they are excellent in mechanical strength, heat resistance, chemical resistance, low water absorption, and the like. In addition, in this specification, an alicyclic structure containing polymer polymer contains a polymerization reaction product and its hydrogenated product.

(1) Norbornene polymer The norbornene polymer is a polymer obtained by polymerizing a norbornene monomer which is a monomer having a norbornene skeleton, or a hydrogenated product thereof. The norbornene-based polymer includes a ring-opening polymer of a norbornene-based monomer; a ring-opening copolymer of a norbornene-based monomer and another monomer; a hydrogenated product thereof; an attachment of a norbornene-based monomer. Addition copolymer: Addition copolymer of norbornene monomer and other monomer.

Examples of norbornene monomers include norbornene (also known as bicyclo [2.2.1] hept-2-ene) and dicyclopentadiene (also known as tricyclo [4.3.0 ^{1,6 .1,2,5} ] deca. 3,7-diene), 1,4-methano -1,4,4a, 9a- tetrahydrofluorene (aka: tetracyclo ^[9.2.1.0 2,10 ^{.0 3,8]} tetradeca-3,5 , 7,12-tetraene or methanotetrahydrofluorene or 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene,), tetracyclododecene (also known as: tetracyclo [4.4 .1 ^2,5 .1 ^7,10 .0] dodec-3-ene) and derivatives thereof (referring to those having a substituent in the ring). A norbornene-type monomer may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the substituent that the derivative has in the ring include an alkyl group, an alkylene group, a vinyl group, an alkoxycarbonyl group, and an alkylidene group.

  Examples of the norbornene-based monomer having a substituent include 8-methoxycarbonyl-tetracyclo [4.4.0.12,5.17,10] dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [ 4.4.12, 5.17,10] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.12,5.17,10] dodec-3-ene, and the like.

  Examples of other monomers that form the ring-opening copolymer include monocyclic cyclic olefin monomers such as cyclohexene, cycloheptene, cyclooctene, and derivatives thereof. Examples of the substituent that the derivative has in the ring include those described above.

  Examples of other monomers that form the addition copolymer include α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, and 1-hexene; cyclobutene, cyclopentene, and cyclohexene. And cycloolefins such as cyclooctene; non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene; and derivatives thereof Is mentioned. Among these, α-olefins are preferable and ethylene is particularly preferable. Examples of the substituent of the derivative include the same ones as described above.

  A method for synthesizing the ring-opening polymer, the ring-opening copolymer, a hydrogenated product thereof, the addition polymer, and the addition copolymer is not particularly limited, and a known method can be used. For example, a method described in JP 2016-147502 A may be used.

  Among the norbornene-based polymers described above, a hydrogenated product of a ring-opening polymer of a norbornene-based monomer is preferable because of excellent mechanical strength, heat resistance, chemical resistance, low water absorption, and the like.

(2) Monocyclic Cyclic Olefin Polymer Examples of the monocyclic cycloolefin polymer include addition polymers of monocyclic cycloolefin monomers such as cyclohexene, cycloheptene, and cyclooctene. The method for synthesizing these polymers is not particularly limited, and a known method may be appropriately selected.

(3) Cyclic conjugated diene-based polymer Examples of the cyclic conjugated diene-based polymer include 1,2- or 1,4-addition polymerization of cyclic conjugated diene monomers such as cyclopentadiene and 1,3-cyclohexadiene. And the hydrogenated product thereof. The method for synthesizing these polymers is not particularly limited, and a known method may be appropriately selected.

(4) Vinyl alicyclic hydrocarbon polymer As examples of vinyl alicyclic hydrocarbon polymers, polymers of vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane, and hydrogenation thereof. Products; hydrogenated products of aromatic ring portions of polymers of vinyl aromatic monomers such as styrene and α-methylstyrene. The vinyl alicyclic hydrocarbon polymer may be a copolymer of a vinyl alicyclic hydrocarbon monomer and / or a vinyl aromatic monomer and another monomer. The vinyl alicyclic hydrocarbon-based polymer may be any copolymer such as a random copolymer or a block copolymer. The method for synthesizing these polymers is not particularly limited, and a known method may be appropriately selected.

  The alicyclic structure-containing polymer is a crystalline alicyclic structure-containing polymer (hereinafter sometimes referred to as “polymer (α)”) because it is easy to form a substrate layer that is superior in heat resistance and the like. Is preferred.

  “Crystallinity” refers to the property that the melting point can be observed by differential scanning calorimetry (DSC) by optimizing the measurement conditions and the like, and is determined by the stereoregularity of the polymer chain.

  As the polymer (α), for example, a dicyclopentadiene ring-opened polymer hydride having syndiotactic stereoregularity described in International Publication No. 2012/033076 (hereinafter referred to as “polymer (α1)”) Dicyclopentadiene ring-opening polymer hydride having isotactic stereoregularity described in JP-A No. 2002-249553, and norbornene ring-opening polymer hydride described in JP-A 2007-16102 Etc. As the polymer (α), the polymer (α1) is preferable.

  The melting point of the polymer (α) is preferably 200 to 300 ° C, more preferably 250 to 300 ° C. The polymer (α) having a melting point in this range has a good balance between properties such as heat resistance and moldability.

  The degree of stereoregularity of the polymer (α1) is not particularly limited, but a polymer having higher degree of stereoregularity is preferable because of excellent mechanical strength, heat resistance, chemical resistance, low water absorption and the like. Specifically, the ratio of racemo dyad to the repeating unit obtained by ring-opening polymerization of dicyclopentadiene and then hydrogenating is preferably 51% or more, and more preferably 60% or more. 70% or more is particularly preferable. The higher the ratio of racemo dyad, that is, the higher the syndiotactic stereoregularity, the higher the polymer (α1) has a melting point.

The ratio of racemo dyad can be determined by ¹³ C-NMR measurement. Specifically, ¹³ C-NMR measurement was performed using ortho-dichlorobenzene-d4 as a solvent and an inverse-gated decoupling method at 150 ° C., and a 43.35 ppm signal derived from meso-dyad and from racemo-dyad The ratio of racemo dyad can be determined from the signal intensity ratio of 43.43 ppm.

  In dicyclopentadiene, there are endo and exo stereoisomers. In the present invention, only one stereoisomer may be used, or a mixture of both isomers in an arbitrary ratio. May be. In the present invention, the crystallinity of the polymer (α1) is enhanced, and it is excellent in mechanical strength, heat resistance, chemical resistance, low water absorption, and the like. Therefore, it is preferable to increase the ratio of the end body or exo body. For example, the ratio of endo-form or exo-form is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more. In addition, since the synthesis | combination is easy, it is preferable that the ratio of an end body is high.

  The method for synthesizing the polymer (α1) is not particularly limited. For example, the polymer (α1) is obtained by performing a ring-opening polymerization reaction and a hydrogenation reaction according to a known method described in JP-A-2016-008283. Can be synthesized.

  What is necessary is just to adjust suitably content of the alicyclic structure containing polymer in an alicyclic structure containing resin layer. For example, it is 50 mass% or more with respect to the total mass of an alicyclic structure containing resin layer, Preferably it is 60 mass% or more, More preferably, it is 80 mass% or more.

  The alicyclic structure-containing resin layer may contain other components in addition to the alicyclic structure-containing polymer. Other components include resins other than alicyclic structure-containing polymers, antioxidants, crystal nucleating agents, fillers, flame retardants, flame retardant aids, colorants, antistatic agents, plasticizers, UV absorbers, light Stabilizers, near infrared absorbers, lubricants and the like can be mentioned.

  What is necessary is just to adjust suitably content of the said other component according to the objective. For example, it is less than 50% by weight, preferably less than 40% by weight, more preferably less than 20% by weight, based on the total mass of the alicyclic structure-containing resin layer.

  The thickness of the alicyclic structure-containing resin layer is not particularly limited, and may be adjusted as appropriate. The thickness of the alicyclic structure-containing resin layer is, for example, 1 to 400 μm, preferably 3 to 200 μm, and more preferably 10 to 100 μm.

  A commercially available product may be used for the alicyclic structure-containing resin layer. Examples of commercially available products include ZEONOR Film (registered trademark) ZF14 and ZF16 manufactured by ZEON Corporation.

  The alicyclic structure-containing resin layer may be surface-treated or untreated. Examples of the surface treatment include a treatment for increasing the adhesive force such as corona discharge treatment, plasma treatment, flame treatment, UV treatment, degreasing treatment, and surface roughening treatment.

<Plating underlayer>
The plating base layer is a layer adjacent to the alicyclic structure-containing resin layer. The plating underlayer contains (A) metal nanoparticles and (B) an organic π-conjugated compound. The plating base layer only needs to be adjacent to the alicyclic structure-containing resin layer, and may be formed only on one side of the alicyclic structure-containing resin layer, or may be formed on both sides.

  The plating underlayer of the laminate according to the present invention is formed by, for example, applying a plating underlayer composition containing (A) metal nanoparticles and (B) an organic π-conjugated compound onto the alicyclic structure-containing resin layer. And it can form by drying. The composition for a plating underlayer will be described by way of example.

  The composition for a plating underlayer contains (A) metal nanoparticles and (B) an organic π-conjugated compound. In addition, (C) a surfactant, (D) a binder, (E) a dispersion medium, and the like may be included as necessary.

(A) Metal nanoparticles As a metal which comprises metal nanoparticles, what is necessary is just to select suitably according to the kind etc. of the plating film formed on a plating base layer. Examples of the metal constituting the metal nanoparticles include Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po and A simple substance, a mixture, an alloy, or a compound of elements selected from the group consisting of At can be used.

  The metal constituting the metal nanoparticles is preferably a noble metal such as gold, silver or platinum, a transition metal such as nickel, or an amphoteric metal such as tin from the viewpoint of activity during plating formation. Here, the noble metal includes one or more selected from the group consisting of gold, silver, copper, platinum, palladium, iridium, rhodium, osmium, and ruthenium.

  Examples of the metal oxide constituting the metal nanoparticles include oxides and mixtures of metals selected from the group consisting of silver, copper, nickel, palladium, iron, aluminum, tin, and zinc.

  The shape of the metal nanoparticles is not particularly limited and may be appropriately selected. Examples thereof include a spherical shape and a substantially spherical shape.

  The particle diameter or maximum diameter of the metal nanoparticles is not particularly limited, and may be appropriately selected. From the viewpoint of stable dispersibility in a solvent or the like, the average particle size is preferably 500 nm or less, 250 nm or less, 200 nm or less, or 50 nm or less. On the other hand, 1 nm or more is preferable from the viewpoint of ease of production. Alternatively, the average particle diameter is more preferably 1 nm to 500 nm, 1 nm to 100 nm, or 1 nm to 50 nm. For example, when the average particle size is 500 nm or less, the ratio of the surface area per particle weight increases, and the dispersibility of the metal nanoparticles in a solvent or the like improves. The average particle size is based on the number standard (JIS Z 8827-1: 2008).

  Further, it is widely known that in metal nanoparticles, a unique absorption spectrum corresponding to the particle diameter is observed for each metal species. This is because the frequency of the irradiated light and the surface charge of the metal nanoparticles cause a strong interaction. For example, it is widely known that a spherical gold fine particle dispersion with a diameter of 20 nm exhibits a red color because it exhibits an absorption peak at about 520 nm, and a spherical silver fine particle dispersion with a diameter of 30 nm exhibits a brown color because it exhibits an absorption peak at a position of about 420 nm. It has been.

  A metal nanoparticle may be used individually by 1 type, and may be used in combination of 2 or more type.

  What is necessary is just to adjust suitably content of the metal nanoparticle in the composition for plating base layers. Content of metal nanoparticles is 0.01 mass% or more, 0.05 mass% or more, 0.5 mass% or more, 5 mass% or more, for example with respect to the total mass of the composition for plating foundation layers. It is 95% by mass or more, 20% by mass or more, 30% by mass or more, or 50% by mass or more, and is 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, or 50% by mass or less.

(B) Organic π-conjugated compound The organic π-conjugated compound has a function of imparting conductivity to the plating underlayer. This is because the organic π orbital of the organic π conjugated compound is close to the surface of the metal nanoparticle, causing a strong interaction between the organic π orbital and the metal nanoparticle orbital, and the organic π conjugated compound exhibits conductivity. It is guessed.

  Examples of the organic π-conjugated compound include organic π-conjugated ligands described in International Publication No. 2011/114713.

  As described above, the basic skeleton of the organic π-conjugated compound may be any as long as it can generate a strong interaction between the organic π orbital and the metal nanoparticle orbital. For example, a phthalocyanine ring or a naphthalocyanine ring may be used. Can be mentioned.

  Organic π-conjugated compounds are amino groups, mercapto groups, hydroxyl groups, carboxyl groups, phosphine groups, phosphonic acid groups, halogen groups, selenol groups, sulfo groups, sulfide groups, selenoether groups, alkylamino groups, amide groups, imides. May have one or more substituents such as a group, a cyano group, and a nitro group, and salts of these substituents (lithium salt, sodium salt, magnesium salt, potassium salt, calcium salt, ammonium salt) You may have.

In the laminate according to the present invention, the (B) organic π-conjugated compound has a phthalocyanine ring or a naphthalocyanine ring,
The (B) organic π-conjugated compound is an amino group, mercapto group, hydroxyl group, carboxyl group, phosphine group, phosphonic acid group, halogen group, selenol group, sulfo group, sulfide group, selenoether group and combinations thereof. It preferably has a substituent selected from the group consisting of

の１つ以上を有することが好ましい。 In the laminate according to the present invention, the (B) organic π-conjugated compound has the following structure:

It is preferred to have one or more of

のいずれか１つ以上であってもよい。これらの有機π共役系化合物の名称は、左から順に、それぞれ、２，３，９，１０，１６，１７，２３，２４−オクタキス［（２−Ｎ，Ｎ−ジメチルアミノエチル）チオ］フタロシアニン（ＯＴＡＰ）；２，３，１１，１２，２０，２１，２９，３０−オクタキス［（２−Ｎ，Ｎ−ジメチルアミノエチル）チオ］ナフタロシアニン（ＯＴＡＮ）；および１，８，１５，２２−テトラキス［（２−Ｎ，Ｎ−ジメチルアミノエチル）チオ］フタロシアニンである。 Further, the organic π-conjugated compound has the following structure:

Any one or more of these may be sufficient. The names of these organic π-conjugated compounds are 2,3,9,10,16,17,23,24-octakis [(2-N, N-dimethylaminoethyl) thio] phthalocyanine (in order from the left). 2,3,11,12,20,21,29,30-octakis [(2-N, N-dimethylaminoethyl) thio] naphthalocyanine (OTAN); and 1,8,15,22-tetrakis [(2-N, N-dimethylaminoethyl) thio] phthalocyanine.

  As the organic π-conjugated compound, those described above may be used alone or in combination of two or more.

  What is necessary is just to adjust suitably content of the organic (pi) conjugated compound in the composition for plating base layers. The content of the organic π-conjugated compound is, for example, 0.001% by mass or more or 0.01% by mass or more, and 10% by mass or less, or the total mass of the metal nanoparticles in the plating underlayer composition. 5% by mass or less.

(C) Surfactant As the surfactant, a known surfactant can be appropriately selected and used. Surfactant may be used individually by 1 type and may be used in combination of 2 or more type.

  Examples of the surfactant include a fluorine-based surfactant; an acetylene-based surfactant; and a silicone-based surfactant such as a polyether-modified silicone.

  The fluorosurfactant is not particularly limited, and examples thereof include anionic, cationic, amphoteric and nonionic fluorosurfactants. Among these, from the viewpoint of sufficiently ensuring the dispersibility of the metal nanoparticles in the dispersion medium while sufficiently improving the coating property of the composition for the plating underlayer, a nonionic fluorine-based surfactant is preferable.

  The fluorine-based surfactant preferably has a perfluoroalkenyl group or a perfluoroalkyl group, and more preferably has a perfluoroalkenyl group. If the fluorine-type surfactant which has the group mentioned above is used, the applicability | paintability of the composition for plating base layers can fully be improved. In addition, the conductivity of the plating base layer can be sufficiently increased.

  Furthermore, the fluorosurfactant is preferably a polyoxyethylene ether having an ethylene oxide chain. If the fluorochemical surfactant which has the structure mentioned above is used, the applicability | paintability of the composition for plating foundation layers can fully be improved. In addition, the conductivity of the plating base layer can be sufficiently increased.

  A commercially available product may be used as the surfactant. Examples of commercially available fluorosurfactants include Neogent's Footage M series such as Footage 251, 208M, 212M, 215M, and 250. Examples of commercially available acetylene surfactants include Olfine PD series such as Olfine PD001, 002W, 004, and 005 manufactured by Nissin Chemical Industry. Examples of commercially available silicone surfactants include Silface SAG series such as Silface SAG002, 005, 008, and 503A manufactured by Nissin Chemical Industry.

  It is preferable that the composition for plating underlayer further contains (C) a surfactant. Thereby, the uniformity of a plating film, the adhesiveness of the plating layer with respect to a base material layer, and electroconductivity improve.

  In the laminate according to the present invention, it is preferable that the plating base layer further includes (C) a surfactant. Thereby, the uniformity of a plating film, the adhesiveness of the plating layer with respect to a base material layer, and electroconductivity improve.

  The plating underlayer composition contains a surfactant, and the surfactant is selected from the group consisting of a fluorosurfactant, an acetylene surfactant, a silicone surfactant, and combinations thereof. Is preferred.

  In the laminate according to the present invention, the (C) surfactant is preferably selected from the group consisting of a fluorine-based surfactant, an acetylene-based surfactant, a silicone-based surfactant, and a combination thereof.

  The amount of the surfactant in the plating underlayer composition is not particularly limited, and may be adjusted as appropriate. For example, with respect to 100 parts by mass of the dispersion medium in the plating underlayer composition, 0.01 parts by mass or more, 0.05 parts by mass or more, 0.1 parts by mass or more, 0.2 parts by mass or more, 0.4 What is necessary is just to set it as 1 part by mass or more or 1 part by mass or more, 10 parts by mass or less, 5 parts by mass or less, 2 parts by mass or less, 1 part by mass or less, or 0.5 parts by mass or less. Moreover, what is necessary is just to adjust the quantity of surfactant suitably in the range which enters between 0.01-5 mass% with respect to the solid content of a plating base layer, for example.

(D) Binder The binder has a function of improving the adhesion of the plating base layer to the substrate and the adhesion of the plating film to the substrate. Further, the strength of the plating base layer itself can be improved. A binder may be used individually by 1 type and may be used in combination of 2 or more type.

  What is necessary is just to select suitably from a well-known binder as a binder. Examples of the binder include acrylic resin, polyester, polyurethane polyethylene resin, polypropylene, polystyrene, polyvinyl pyrrolidone, polyethylene glycol, polyamide, polyepoxy, polyvinyl alcohol, polysaccharide, protein; polyethyleneimine, polystyrene sulfonic acid, aromatic polyamide, carboxy. Methyl cellulose; cellulose nanofiber, chitin nanofiber, and the like.

  It is preferable that the composition for plating base layer further contains a binder. Thereby, the adhesiveness of the plating layer with respect to a base material layer improves.

  In the laminate according to the present invention, it is preferable that the plating base layer further contains (D) a binder. Thereby, the adhesiveness of the plating layer with respect to a base material layer improves.

  The amount of the binder in the plating underlayer composition is not particularly limited, and may be adjusted as appropriate. For example, 1 part by mass or more, 3 parts by mass or more, 5 parts by mass or more, 10 parts by mass or more, 20 parts by mass or more, 50 parts by mass or more, 70 parts by mass or less, 30 parts by mass with respect to 100 parts by mass of the metal nanoparticles. Or less, 20 parts by mass or less, 10 parts by mass or less, 5 parts by mass or less, or 3 parts by mass or less.

(E) Dispersion medium A dispersion medium has a function which adjusts the coating property of the composition for plating base layers. A dispersion medium may be used individually by 1 type, and may be used in combination of 2 or more type.

  The dispersion medium may be appropriately selected and used. For example, water alone or a mixed solution of water and a polar organic solvent miscible with water can be used. In these polar solvents containing water, dispersibility is easily secured by electrostatic repulsion between metal nanoparticles. As a polar organic solvent miscible with water, for example, a polar organic solvent having an SP value of 9.5 or more known as a solubility parameter can be exemplified. More specifically, for example, methanol, ethanol, propanol, 2-ethylhexanol, acetone, acetonitrile, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, dioxane, phenol, cresol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol Examples include ethylene glycol and glycerin.

  The amount of the dispersion medium in the plating underlayer composition is not particularly limited, and may be adjusted as appropriate. For example, 20% by mass or more, 30% by mass or more, 50% by mass or more, 70% by mass or more, 95% by mass or more, or 99% by mass or less, 90% by mass or less, based on the total mass of the composition for the plating underlayer. What is necessary is just to set it as 80 mass% or less, 50 mass% or less, or 30 mass% or less.

  The method for preparing the composition for the plating underlayer is not particularly limited, and can be obtained by mixing each component according to a conventional method.

  The method for forming the plating underlayer is not particularly limited. Examples of the method for forming the plating underlayer include a printing method, a coating method, and an immersion method.

  Examples of the printing method include screen printing, flexographic printing, offset printing, dip printing, inkjet printing, dispenser printing, gravure printing, gravure offset printing, pad printing, and the like.

  Application methods include spin coaters, air knife coaters, curtain coaters, die coaters, blade coaters, roll coaters, gate roll coaters, bar coaters, rod coaters, gravure coaters, spray coaters, wire bars, etc. Is mentioned.

  The drying method after apply | coating the composition for plating base layers is not specifically limited. For example, a method of heating at normal temperature or under any condition of the atmosphere, an inert gas atmosphere, a reducing atmosphere, or a reduced pressure can be used. For example, it is preferable to heat from 40 ° C. to 150 ° C. in the atmosphere. Moreover, you may heat from 50 degreeC to 95 degreeC under air | atmosphere.

  The film thickness of the plating base layer is not limited and may be adjusted as appropriate. For example, the film thickness may be 30 μm or less, 10 μm or less, 5 μm or less, or 1 μm or less, 50 nm or more, 100 nm or more, 200 nm or more, or 500 nm or more.

  By including the metal nanoparticles and the organic π-conjugated compound as described above, the plating base layer is excellent in adhesion and conductivity of the plating layer to the base material layer. Moreover, the uniformity of the plating film adjacent to the plating base layer is also excellent.

  The content of the metal nanoparticles in the plating underlayer is measured by TG-DTA analysis which is one type of thermogravimetric analysis. In the present invention, in the TG-DTA analysis, the weight at the time of 150 ° C. when the temperature is raised from room temperature is defined as the coating weight, and the remaining weight at the time of further heating is 600 ° C. Weight). The specific measurement method is to measure the weight and differential heat while raising the temperature from room temperature to 600 ° C. under a temperature rise condition of 10.0 ° C./min. Observe fluctuations. Thereby, measurement data can be obtained.

  Since the plating underlayer is excellent in conductivity as described above, the surface resistivity can be 0.5Ω / □ or less or 0.1Ω / □ or less even if the film thickness is, for example, 1 μm or less. It is also possible to form a copper plating film by electroplating by energizing the plating base layer. The surface resistivity is measured by Loresta-GX MCP-T610 manufactured by Mitsubishi Chemical Analytic.

  In the plating underlayer, a part of the metal nanoparticles can be exposed on the surface of the plating underlayer. Thereby, conductivity is obtained even after low temperature treatment, and there is an effect that it works as a better plating base.

  In one embodiment, the laminate according to the present invention is a laminated film. In the case of a laminated film, the thickness is, for example, 5 to 500 μm, preferably 10 to 300 μm, more preferably 12 to 250 μm. By setting it as this range, the balance of handling property and flexibility of the laminated film is good.

The laminate according to the present invention is
In order, adjacent to the alicyclic structure-containing resin layer,
A plating underlayer;
Plating film,
It is a laminated body in any one of the above which has. Thereby, it is excellent in the transparency of a base material layer, the uniformity of a plating film, the adhesiveness of the plating layer with respect to a base material layer, and electroconductivity.

(Plating film)
The plating film is not particularly limited and may be appropriately selected. For example, either electrolytic plating or electroless plating may be used. The type of plating metal is not particularly limited. Examples thereof include copper, nickel, zinc, tin, silver, gold, platinum, chromium, cadmium, combinations thereof, alloys thereof, complex ions thereof, and the like. Also, for example, surface technology, Vol. 42, no. 4, 1991, pp 425-430, etc., an electroless copper plating solution can be obtained. In addition, a commercially available plating solution may be used.

  Since the laminated body which has a plating layer which concerns on this invention has the advantage mentioned above, it can be used conveniently for a transparent flexible circuit board, a transparent sensor, a transparent film antenna, etc.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, these Examples aim at the illustration of this invention, and do not limit this invention at all. Unless otherwise specified, the blending amount means parts by mass.

The materials used in the examples are as follows.
(Base material layer)
Alicyclic structure-containing resin layer 2: ZEONOR film (registered trademark) ZF14-050 (thickness 50 μm) manufactured by ZEON Corporation
Comparative substrate layer 1: PET film manufactured by Teijin Film Solutions (trade name: Tetoron HL92W, thickness: 50 μm)
(Surfactant)
Surfactant 1: Trade name FT 251 manufactured by Neos (Fluorosurfactant having a nonionic oxyethylene ether structure)
Surfactant 2: Trade name Olphine PD002W (acetylene glycol surfactant) manufactured by Nissin Chemical Industry Co., Ltd.
(binder)
Binder: Trade name AQ nylon A-90 (water-soluble nylon) manufactured by Toray Industries, Inc.
(Comparative plating underlayer composition)
Comparative plating underlayer composition: DOWA Electronics Co., Ltd. (aqueous solvent, silver concentration 40-60 mass%)
(Other)
Hydrotalcite-like compound: Kyoward (registered trademark) 2000 manufactured by Kyowa Chemical Industry Co., Ltd.
Filtration aid: trade name Radiolite (registered trademark) # 1500 manufactured by Showa Chemical Industry Co., Ltd.
Antioxidant: Tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, trade name of Irganox (registered trademark) 1010 manufactured by BASF Japan
Electroless copper plating solution: Trade name ARG Copper Cellophane adhesive tape manufactured by Okuno Pharmaceutical Co., Ltd .: Nichiban Co., Ltd.

The apparatus used in the examples is as follows.
PP pleated cartridge filter: Product name TCP-HX manufactured by ADVANTEC Toyo
Twin screw extruder: TEM-37B manufactured by Toshiba Machine Co., Ltd.
Hot Melt Extrusion Film Forming Machine: Product Name Measuring Extruder Type Me-20 / 2800V3 manufactured by Optical Control Systems
UV-ozone treatment apparatus: Model SSP16-110 manufactured by Sen Special Light Company
Wire bar: # 05 manufactured by Daiichi Rika Co., Ltd.
Resistivity meter: Loresta-GX MCP-T610 manufactured by Mitsubishi Chemical Analytic Co.
Spectrophotometer: Model number U-4100 manufactured by Hitachi High-Technologies Corporation
Differential heat / thermogravimetric measuring instrument: Model number manufactured by Shimadzu Corporation: DTG-60H
Viscometer: Trade name TV-22 manufactured by Toki Sangyo Co., Ltd.
Surface tension meter: Product name DG-1 manufactured by Surface Sokki Seisakusho
Transmission electron microscope: Model number manufactured by Hitachi High-Technologies Corporation: H-7500

  Each measurement in the examples was performed by the following method.

Glass transition temperature and melting point Using a differential scanning calorimeter (DSC), according to JIS K7121, differential scanning calorimetry was performed under the condition of a heating rate of 10 ° C / min, and the glass transition temperature and melting point of the polymer were measured.

Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
Gel permeation chromatography (GPC) was performed at 40 ° C. using tetrahydrofuran as a solvent, and the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were determined as polystyrene equivalent values.
Measuring apparatus: Gel permeation chromatography (GPC) system “HLC-8220” (manufactured by Tosoh Corporation)
Column: “H type column” (manufactured by Tosoh Corporation)

Hydrogenation rate of unsaturated bonds
^{Based on the 1} H-NMR measurement, the hydrogenation rate of the unsaturated bond in the polymer was determined.

(Synthesis of crystalline alicyclic structure-containing polymer)
In a pressure-resistant reaction vessel made of metal whose inside is replaced with nitrogen, 154.5 parts by mass of cyclohexane, 42.8 parts by mass of a cyclohexane solution (concentration 70%) of dicyclopentadiene (endo content 99% or more) (as dicyclopentadiene) 30 parts by mass) and 1.9 parts by mass of 1-hexene were added, and the container was heated to 53 ° C. On the other hand, a solution obtained by dissolving 0.014 parts by mass of tetrachlorotungstenphenylimide (tetrahydrofuran) complex in 0.70 parts by mass of toluene was added to an n-hexane solution of diethylaluminum ethoxide (concentration 19%). 061 parts by mass were added and stirred for 10 minutes to prepare a catalyst solution. This catalyst solution was added to the reaction vessel, and a ring-opening polymerization reaction was performed at 53 ° C. for 4 hours to obtain a solution containing a dicyclopentadiene ring-opening polymer. To 200 parts by mass of the resulting solution containing dicyclopentadiene ring-opening polymer, 0.037 part of 1,2-ethanediol was added as a terminator and stirred at 60 ° C. for 1 hour to stop the polymerization reaction. . Thereafter, 1 part by mass of a hydrotalcite-like compound was added, heated to 60 ° C., and stirred for 1 hour. 0.4 parts by mass of a filter aid was added, and the adsorbent was filtered off using a PP pleated cartridge filter to obtain a solution containing a dicyclopentadiene ring-opening polymer. A part of this solution was used to measure the molecular weight of the dicyclopentadiene ring-opened polymer. The weight average molecular weight (Mw) was 28,100, the number average molecular weight (Mn) was 8,750, the molecular weight distribution (Mw / Mn) was 3.21.

  After purification, 200 parts by mass of a solution containing dicyclopentadiene ring-opened polymer (polymer content 30 parts by mass), 100 parts by mass of cyclohexane, 0.0043 parts by mass of chlorohydridocarbonyltris (triphenylphosphine) ruthenium The hydrogenation reaction was carried out at 6 MPa and 180 ° C. for 4 hours. The reaction liquid was a slurry liquid in which a solid content was deposited. The reaction solution is centrifuged to separate the solid content and the solution, and the solid content is dried under reduced pressure at 60 ° C. for 24 hours to obtain a hydrogenated dicyclopentadiene ring-opening polymer (crystalline alicyclic structure-containing polymer). 28.5 parts by mass were obtained. The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride was 99% or more, the glass transition temperature was 98 ° C., and the melting point was 262 ° C.

(Manufacture of alicyclic structure-containing resin layer 1)
After 100 parts by mass of the dicyclopentadiene ring-opening polymer hydride is mixed with 0.8 parts by mass of an antioxidant, the mixture is put into a twin screw extruder, and a strand-like molded product is obtained by hot melt extrusion molding. After being obtained, this was chopped with a strand cutter to obtain pellets. The operating conditions of the twin screw extruder are as follows.
-Barrel set temperature: 270-280 ° C
・ Die setting temperature: 250 ℃
・ Screw speed: 145rpm
・ Feeder rotation speed: 50 rpm

The obtained pellets were wound on a roll at a speed of 4 m / min using a hot melt extrusion film forming machine equipped with a T die, and a 50 μm thick film molded body (grease without surface treatment) A ring structure-containing resin layer 1) was obtained. The operating conditions of the film forming machine are as follows.
・ Barrel temperature setting: 280 ℃ ～ 290 ℃
-Die temperature: 270 ° C
-Screw rotation speed: 30rpm

(Surface treatment of alicyclic structure-containing resin layer 1)
With respect to a part of the plurality of alicyclic structure-containing resin layers 1 obtained as described above, on both surfaces thereof, using a UV-ozone treatment apparatus, surface treatment (UV illuminance: 16 mW / cm ² ) UV-ozone treatment).

深田らの合成方法（工業化学雑誌 第６４巻 第１０号（１９６１）１８１７−１８１９および米国特許第４５２２７５５号を参考に上記構造式で表されるテトラカルボン酸フタロシアニン（ＴＣＡＰ）の合成を行った。 (Synthesis of phthalocyanine tetracarboxylic acid (TCAP) tetrasodium salt)

Synthesis of tetracarboxylic acid phthalocyanine (TCAP) represented by the above structural formula was performed with reference to the synthesis method of Fukada et al. (Industrial Chemical Journal, Vol. 64, No. 10 (1961) 1817-1819 and US Pat. No. 4,522,755).

  Specifically, 41.8 g (217.5 mmol) of trimellitic anhydride, 145 g of urea, and 11.5 g of ammonium molybdate were added to a 1 L reaction vessel containing a stirring bar, respectively, and 220 mL of triethylene glycol dimethyl ether was added thereto. In addition, the inside of the container was replaced with nitrogen. When the mixture was heated to 140 ° C. with stirring, the solid content began to become viscous. After stirring at 140 ° C. for 1 hour, the reaction temperature was raised to 210 ° C., and a green solid began to be obtained with foaming. When heated at 210 ° C. for 2 hours, the heating was stopped and the reaction system was cooled to room temperature. A small amount of formic acid was added and dissolved in the remaining ammonium carbonate, and then the green solid was crushed small enough for washing. This green solid was suspended in methanol and centrifuged, and then the supernatant was removed. By repeating this operation twice, triethylene glycol dimethyl ether was removed. Subsequently, the obtained solid was stirred in 300 mL of a 3% aqueous sodium hydroxide solution and refluxed for 1 hour to hydrolyze the amide and carboxylate. 650 mL of 2-propanol was added to form a precipitate, and a green solid was obtained by centrifugation. This green solid was subjected to centrifugal purification in the order of acetone, methanol, and acetone, and then dried overnight using a vacuum pump to obtain 32.8 g of TCAP tetrasodium salt (crude yield 77.5% as tetrasodium salt). It was.

(Preparation of silver nanoparticle dispersion)
J. et al. Phys. Chem. , 1982, 86 (17), pp 3391-3395 (DOI: 10.1021 / j100214a025), 100 L of silver nanoparticle dispersion liquid protected with citric acid (silver solid content concentration: 0.02%) ) To this, 5 L of 4 mM aqueous solution of the TCAP tetrasodium salt was added and stirred well. Subsequently, a silver nanoparticle dispersion liquid protected with a small amount of an aromatic compound (organic π-conjugated compound) was obtained by centrifugal filtration purification. The silver nanoparticle dispersion liquid had a solid content weight of 52.2%. Moreover, when Tg-DTA analysis was performed about solid content of this silver nanoparticle dispersion liquid, organic substance content in solid content was 0.4 weight%. Further, when the ultraviolet-visible absorption spectrum of the diluted solution of the silver nanoparticle dispersion was measured with a spectrophotometer, absorption due to the surface plasmon band of the silver nanoparticles was observed near the wavelength of 395 nm. Moreover, when this silver nanoparticle dispersion liquid was dried on the support grid and observed with the scanning electron microscope, the number average particle diameter of the silver nanoparticle was 0.03 micrometer.

(Preparation of composition 1 for plating underlayer)
9 parts by mass of binder (water-soluble nylon), 28 parts by mass of pure water, 108 parts by mass of ethylene glycol, 2 parts by mass of 2-ethylhexanol, and surfactant with respect to 100 parts by mass of the silver nanoparticle dispersion. By adding 0.1 part by mass of 1, a composition 1 for a plating underlayer having a solid content concentration of 25%, a viscosity of 4 cps, and a surface tension of 29 mN was prepared.

(Preparation of composition 2 for plating underlayer)
In the preparation of the composition 1 for plating underlayer, except that 0.1 part by mass of the surfactant 1 is changed to 0.2 parts by mass of the surfactant 2, the solid content concentration is 25% and the viscosity is the same. A composition 2 for plating underlayer having 4 cps and a surface tension of 29 mN was prepared.

Example 1
The two surface-treated alicyclic structure-containing resin layers 1 are allowed to stand on a hot plate set at 75 ° C. with the treated surface as the upper surface, and then the composition 1 for plating underlayer is greased using a wire bar. It apply | coated to the center part of the width direction of the ring structure containing resin layer 1. FIG. After drying on the hot plate until the fluidity of the coating film disappeared, it was further dried on a hot plate at 85 ° C. for 10 minutes. This was further heat-treated in an oven at 180 ° C. for 30 minutes to obtain two alicyclic structure-containing resin layers 1 having a silver film (plating underlayer) formed on one side. The thickness of the plating underlayer was 0.5 to 1 μm. Further, similarly, a plating base layer is formed on the other surface of one of the two alicyclic structure-containing resin layers 1, and a silver film (plating) is formed on both surfaces of the alicyclic structure-containing resin layer 1. A laminated body on which an underlayer was formed was obtained.

(Examples 2-6 and Comparative Examples 1-4)
In Example 1, as shown in Table 1, the type of base material, the presence or absence of surface treatment (UV-ozone treatment) of the base material, the heat treatment temperature when forming the plating base layer, and the type of composition for the plating base layer In the same manner as described above, a laminate in which a plating base layer (or comparative plating base layer) was formed on one or both surfaces of the base material layer was obtained.

(Formation of plating film)
The laminates obtained in each Example and Comparative Example were immersed in an electroless copper plating solution heated to 45 ° C. for 5 minutes, and then washed with ion-exchanged water. Furthermore, the laminated body which has a copper plating film | membrane on one side or both surfaces was obtained by drying for 30 minutes in 100 degreeC oven. When the cross section of this laminated body was observed by SEM, the thickness of the copper plating film was in the range of 0.5 to 1 μm.

  Using the laminates obtained in each Example and Comparative Example, the transparency of the substrate, the state (uniformity) of the copper plating film, the adhesion, the conductivity and the insulation were evaluated by the following methods. These results are also shown in Table 1.

(transparency)
Of the laminate having a copper plating film on one side, the width direction end (surface of the alicyclic structure-containing resin layer) of the laminate in which the copper plating film is not formed, and the alicyclic structure before forming another plating base layer The surface of the containing resin layer was visually observed, and the transparency was evaluated according to the following criteria.
○: No change ×: Change such as yellowing or whitening

(Plating film state)
The copper plating film of the laminated body which has a copper plating film on both surfaces was observed visually, and the state of the plating film was evaluated according to the following criteria.
○: No copper plating film peeling or pinhole ×: Copper plating film peeling or pinhole

(Adhesion)
Regarding the laminate immediately after the copper plating film is formed on both sides and the laminate after the plating film is formed and further subjected to a moisture absorption treatment for 1000 hours under conditions of a temperature of 85 ° C. and a humidity of 85%, JIS K5600 In accordance with the same, use a guide at any part of the copper plating film on both sides to cut into 6 vertical and horizontal incisions with a cutter and divide into 25 (1 mm width and 1 mm width), then cross-cut with cellophane adhesive tape. A tape peel test was performed and evaluated according to the following criteria. The number of grids to be evaluated is 50.
A: No. of peeled lattices 0: No. of peeled lattices is 1 or more and 5 or less Δ: No. of peeled lattices is 6 or more, 25 or less ×: Number of peeled lattices is 26 50 or less

(Conductivity)
The surface resistivity of a layered body having a copper plating film on one side of the copper plating film and the plating base layer was measured at four points with a resistivity meter, and the average value was evaluated according to the following criteria.
A: The average value of the surface resistivity is less than 0.1Ω / □, ○: The average value of the surface resistivity is 0.1Ω / □ or more and less than 0.5Ω / □, and the average value of the surface resistivity is 0. .5Ω / □ or more, less than 1Ω / □ ×: The average surface resistivity is 1Ω / □ or more

(Insulation)
Four test pieces of 1 cm in length and width were cut out from a laminate having a copper plating film on both surfaces, and a test of applying a voltage of 50 V under conditions of a temperature of 85 ° C. and a humidity of 85% was performed for 1000 hours. When the resistance value during the test was less than 1.0 × 10 ⁶ Ω, the insulation was poor, and evaluation was performed according to the following criteria.
○: The number of test pieces with poor insulation is zero. ×: The number of test pieces with poor insulation is one or more.

  From Table 1, in the Example, the laminated body excellent in transparency of a base material, the uniformity of a plating film, the adhesiveness of the plating layer with respect to a base material layer, electroconductivity, and insulation was obtained. Furthermore, when Examples 1 and 2 are compared with Comparative Examples 1 and 3, in Examples 1 and 2, the transparency of the substrate is increased even when the temperature of the heat treatment during plating formation is set to a high temperature such as 180 ° C. While being excellent in the uniformity of the plating film, a laminate having improved adhesion of the plating layer to the base material layer was obtained.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body excellent in transparency of a base material layer, the uniformity of a plating film, the adhesiveness of the plating layer with respect to a base material layer, and electroconductivity can be provided. Such a laminate can be suitably used for a transparent flexible circuit board, a transparent sensor, a transparent film antenna, and the like.

Claims (7)

In order, adjacent to the alicyclic structure-containing resin layer,
A plating underlayer;
A laminate having
The plating base layer is
(A) metal nanoparticles,
(B) an organic π-conjugated compound;
The laminated body characterized by including.   The laminate according to claim 1, wherein the plating base layer further comprises (C) a surfactant.   The laminate according to claim 2, wherein the (C) surfactant is selected from the group consisting of a fluorosurfactant, an acetylene surfactant, a silicone surfactant, and a combination thereof. The (B) organic π-conjugated compound has a phthalocyanine ring or a naphthalocyanine ring,
The (B) organic π-conjugated compound is an amino group, mercapto group, hydroxyl group, carboxyl group, phosphine group, phosphonic acid group, halogen group, selenol group, sulfo group, sulfide group, selenoether group and combinations thereof. The laminated body as described in any one of Claims 1-3 which has a substituent selected from consisting of. The (B) organic π-conjugated compound has the following structure:

The laminated body as described in any one of Claims 1-4 which has one or more of these.   The laminate according to any one of claims 1 to 5, wherein the plating base layer further contains (D) a binder. In order, adjacent to the alicyclic structure-containing resin layer,
A plating underlayer;
Plating film,
The laminate according to any one of claims 1 to 6, which has