JP2018079645A - Laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated film which includes a substrate layer and a silver coating film adjacent to the substrate layer and is excellent in transparency of the substrate layer, interlayer adhesion, insulating properties, and conductivity of the silver coating film.SOLUTION: The laminated film includes the substrate layer and the silver coating film adjacent to the substrate layer. The substrate layer is formed of an alicyclic structure-containing resin film. The silver coating film is obtained by sintering a coating film containing silver nanoparticles formed on the substrate layer. The silver nanoparticles are obtained by thermally decomposing a mixture containing an amine compound having 6 or more carbon atoms, an amine compound having 5 or less carbon atoms, and a silver compound.SELECTED DRAWING: None

Description

  The present invention relates to a laminated film having a base material layer and a silver coating adjacent to the base material layer and excellent in transparency, interlayer adhesion, insulation, and silver coating conductivity of the base material layer.

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.

However, according to the study of the present inventor, the laminated film obtained using the metal fine particles described in Patent Document 1 is inferior in transparency of the base material layer, inferior in conductivity of the metal layer, or insulated. It turned out that it may be inferior.
For this reason, the laminated | multilayer film which is excellent in the transparency of a base material layer, interlayer adhesiveness, insulation, and the electroconductivity of a silver film was requested | required.

JP 2012-162767 A

  The present invention has been made in view of the above-described circumstances, and has a base material layer and a silver coating adjacent to the base material layer, and the transparency of the base material layer, interlayer adhesion, insulation, and It aims at providing the laminated | multilayer film which is excellent in the electroconductivity of a silver film.

  In order to solve the above-mentioned problems, the present inventor has intensively studied a laminated film having a base material layer and a silver coating adjacent to the base material layer. As a result, the base material layer is formed by using the alicyclic structure-containing resin film and sintering the coating film containing silver nanoparticles obtained by a specific method to form a silver coating film. It has been found that a laminated film having excellent layer transparency, interlayer adhesion, insulation, and silver film conductivity can be obtained. The present invention has been made based on such findings.

Thus, according to the present invention, the following laminated films [1] to [6] are provided.
[1] A laminated film having a base material layer and a silver film adjacent to the base material layer, wherein the base material layer is composed of an alicyclic structure-containing resin film, It is formed by sintering a coating film containing silver nanoparticles formed on a base material layer, and the silver nanoparticles are an amine compound having 6 or more carbon atoms, an amine compound having 5 or less carbon atoms, And a laminated film obtained by heating a mixture obtained by mixing a silver compound.
[2] The laminated film according to [1], wherein the alicyclic structure-containing polymer contained in the alicyclic structure-containing resin film is a crystalline alicyclic structure-containing polymer.
[3] The laminated film according to [1] or [2], wherein the silver nanoparticles have an average particle size of 0.5 to 100 nm.
[4] The amine compound having 6 or more carbon atoms is represented by the following formula (1):

(R ¹ represents a hydrocarbon group having 6 or more carbon atoms.)
Wherein the amine compound having 5 or less carbon atoms is represented by the following formula (2):

(R ² represents a hydrocarbon group having 5 or less carbon atoms.)
The laminated film according to any one of [1] to [3], which is an amine compound represented by:
[5] The laminated film according to any one of [1] to [4], wherein the amount of the amine compound having 5 or less carbon atoms is 10 to 80 mol% in the total amount of the amine compound.
[6] The laminated film according to any one of [1] to [5], wherein the silver compound is silver oxalate.

  According to this invention, it has a base material layer and the silver film adjacent to the said base material layer, and is the laminated | multilayer film which is excellent in the transparency of a base material layer, interlayer adhesiveness, insulation, and the electroconductivity of a silver film. Is provided.

  The laminated film of the present invention is a laminated film having a base material layer and a silver coating adjacent to the base material layer, wherein the base material layer is composed of an alicyclic structure-containing resin film, and the silver The coating is formed by sintering a coating film containing silver nanoparticles formed on the base material layer, and the silver nanoparticles are an amine compound having 6 or more carbon atoms, and 5 or less carbon atoms. It is obtained by heating a mixture obtained by mixing the amine compound and silver compound.

[Base material layer]
The base material layer which comprises the laminated | multilayer film of this invention consists of an alicyclic structure containing resin film.
The alicyclic structure-containing resin film is a film containing an alicyclic structure-containing polymer as a resin component. The alicyclic structure-containing polymer is a polymer having an alicyclic structure in the main chain and / or side chain. Among them, those having an alicyclic structure in the main chain are preferable because a substrate layer excellent in mechanical strength, heat resistance, chemical resistance, low water absorption and the like can be easily formed.
Examples of the alicyclic structure include a saturated cyclic hydrocarbon (cycloalkane) structure and an unsaturated cyclic hydrocarbon (cycloalkene) structure. Among these, a cycloalkane structure is preferable because it is easy to form a substrate layer that is excellent in mechanical strength, heat resistance, chemical resistance, low water absorption, and the like.
Although the carbon atom number which comprises an alicyclic structure is not specifically limited, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is the range of 5-15 pieces. When the number of carbon atoms constituting the alicyclic structure is within these ranges, it is easy to form a base material layer that has a higher balance of properties such as mechanical strength, heat resistance, chemical resistance, and low water absorption. Become.

  The ratio of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer can be appropriately selected. The ratio of this repeating unit is usually 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 of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer is 30% by weight or more, a base material layer having excellent mechanical strength, heat resistance, chemical resistance, low water absorption and the like is formed. It becomes easy. The remainder other than the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer is not particularly limited and is appropriately selected.

Although the weight average molecular weight (Mw) of an alicyclic structure containing polymer is not specifically limited, Usually, 5,000-500,000, Preferably it is 8,000-200,000, More preferably, it is 10,000-100,000. It is. When the weight average molecular weight (Mw) of the alicyclic structure-containing polymer is within these ranges, various properties such as mechanical strength of the base material layer, and workability when producing the alicyclic structure-containing resin film, Is more highly balanced.
Although molecular weight distribution (Mw / Mn) of an alicyclic structure containing polymer is not specifically limited, Usually, 1.0-4.0, Preferably it is 1.0-3.0, More preferably, it is 1.0-2. 5.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the alicyclic structure-containing polymer can be determined according to the method described in Examples.

Although the glass transition temperature (Tg) of an alicyclic structure containing polymer is not specifically limited, Usually, it is 50-200 degreeC, Preferably it is 80-170 degreeC.
It becomes easy to form the base material layer which is excellent in heat resistance because the glass transition temperature (Tg) of an alicyclic structure containing polymer is 80 degreeC or more.
The glass transition temperature (Tg) can be measured based on JIS K 6911.

Specific examples of the alicyclic structure-containing polymer include (1) norbornene polymer, (2) monocyclic olefin polymer, (3) cyclic conjugated diene polymer, and (4) vinyl alicyclic carbonization. Examples thereof include hydrogen-based polymers. Among these, norbornene-based polymers are preferable because they easily form a base layer having excellent mechanical strength, heat resistance, chemical resistance, low water absorption, and the like.
In the present specification, these polymers mean not only a polymerization reaction product but also a hydrogenated product thereof.

(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 polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization, and these ring-opening polymers. And an addition polymer of a norbornene monomer, an addition polymer of a norbornene monomer and another monomer copolymerizable therewith, and the like.

Examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene) and its derivatives (which have a substituent in the ring), tricyclo [4.3.0]. ^1,6 . 1 ^2,5] deca-3,7-diene (trivial name: dicyclopentadiene) and derivatives thereof, tetracyclo ^{[9.2.1.0 2,10.} 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (methanotetrahydrofluorene, 7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene, 1,4- Methano-1,4,4a, 9a-tetrahydrofluorene) and its derivatives, tetracyclo [4.4.1 ^2,5 . 1 ^7,10 . 0] dodec-3-ene (common name: tetracyclododecene) and its derivatives.

Examples of the substituent 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 [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene, 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene and the like.
These norbornene monomers can be used singly or in combination of two or more.

  Examples of other monomers capable of ring-opening copolymerization with norbornene monomers include monocyclic olefin monomers such as cyclohexene, cycloheptene, cyclooctene, and derivatives thereof. Examples of these substituents are the same as those shown as the substituents of the norbornene monomer.

  Other monomers capable of addition copolymerization with norbornene monomers include α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene and 1-hexene, and derivatives thereof. Cycloolefins such as cyclobutene, cyclopentene, cyclohexene, cyclooctene, and derivatives thereof; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene Non-conjugated dienes such as; Among these, α-olefins are preferable and ethylene is particularly preferable. Examples of these substituents are the same as those shown as the substituents of the norbornene monomer.

A ring-opening polymer of a norbornene-based monomer, or a ring-opening polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization with a monomer component is a known ring-opening polymerization. It can be synthesized by polymerizing in the presence of a catalyst. Examples of the ring-opening polymerization catalyst include a catalyst comprising a metal halide such as ruthenium or osmium, a nitrate or an acetylacetone compound, and a reducing agent, or a metal halide or acetylacetone such as titanium, zirconium, tungsten, or molybdenum. Examples thereof include a catalyst composed of a compound and an organoaluminum compound.
The ring-opening polymer hydrogenated product of norbornene-based monomer is usually obtained by adding a known hydrogenation catalyst containing a transition metal such as nickel or palladium to the polymerization solution of the ring-opening polymer, and carbon-carbon unsaturation. It can be obtained by hydrogenating the bond.

  An addition polymer of a norbornene monomer, or an addition polymer of a norbornene monomer and another monomer copolymerizable with the norbornene monomer, in the presence of a known addition polymerization catalyst. It can be synthesized by polymerization. Examples of the addition polymerization catalyst include a catalyst composed of a titanium, zirconium or vanadium compound and an organoaluminum compound.

  Among these norbornene-based polymers, a ring-opening polymer hydrogenated product of norbornene-based monomers is easy to form a base layer having excellent mechanical strength, heat resistance, chemical resistance, low water absorption, etc. preferable.

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

(3) Cyclic conjugated diene polymer As the cyclic conjugated diene polymer, for example, a polymer obtained by subjecting a cyclic conjugated diene monomer such as cyclopentadiene or cyclohexadiene to 1,2- or 1,4-addition polymerization, and Examples thereof include hydrogenated products.
A method for synthesizing these addition polymers is not particularly limited, and a known method can be appropriately used.

(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. A hydrogenated product of an aromatic ring portion of a polymer of a vinyl aromatic monomer such as styrene or α-methylstyrene. Further, it may be a copolymer of a vinyl alicyclic hydrocarbon monomer or vinyl aromatic monomer and another monomer copolymerizable with these monomers. Examples of such a copolymer include a random copolymer and a block copolymer.
The method for synthesizing these polymers is not particularly limited, and known methods can be used as appropriate.

A crystalline alicyclic structure-containing polymer (hereinafter sometimes referred to as “polymer (α)”) is preferred as the alicyclic structure-containing polymer because it is easy to form a substrate layer that is superior in heat resistance and the like.
“Crystallinity” refers to the property that the melting point can be observed with a differential scanning calorimeter (DSC) by optimizing the measurement conditions and the like, and is determined by the stereoregularity of the polymer chain.

  As the polymer (α), a dicyclopentadiene ring-opened polymer hydride having syndiotactic stereoregularity described in International Publication No. 2012/033076 pamphlet, an isoform described in JP-A No. 2002-249553 Examples thereof include dicyclopentadiene ring-opened polymer hydrides having tactic stereoregularity, norbornene ring-opened polymer hydrides described in JP-A-2007-16102, and the like.

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 polymer (α) is preferably a dicyclopentadiene ring-opened polymer hydride having syndiotactic stereoregularity (hereinafter sometimes referred to as “polymer (α1)”).

The degree of stereoregularity of the polymer (α1) is not particularly limited. However, the degree of stereoregularity is easy because it is easy to form a substrate layer that is superior in mechanical strength, heat resistance, chemical resistance, low water absorption, and the like. Higher ones are preferred.
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 more dicyclopentadiene ring-opening polymer hydride having a higher melting point.
The ratio of racemo dyad can be measured and quantified by ¹³ C-NMR spectrum analysis. Specifically, ¹³ C-NMR measurement was performed using ortho-dichlorobenzene-d4 as a solvent and an inverse-gated decoupling method applied at 150 ° C., and the 127.5 ppm peak of orthodichlorobenzene-d4 was used as a reference shift. The ratio of racemo dyad can be determined from the intensity ratio of the 43.35 ppm signal derived from meso dyad and the 43.43 ppm signal derived from racemo dyad.

  In dicyclopentadiene, there are stereoisomers of endo and exo, both of which can be used as monomers in the present invention. Moreover, only one isomer may be used alone, or an isomer mixture in which an endo isomer and an exo isomer are present in an arbitrary ratio may be used. In the present invention, the crystallinity of the polymer (α1) is increased, and it is easy to form a substrate layer that is excellent due to mechanical strength, heat resistance, chemical resistance, low water absorption, etc., so the ratio of one stereoisomer Is preferably increased. 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.

When synthesizing the polymer (α1), only dicyclopentadiene may be used as the monomer, or another monomer copolymerizable with dicyclopentadiene may be used. Examples of other monomers include norbornenes other than dicyclopentadiene, cyclic olefins, and dienes.
When other monomers are used, the amount used is preferably 10% by weight or less, more preferably 5% by weight or less, based on the total amount of monomers.
A method for synthesizing the polymer (α1) is not particularly limited, and the polymer (α1) can be synthesized by performing a ring-opening polymerization reaction and a hydrogenation reaction according to a known method.

The alicyclic structure-containing resin film may contain components other than the alicyclic structure-containing polymer.
Components other than alicyclic structure-containing polymers include resins other than alicyclic structure-containing polymers, antioxidants, crystal nucleating agents, fillers, flame retardants, flame retardant aids, colorants, antistatic agents, and plasticizers. , Ultraviolet absorbers, light stabilizers, near infrared absorbers, lubricants and the like.

The content of the alicyclic structure-containing polymer in the alicyclic structure-containing resin film is usually 50% by weight or more, preferably 60% by weight or more, and more preferably 80% by weight with respect to the alicyclic structure-containing resin film. That's it.
The content of the other components can be appropriately determined according to the purpose, but is usually less than 50% by weight, preferably less than 40% by weight, more preferably 20% by weight with respect to the alicyclic structure-containing resin film. %.

  The thickness of the alicyclic structure-containing resin film is not particularly limited. The thickness of the alicyclic structure-containing resin film is usually 1 to 500 μm, preferably 5 to 250 μm.

The alicyclic structure-containing resin film may be subjected to easy adhesion treatment.
Examples of the easy adhesion treatment include corona discharge treatment, plasma treatment, flame treatment, UV treatment, degreasing treatment, and surface roughening treatment.

[Silver coating]
The silver film which comprises the laminated | multilayer film of this invention is a layer adjacent to the said base material layer, and is formed by sintering the coating film containing the silver nanoparticle formed on the said base material layer.

Silver nanoparticles refer to silver particles having a particle size of nanoscale.
The average particle diameter of the silver nanoparticles is preferably 1 to 100 nm, more preferably 10 to 50 nm.
The average particle diameter of the silver nanoparticles can be measured by a dynamic light scattering method.

Silver nanoparticles used in the present invention are obtained by heating a mixture formed by mixing an amine compound having 6 or more carbon atoms, an amine compound having 5 or less carbon atoms, and a silver compound.
At least a part of these amine compounds is considered to function as a ligand that coordinates to silver ions in the mixture. As a result, the silver ion derived from the silver compound is considered to exist as a silver complex in which these amine compounds are coordinated in the mixture.
Then, the silver complex is thermally decomposed by heating, and silver ions are reduced, whereby silver nanoparticles are generated.
The produced silver nanoparticles are stabilized as a result of interaction with surrounding amine compounds, and aggregation of silver nanoparticles is unlikely to occur. In addition, since the interaction between the silver nanoparticles and the amine compound is relatively small, these amine compounds can be easily removed as needed, and high-purity silver nanoparticles can be obtained.
By using silver nanoparticles obtained by such a method, it is possible to efficiently form a silver coating having excellent adhesion to the base material layer, excellent uniformity, and small resistance value variation, for example.

  In the present invention, aggregation of silver nanoparticles can be more efficiently suppressed by using an amine compound having 6 or more carbon atoms.

  Examples of the amine compound having 6 or more carbon atoms include n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, and n-tridecylamine. , N-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, isohexylamine, 2-ethylhexylamine, tert-octylamine, cyclohexylamine, oleylamine, etc. Primary amine: di-n-propylamine, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-peptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, di n-undecylamine, di-n-dodecylamine, N-me Secondary amines such as ru-N-propylamine, N-ethyl-N-propylamine, N-propyl-N-butylamine; tertiary amines such as triethylamine, tri-n-butylamine, tri-n-hexylamine; Can be mentioned.

  Among these, as the amine compound having 6 or more carbon atoms, an amine compound represented by the following formula (1) is preferable.

In formula (1), R ¹ represents a hydrocarbon group having 6 or more carbon atoms.
The R ^1, n- hexyl, n- heptyl, n- octyl, n- nonyl, n- decyl, n- undecyl, n- dodecyl group, n- tridecyl, n- tetradecyl, linear alkyl groups such as n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group; branched alkyl groups such as isohexyl group, 2-ethylhexyl group and tert-octyl group; cyclohexane such as cyclohexyl group An alkyl group; an alkenyl group such as an oleyl group; and the like.
In the present invention, amine compounds having 6 or more carbon atoms can be used singly or in combination of two or more.

In the present invention, by using an amine compound having 5 or less carbon atoms, a complex formation reaction with silver ions can be performed more rapidly. In addition, since the amine compound having 5 or less carbon atoms has a relatively low boiling point, the work for volatilizing and removing the amine compound can be performed more efficiently.
Examples of the amine compound having 5 or less carbon atoms include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, isopentylamine, tert- Primary amines such as pentylamine; secondary amines such as dimethylamine and diethylamine; tertiary amines such as trimethylamine;

  Among these, as the amine compound having 5 or less carbon atoms, an amine compound represented by the following formula (2) is preferable.

In formula (2), R ² represents a hydrocarbon group having 5 or less carbon atoms.
R ² is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group; Etc.
In the present invention, amine compounds having 5 or less carbon atoms can be used singly or in combination of two or more.

The amount of amine compound used in preparing the mixture (total amount of amine compound) is usually 1 mol or more, preferably 1 to 50 mol, more preferably 1 to 30 mol, per 1 mol of silver ions. .
Moreover, 10-80 mol% is preferable in the amine compound whole quantity, and, as for the usage-amount of an amine compound with 5 or less carbon atoms, 20-60 mol% is more preferable.
By using the amount of the amine compound having 5 or less carbon atoms within the above range, the characteristics of the amine compound having 6 or more carbon atoms and the amine compound having 5 or less carbon atoms can be fully utilized.

The silver compound used for the preparation of the mixture is used as a raw material for silver nanoparticles (metallic silver). The silver compound is not particularly limited as long as it generates metallic silver by thermal decomposition.
Silver compounds include silver formate, silver acetate, silver oxalate, silver malonate, silver benzoate, silver phthalate, and other carboxylates; silver fluoride, silver chloride, silver bromide, silver iodide, and other halides Silver, silver sulfate, silver nitrate, silver carbonate, and the like.
Among these, silver oxalate is preferable because high-purity silver nanoparticles can be easily obtained.
In this invention, a silver compound can be used individually by 1 type or in combination of 2 or more types.

You may mix | blend carboxylic acid with a mixture. The dispersibility of silver nanoparticles improves by mix | blending carboxylic acid.
As carboxylic acids, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, And saturated aliphatic monocarboxylic acids such as nonadecanoic acid, icosanoic acid, and eicosenoic acid; and unsaturated aliphatic monocarboxylic acids such as oleic acid, elaidic acid, linoleic acid, and palmitoleic acid.

Among these, since silver nanoparticles can be more efficiently dispersed, a carboxylic acid having 8 or more carbon atoms is preferable, a carboxylic acid having 8 to 18 carbon atoms is more preferable, and octanoic acid or oleic acid is more preferable.
In this invention, carboxylic acid can be used individually by 1 type or in combination of 2 or more types.
When mix | blending carboxylic acid, the usage-amount is 0.05-10 mol normally with respect to 1 mol of silver ions, Preferably it is 0.1-5 mol.
When there is too little usage-amount of carboxylic acid, it will become difficult to obtain the dispersibility improvement effect. On the other hand, if the amount of carboxylic acid used is too large, the operation may be difficult in the step of finally removing the carboxylic acid.

A mixture can be obtained by mixing each component according to a conventional method.
By heating the obtained mixture, the silver complex in the mixture is thermally decomposed to produce silver nanoparticles.
The heating conditions of the mixture are not particularly limited as long as silver nanoparticles are generated.
The heating temperature is usually 80 to 140 ° C, preferably 100 to 120 ° C.
The heating time is usually 1 minute to 2 hours, preferably 5 to 30 minutes.

A dispersion containing silver nanoparticles can be obtained by adding a solvent to the reaction product.
In addition, after the silver nanoparticles in the dispersion liquid are settled, the supernatant may be removed, and the silver nanoparticles may be washed by suspending the remaining silver nanoparticles in a new solvent.

Solvents used in these operations include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, and tetradecane; aromatic hydrocarbon solvents such as toluene, xylene, and mesitylene; methanol Alcohol solvents such as ethanol, propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, terpineol, and the like.
The silver concentration in the dispersion containing silver nanoparticles is usually 30 to 70% by weight, preferably 40 to 60% by weight.

The obtained dispersion liquid containing silver nanoparticles is used as a coating liquid for forming a coating film containing silver nanoparticles on a base material layer.
The formation method of the coating film containing silver nanoparticles is not particularly limited. Examples of the method for forming the coating film 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, ink jet printing, dispenser printing, gravure printing, gravure offset printing, pad printing, and the like.
Examples of the coating method include spin coaters, air knife coaters, curtain coaters, die coaters, blade coaters, roll coaters, gate roll coaters, bar coaters, rod coaters, gravure coaters, and other methods such as wire bars. It is done.

Subsequently, after performing the drying process of a coating film as needed, a silver film can be formed by sintering a coating film.
The sintering conditions are not particularly limited.
The sintering temperature is usually 50 to 200 ° C, preferably 80 to 180 ° C.
The sintering time is usually 10 seconds to 8 hours, preferably 1 minute to 2 hours.

The film thickness of the silver film which comprises the laminated | multilayer film of this invention is not specifically limited. The film thickness of the silver coating is usually 0.1 to 100 μm, preferably 1 to 10 μm.
The laminated film of the present invention may have a silver coating only on one side of the base material layer, or may have a silver coating on both sides of the base material layer.

The laminated film of the present invention has a silver coating formed by sintering a coating film containing the silver nanoparticles. For this reason, the laminated | multilayer film of this invention is excellent in interlayer adhesiveness and the electroconductivity of a silver film.
For example, when the crosscut tape peel test is performed according to the method described in the examples, the number of peels is preferably 5/50 or less, both after formation of the silver film and after the moisture absorption test. Is more preferable.

The laminated film of the present invention has a base material layer made of an alicyclic structure-containing resin film. For this reason, the laminated | multilayer film of this invention are excellent in the transparency and insulation of a base material layer.
In particular, when the alicyclic structure-containing polymer contained in the alicyclic structure-containing resin film is a crystalline alicyclic structure-containing polymer, problems of coloring and deformation of the base material layer hardly occur even if the firing temperature is considerably increased. . For this reason, since it can bake at high temperature, the laminated | multilayer film which is extremely excellent in interlayer adhesiveness and the electroconductivity of a silver film can be manufactured.

Since the laminated film of the present invention has the above properties, it is suitably used as a material for transparent flexible circuit boards, transparent sensors, transparent film antennas and the like.
The laminated film of the present invention can also be used as an optical film, a highly designable film, an antibacterial film, and the like.

Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” are based on weight unless otherwise specified.
The measurement in each example was performed by the following method.

[Glass transition temperature and melting point]
Using a differential scanning calorimeter (DSC), differential scanning calorimetry was carried out at a temperature rising 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 the 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 bond]
^{Based on the 1} H-NMR measurement, the hydrogenation rate of the unsaturated bond in the polymer was determined.

[Functional group content]
^{Based on 1} H-NMR measurement, the content ratio of functional groups in the polymer (number of functional groups: number of repeating units of the polymer) was determined.

[Production Example 1] [Synthesis of alicyclic structure-containing polymer (A)]
In a metal pressure-resistant reaction vessel purged with nitrogen inside, 154.5 parts of cyclohexane, 42.8 parts of cyclohexane solution (concentration 70%) of dicyclopentadiene (end content 99% or more) (30 parts as dicyclopentadiene) 1-hexene 1.9 parts was added and the whole was heated to 53 ° C.
On the other hand, in a solution obtained by dissolving 0.014 part of tetrachlorotungstenphenylimide (tetrahydrofuran) complex in 0.70 part of toluene, 0.061 part of n-hexane solution of diethylaluminum ethoxide (concentration 19%). And stirred for 10 minutes to prepare a catalyst solution. This catalyst solution was added to the reactor 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 of the solution containing the obtained dicyclopentadiene ring-opened 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 of a hydrotalcite-like compound (product name “KYOWARD (registered trademark) 2000”, manufactured by Kyowa Chemical Industry Co., Ltd.) was added, heated to 60 ° C., and stirred for 1 hour. 0.4 parts of filter aid (product name “Radiolite (registered trademark) # 1500” manufactured by Showa Chemical Industry Co., Ltd.) is added, and PP pleated cartridge filter (product name “TCP-HX”, manufactured by ADVANTEC Toyo Co., Ltd.) is used. The adsorbent was filtered off 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.

100 parts cyclohexane and 0.0043 parts chlorohydridocarbonyltris (triphenylphosphine) ruthenium are added to 200 parts solution (polymer content 30 parts) containing dicyclopentadiene ring-opening polymer after purification treatment, and hydrogen Hydrogenation reaction was performed 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 was centrifuged to separate the solid content and the solution, and the solid content was dried under reduced pressure at 60 ° C. for 24 hours to obtain 28.5 parts of the alicyclic structure-containing polymer (A).
The hydrogenation rate of the alicyclic structure-containing polymer (A) was 99% or more, the glass transition temperature was 98 ° C., and the melting point was 262 ° C.

[Production Example 2] [Production of alicyclic structure-containing resin film (A)]
To 100 parts of the alicyclic structure-containing polymer (A) obtained in Production Example 1, an antioxidant (tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate]) was added. After mixing 0.8 part of methane, product name “Irganox (registered trademark) 1010” (manufactured by BASF Japan), the mixture is put into a twin screw extruder (TEM-37B, manufactured by Toshiba Machine Co., Ltd.) and melted by heat. By extrusion molding, a strand-shaped molded body was obtained, which was chopped with a strand cutter to obtain pellets.
The operating conditions of the twin screw extruder are shown below.
-Barrel set temperature: 270-280 ° C
・ Die setting temperature: 250 ℃
・ Screw speed: 145rpm
・ Feeder rotation speed: 50 rpm

The obtained pellets were put into a hot melt extrusion film forming machine (product name “Measuring Extruder Type Me-20 / 2800V3”, manufactured by Optical Control Systems) equipped with a T-die, and the forming process was performed. The width was 120 mm and the thickness was 50 μm. An alicyclic structure-containing resin film (A) was obtained.
The operating conditions of the film forming machine are shown below.
・ Barrel temperature setting: 280 ℃ ～ 290 ℃
-Die temperature: 270 ° C
-Screw rotation speed: 30rpm
-Film winding speed: 4 m / min

[Production Example 3] [Preparation of silver nanoparticle dispersion]
To a 50 mL flask was added 1.45 g (20 mmol) of n-butylamine, 0.73 g (5.6 mmol) of n-octylamine, 3.46 g (34 mmol) of n-hexylamine, and 0.12 g (0.42 mmol) of oleic acid. The whole volume was stirred at 25 ° C. to obtain a uniform mixed solution. To this mixed solution, 3.047 g (10 mmol) of silver oxalate [Ag ₂ (C ₂ O ₄ )] was added, and the whole volume was stirred at 25 ° C. At this time, the contents of the flask changed to a viscous white substance.

Next, the contents of the flask were transferred to an aluminum block heat stirrer and heated and stirred at 100 to 110 ° C. The reaction with the generation of carbon dioxide started immediately after the start of stirring, and then the stirring was continued until no carbon dioxide was generated to obtain a blue glossy suspension containing silver nanoparticles.
10 mL of methanol was added to the obtained suspension, and this was stirred. Next, this suspension was subjected to a centrifugal separation treatment to precipitate silver nanoparticles, and the supernatant was removed. The obtained silver nanoparticles were suspended in methanol again, and then centrifuged and the supernatant was removed to isolate the silver nanoparticles. A 1-butanol / octane mixed solvent (volume ratio = 1/4) was added to the silver nanoparticles so that the silver concentration was 50% by weight and stirred to prepare a silver nanoparticle dispersion.

[Example 1]
On both sides of the alicyclic structure-containing resin film (A) obtained in Production Example 2, using a corona treatment device (model A3SW-FLNW type, manufactured by Wedge Corporation), the distance between the discharge tube and the film is 1 mm, and the output is 0.06 kW. The corona treatment was performed under the condition of a conveyance speed of 1 m / min.
It obtained, after apply | coating the silver nanoparticle dispersion liquid obtained by manufacture example 3 to the single side | surface of the corona-treated film obtained in this way using a wire bar (made by NO.04 Daiichi Rika Co., Ltd.). The coating film was sintered at 160 ° C. for 30 minutes to form a silver film. The thickness of the silver film was about 3 to 5 μm.
Furthermore, a silver film was formed on the surface of the film where the silver film was not formed by the same method, and a laminated film having a silver film on both surfaces of the alicyclic structure-containing resin film (A) was obtained.
In this laminated film, the silver film was not formed on the entire surface of the alicyclic structure-containing resin film (A), and the alicyclic structure-containing resin film (A) was partially exposed, The state of the layer (alicyclic structure-containing resin film (A)) can be observed.

Moreover, the film in which the conductor circuit was formed was produced with the following method.
First, the corona-treated film was processed to obtain a square film having a side of 100 mm. One side was covered with a masking tape having a thickness of 25 μm except for a region having a width of 5 mm and a length of 100 mm. Next, the silver nanoparticle dispersion liquid was applied to the entire film covered with the masking tape with a glass rod, and the obtained coating film was sintered at 160 ° C., and then the masking tape was peeled off to peel off the masking tape. A film on which a 100 mm conductor circuit was formed was obtained.

[Example 2]
A film on which a laminated film and a conductor circuit were formed was obtained in the same manner as in Example 1 except that the sintering temperature of the coating film containing silver nanoparticles was changed to 100 ° C.

Example 3
A laminated film in the same manner as in Example 1 except that the alicyclic structure-containing resin film (A) was not subjected to corona treatment and the sintering temperature of the coating film containing silver nanoparticles was changed to 100 ° C. And the film in which the conductor circuit was formed was obtained.

Example 4
Instead of the alicyclic structure-containing resin film (A), an alicyclic structure-containing resin film (B) (manufactured by Nippon Zeon Co., Ltd., ZEONOR film, ZF14-050, thickness 50 μm) was used, and silver nanoparticles were used. A laminated film and a film on which a conductor circuit was formed were obtained in the same manner as in Example 1 except that the sintering temperature of the coating film was changed to 100 ° C.

Example 5
The use of the alicyclic structure-containing resin film (B) instead of the alicyclic structure-containing resin film (A), the absence of corona treatment on the alicyclic structure-containing resin film (B), and silver nanoparticles A laminated film and a film on which a conductor circuit was formed were obtained in the same manner as in Example 1 except that the sintering temperature of the coating film containing was changed to 100 ° C.

[Comparative Example 1]
Instead of the alicyclic structure-containing resin film (A), a polyethylene terephthalate (PET) film (A) (Toyobo Co., Ltd., Cosmo Shine A4300, double-sided easy-adhesion treated product, thickness 50 μm) was used, and PET film A film on which a laminated film and a conductor circuit were formed was obtained in the same manner as in Example 1 except that (A) was not subjected to corona treatment.

[Comparative Example 2]
Instead of the alicyclic structure-containing resin film (A), the PET film (A) was used, the PET film (A) was not corona-treated, and the sintering temperature of the coating film containing silver nanoparticles A film on which a laminated film and a conductor circuit were formed was obtained in the same manner as in Example 1 except that was changed to 100 ° C.

[Comparative Example 3]
Instead of the alicyclic structure-containing resin film (A), a polypropylene (PP) film (Futamura Chemical Co., Ltd., FOS-BT, double-sided corona-treated product, thickness 50 μm) and a coating containing silver nanoparticles are used. A laminated film and a film on which a conductor circuit was formed were obtained in the same manner as in Example 1 except that the sintering temperature of the film was changed to 100 ° C.

[Comparative Example 4]
Instead of the silver nanoparticle dispersion obtained in Production Example 3, a commercially available silver nanoink (DOWA Electronx, aqueous solvent, silver concentration 40 to 60%) was used in the same manner as in Example 1. Thus, a laminated film and a film on which a conductor circuit was formed were obtained.

[Comparative Example 5]
Instead of the silver nanoparticle dispersion obtained in Production Example 3, a commercially available silver nanoink (aqueous solvent, silver concentration 40 to 60%, manufactured by DOWA Electronics) was used, and a coating film containing silver nanoparticles A laminated film and a film on which a conductor circuit was formed were obtained in the same manner as in Example 1 except that the sintering temperature was changed to 100 ° C.

  Using the laminated film obtained in each example, the transparency, interlayer adhesion, and insulation of the base material layer were evaluated by the following methods. Moreover, the electroconductivity was evaluated with the following method using the film in which the conductor circuit was formed. These results are shown in Table 2.

[Transparency of base material layer]
The part where the silver film of the laminated film obtained in Examples and Comparative Examples was not formed, and the alicyclic structure-containing resin film used for the formation of the laminated film were visually observed and evaluated according to the following criteria. .
○: No change ×: Change such as yellowing or whitening

[Interlayer adhesion]
According to JIS K5600 standard, the adhesion was evaluated by the following method.
After dividing into 25 cuts (total of 50 squares on both sides) by making a cut in 1 mm width x 5 rows with a cutter using a guide at any part of the silver film on both sides of the laminated film obtained in Examples and Comparative Examples Using a cellophane adhesive tape (manufactured by Nichiban Co., Ltd.), a cross-cut tape peeling test was conducted, and interlayer adhesion was evaluated according to the following criteria.
This test was conducted under two conditions, immediately after obtaining the laminated film (after forming the silver film) and after leaving the obtained laminated film at 85 ° C. and 85% relative humidity for 1000 hours (after the moisture absorption test). I went there.
A: peeling is 0/50
○: peeling is 1/50 or more, 5/50 or less Δ: peeling is 6/50 or more, 25/50 or less ×: peeling is 26/50 or more

[Insulation]
The part in which the silver film was formed on both surfaces of the laminated film obtained in the Example and the Comparative Example was cut out by 1 cm square, and a test for applying a voltage of 50 V under 85 ° C. and 85% relative humidity was performed for 1000 hours. . For each example and comparative example, the test was performed on four test pieces. When the resistance value during the test was less than 1.0 × 10 ⁶ , it was determined that the insulation was defective, and evaluation was performed according to the following criteria.
○: No insulation failure by 1000 hours.
X: Insulation failure occurred by 1000 hours.

[Conductivity of silver coating]
The resistance value of the conductor circuit of the film on which the conductor circuit obtained in Examples and Comparative Examples was formed was measured with a 3540 milliohm high tester (manufactured by Hioki Electric Co., Ltd.). The measurement was performed on 10 conductor circuits for each example and comparative example, and the variation of the average resistance value and the resistance value was evaluated according to the following criteria.
<Average resistance value>
: Less than 0.1Ω ○: 0.1Ω or more, less than 1Ω ×: 1Ω or more <Dispersion of resistance value>
◎: Less than ± 20% ○: ± 20% or more, less than ± 50% ×: ± 50% or more

The following can be seen from Tables 1 and 2.
The laminated films obtained in Examples 1 to 5 are excellent in transparency of the base layer, interlayer adhesion, insulation, and conductivity of the silver coating.
On the other hand, since the laminated film obtained in Comparative Examples 1 to 3 does not have a base material layer made of an alicyclic structure-containing resin film, it is inferior in transparency and insulation of the base material layer, or in the conductivity of the silver coating. Variations are occurring.
Moreover, since the laminated film obtained in Comparative Examples 4 and 5 does not have a silver film formed by a specific method, the interlayer adhesion is inferior or the conductivity of the silver film varies.

Claims (6)

A laminated film having a base material layer and a silver coating adjacent to the base material layer,
The base material layer is composed of an alicyclic structure-containing resin film,
The silver coating is formed by sintering a coating containing silver nanoparticles formed on the base material layer,
A laminated film in which the silver nanoparticles are obtained by heating a mixture obtained by mixing an amine compound having 6 or more carbon atoms, an amine compound having 5 or less carbon atoms, and a silver compound.   The laminated film according to claim 1, wherein the alicyclic structure-containing polymer contained in the alicyclic structure-containing resin film is a crystalline alicyclic structure-containing polymer.   The laminated film according to claim 1 or 2, wherein the silver nanoparticles have an average particle diameter of 0.5 to 100 nm. The amine compound having 6 or more carbon atoms is represented by the following formula (1).

(R ¹ represents a hydrocarbon group having 6 or more carbon atoms.)
Wherein the amine compound having 5 or less carbon atoms is represented by the following formula (2):

(R ² represents a hydrocarbon group having 5 or less carbon atoms.)
The laminated film according to claim 1, which is an amine compound represented by the formula:   The laminated film according to any one of claims 1 to 4, wherein the amount of the amine compound having 5 or less carbon atoms is 10 to 80 mol% in the total amount of the amine compound.   The laminated film according to any one of claims 1 to 5, wherein the silver compound is silver oxalate.