WO2019009409A1 - 基材フィルム付き導電構造体含有フィルムの製造方法 - Google Patents
基材フィルム付き導電構造体含有フィルムの製造方法 Download PDFInfo
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- WO2019009409A1 WO2019009409A1 PCT/JP2018/025684 JP2018025684W WO2019009409A1 WO 2019009409 A1 WO2019009409 A1 WO 2019009409A1 JP 2018025684 W JP2018025684 W JP 2018025684W WO 2019009409 A1 WO2019009409 A1 WO 2019009409A1
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- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/84—Heating arrangements specially adapted for transparent or reflecting areas, e.g. for demisting or de-icing windows, mirrors or vehicle windshields
- H05B3/86—Heating arrangements specially adapted for transparent or reflecting areas, e.g. for demisting or de-icing windows, mirrors or vehicle windshields the heating conductors being embedded in the transparent or reflecting material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays
- B32B2457/208—Touch screens
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
- B32B2605/006—Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/011—Heaters using laterally extending conductive material as connecting means
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/013—Heaters using resistive films or coatings
Definitions
- the present invention relates to a method for producing a conductive film containing a substrate film.
- the present invention also relates to a substrate film-containing conductive structure-containing film obtained based on the above production method, a conductive structure-containing film obtainable from the film, a method for producing the same, and a laminated glass using the conductive structure-containing film And a heating member, and a method of manufacturing the laminated glass.
- Patent Document 1 discloses a method of manufacturing a laminated glass having a conductive structure by bonding two transparent plates and at least one sheet A and at least one sheet B, wherein Describes a method of containing polyvinyl acetal PA and plasticizer WA, and having a conductive structure, and sheet B containing polyvinyl acetal PB and plasticizer WB.
- Patent Document 2 describes a method for producing laminated glass for shielding electromagnetic waves, in which a metal foil is bonded to a carrier resin through an adhesive film, and the metal foil is etched to form a metal mesh. A first glass plate is bonded from above through an adhesive film, and then the carrier resin is peeled off, and a second glass plate is bonded to the peeling surface of the carrier resin through an adhesive film. The manufacturing method of is described.
- the present invention solves the above problems, and a conductive structure-containing film with a base film with few defects such as deformation and breakage of the conductive structure and bubbles without requiring a film forming equipment with high accuracy. It is an object of the present invention to provide a method that can be produced with high production efficiency and production yield.
- another subject of the present invention is a conductive film-containing film with a base film obtained by the above-mentioned production method, a conductive structure-containing film obtainable from the film, a method for producing the same, and the conductive structure-containing film To provide a laminated glass, a heating member, and a method of manufacturing the laminated glass.
- thermoplastic resin composition (A) containing at least one thermoplastic resin selected from the group consisting of polyvinyl acetal resin, ionomer resin and ethylene vinyl acetate copolymer resin is coated on one side of a substrate film
- a method for producing a conductive structure-containing film with a base film comprising: a step (1) of forming a resin layer (X); and a step (2) of forming a conductive structure on the resin layer (X).
- thermoplastic resin composition (A) containing at least one thermoplastic resin selected from the group consisting of polyvinyl acetal resin, ionomer resin and ethylene vinyl acetate copolymer resin is coated on one side of a metal foil
- a step (3) of forming a resin layer (X); a step (4) of laminating a base film on the resin layer (X); and a step (5) of processing a metal foil to form a conductive structure The manufacturing method of the base material film with a conductive structure containing film containing.
- the method of applying the thermoplastic resin composition (A) is by melting and applying the thermoplastic resin composition (A), The manufacturing method of the conductive structure containing film with a base film as described in said [1] or [2].
- the method of applying the thermoplastic resin composition (A) is by a method of applying a solution or dispersion of the thermoplastic resin composition (A) The manufacturing method of the conductive structure containing film with a base film as described in said [1] or [2] which exists.
- thermoplastic resin composition (A) contains 50% by mass or more of a polyvinyl acetal resin based on the total mass of the thermoplastic resin composition (A)
- the viscosity of the 10% by mass toluene / ethanol 1/1 (mass ratio) solution of the polyvinyl acetal resin measured at 30 rpm using a Brookfield type (B type) viscometer at 200 rpm -The manufacturing method of the conductive structure containing film with a base film as described in said [5] larger than s.
- thermoplastic resin composition (A) according to the above [5] or [6], which comprises 0 to 20% by mass of a plasticizer based on the total mass of the thermoplastic resin composition (A)
- the manufacturing method of the conductive structure containing film with a base film [8] Any of the above-mentioned [1] to [7], wherein the thermoplastic resin composition (A) contains 80% by mass or more of a polyvinyl acetal resin based on the total mass of the thermoplastic resin composition (A) The manufacturing method of the conductive structure containing film with a base film as described in 4.
- a conductive structure-containing film comprising the step (6) of removing the base film from the conductive structure-containing film with a base film obtained by the manufacturing method according to any one of the above [1] to [11]. Manufacturing method.
- a method for producing laminated glass comprising a step (7) of sandwiching and laminating the conductive structure-containing film obtained by the production method according to [13] between at least two sheets of glass.
- a laminate is obtained by laminating and laminating glass on the surface of the conductive structure-containing film with a base film obtained by the manufacturing method according to any one of the above [1] to [11] which does not have a base film.
- the manufacturing method of laminated glass including the process of obtaining (8), and the process (9) which removes a base film from this laminated body, and laminates
- Between the conductive film containing a substrate film and the glass in the step (8) and / or between the laminate after removing the substrate film in the step (9) and the glass The manufacturing method of the laminated glass as described in said [16] which pinches
- a conductive structure-containing film with a base film which is less in defects such as deformation and breakage of the conductive structure and air bubbles without requiring high-precision film forming equipment. It can be produced in a yield.
- a laminated glass and a heating member can be produced using the conductive structure-containing film.
- the production method of the present invention comprises a thermoplastic resin composition (A) comprising at least one thermoplastic resin selected from polyvinyl acetal resin, ionomer resin and ethylene vinyl acetate copolymer resin on one side of a substrate film Step (1) of applying a “resin composition (A)” in some cases to form a resin layer (X); and a step of forming a conductive structure on the resin layer (X) (2);
- another aspect of the production method of the present invention is a resin composition comprising, on one side of a metal foil, at least one thermoplastic resin selected from the group consisting of polyvinyl acetal resin, ionomer resin and ethylene vinyl acetate copolymer resin.
- the resin composition (A) used in step (1) and step (3) contains at least one thermoplastic resin selected from the group consisting of polyvinyl acetal resin, ionomer resin, and ethylene vinyl acetate copolymer resin.
- the resin composition (A) preferably contains a polyvinyl acetal resin and / or an ionomer resin, and preferably contains a polyvinyl acetal resin.
- the content of the polyvinyl acetal resin in the resin composition (A) is preferably 50% by mass or more based on the total mass of the resin composition (A), 70 % By mass or more is preferable, 80% by mass or more is more preferable, 85% by mass or more is particularly preferable, 90% by mass or more is extremely preferable, 95% by mass or more is the most preferable, and 100% by mass may be sufficient.
- the resin composition (A) contains one type of polyvinyl acetal resin, viscosity average degree of polymerization, degree of acetalization, amount of acetyl group, amount of hydroxyl group, ethylene content, molecular weight of aldehyde used for acetalization, and Two or more types of polyvinyl acetal resins may be included, one or more of the chain lengths being different.
- Polyvinyl acetal resin is manufactured by acetalization of polyvinyl alcohol-type resin, such as polyvinyl alcohol or ethylene vinyl alcohol copolymer.
- polyvinyl alcohol-type resin such as polyvinyl alcohol or ethylene vinyl alcohol copolymer.
- polyvinyl alcohol-type resin such as polyvinyl alcohol or ethylene vinyl alcohol copolymer.
- aqueous solution of polyvinyl alcohol or ethylene vinyl alcohol copolymer having a concentration of 3 to 30% by mass is maintained in a temperature range of 80 to 100 ° C., and then gradually cooled over 10 to 60 minutes. When the temperature drops to -10 to 30 ° C., an aldehyde and an acid catalyst are added, and the acetalization reaction is carried out for 30 to 300 minutes while keeping the temperature constant.
- the reaction solution is heated to a temperature of 20 to 80 ° C.
- reaction solution is filtered if necessary, and then neutralized by adding a neutralizing agent such as an alkali, and filtered, washed with water and dried to produce a polyvinyl acetal resin.
- a neutralizing agent such as an alkali
- the acid catalyst used for the acetalization reaction is not particularly limited, and any of organic acids and inorganic acids can be used.
- the acid catalyst include acetic acid, p-toluenesulfonic acid, nitric acid, sulfuric acid and hydrochloric acid.
- hydrochloric acid, sulfuric acid and nitric acid are preferable from the viewpoint of acid strength and ease of removal at the time of washing.
- the aldehyde used for the preparation of the polyvinyl acetal resin is preferably a linear, branched or cyclic aldehyde having 2 to 10 carbon atoms, and may be a linear or 2 to 10 carbon atoms. It is more preferably a branched aldehyde, still more preferably a linear aliphatic aldehyde having 2 to 10 carbon atoms, and particularly preferably n-butyraldehyde. When the above aldehyde is used, a polyvinyl acetal resin having suitable breaking energy can be easily obtained.
- the amount of n-butyraldehyde used is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 95% by mass or more, and even more preferably 99% by mass or more based on the total mass of aldehydes used in the acetalization reaction. Particularly preferred is 100% by mass. Also, a single aldehyde may be used, or a mixture of multiple aldehydes may be used.
- the viscosity average polymerization degree of the polyvinyl alcohol resin is preferably 5000 or less, more preferably 3000 or less, still more preferably 2500 or less, particularly preferably 2300 or less, and most preferably 2000 or less.
- the viscosity average polymerization degree of the polyvinyl alcohol-based resin is less than or equal to the above upper limit value, good film forming properties can be easily obtained.
- the viscosity average polymerization degree of polyvinyl alcohol-type resin can be measured based on JISK6726 "polyvinyl alcohol test method", for example.
- the preferable viscosity average polymerization degree of polyvinyl acetal resin is the same as the said viscosity average polymerization degree of polyvinyl alcohol-type resin used as a raw material.
- the viscosity average polymerization degree of at least one type of polyvinyl acetal resin is not less than the lower limit and not more than the upper limit.
- Acetyl group content of the polyvinyl acetal resin based on the ethylene unit of the polyvinyl acetal main chain that is, a unit consisting of two carbons of the main chain in the polyvinyl alcohol-based resin which is a raw material for producing polyvinyl acetal resin
- the content of vinyl acetate units is preferably 0.1 to 20 mol%, more preferably 0. 0 to 20 mol%, where alcohol units, vinyl acetate units, ethylene units and the like are one repeating unit, and the one repeating unit is used as a reference. 5 to 3 mol% or 5 to 8 mol%.
- the amount of acetyl groups can be adjusted within the above range by appropriately adjusting the degree of saponification of the raw material polyvinyl alcohol resin.
- the amount of acetyl group affects the polarity of the polyvinyl acetal resin, which may change the plasticizer compatibility and mechanical strength of the resin layer (X).
- the amount of acetyl groups of at least one type of polyvinyl acetal resin is preferably in the above range.
- the degree of acetalization of the polyvinyl acetal resin is not particularly limited, but is preferably 40 to 86 mol%, more preferably 45 to 84 mol%, still more preferably 50 to 82 mol%, and still more preferably 60 to 82 mol%. -82 mol% is particularly preferred.
- the “degree of acetalization” means a unit (for example, a vinyl alcohol unit, a vinyl acetate unit, an ethylene unit, etc.) consisting of two carbons of the main chain in a polyvinyl alcohol resin which is a raw material for producing polyvinyl acetal resin.
- the degree of acetalization of the polyvinyl acetal resin can be adjusted within the above range by appropriately adjusting the amount of aldehyde used in acetalizing the polyvinyl alcohol-based resin.
- the degree of acetalization is in the above range, the compatibility between the polyvinyl acetal resin and the plasticizer is unlikely to decrease, and the mechanical strength of the conductive structure-containing film with a base film obtained by the production method of the present invention is sufficient. It is easy to become a thing.
- the degree of acetalization of at least one type of polyvinyl acetal resin is preferably within the above range.
- the amount of hydroxyl groups of the polyvinyl acetal resin based on the ethylene unit of the polyvinyl acetal main chain that is, a unit consisting of two carbons of the main chain in the polyvinyl alcohol-based resin which is a raw material for producing polyvinyl acetal resin
- the content of the vinyl alcohol unit is preferably 6 to 26% by mass, more preferably 12 to 24% by mass, based on the unit, vinyl acetate unit, ethylene unit, etc., as one repeating unit, based on the one repeating unit.
- the content is preferably 15 to 22% by mass, particularly preferably 18 to 21% by mass, and in the case of the purpose of providing sound insulation performance, preferably 6 to 20% by mass, more preferably 8 to 18% by mass, still more preferably 10 to It is 15% by mass, particularly preferably 11 to 13% by mass.
- the amount of hydroxyl groups can be adjusted within the above range by adjusting the amount of aldehyde used in acetalizing the polyvinyl alcohol resin.
- the amount of hydroxyl groups of at least one type of polyvinyl acetal resin is preferably within the above range.
- the polyvinyl acetal resin is usually composed of an acetal group unit, a hydroxyl group unit and an acetyl group unit, and the amount of each unit thereof is, for example, JIS K 6728 "polyvinyl butyral test method” or nuclear magnetic resonance (NMR) It can be measured by
- the viscosity of a 10% by weight toluene / ethanol (1/1 (mass ratio) solution of the polyvinyl acetal resin measured at 30 rpm using a Brookfield type (B type) viscometer is preferably 200 mPa. S or more, more preferably 200 mPa ⁇ s or more, further preferably 240 mPa ⁇ s or more, particularly preferably 265 mPa ⁇ s or more.
- the viscosity of polyvinyl acetal resin can be adjusted more than the said lower limit by using or using together polyvinyl acetal resin manufactured using polyvinyl alcohol-type resin with a high viscosity average polymerization degree as a raw material or a part of raw material.
- the resin composition (A) comprises a mixture of a plurality of polyvinyl acetal resins
- the viscosity of the mixture is equal to or more than the lower limit.
- the viscosity of the polyvinyl acetal resin is at least the lower limit value, deformation and breakage of the conductive structure are easily suppressed at the time of producing the laminated glass, and in the obtained laminated glass, the phenomenon of the glass being shifted by heat is easily prevented.
- the viscosity is preferably 1000 mPa ⁇ s or less, more preferably 800 mPa ⁇ s or less, still more preferably 500 mPa ⁇ s or less, particularly preferably 450 mPa ⁇ s or less, from the viewpoint that good film forming properties can be easily obtained. It is 400 mPa ⁇ s or less.
- the resin composition (A) preferably contains 0 to 20% by mass of a plasticizer based on the total mass of the resin composition (A).
- the content of the plasticizer in the resin composition (A) is more preferably 0 to 19% by mass, still more preferably 0 to 15% by mass, particularly preferably 0 to 10% by mass, most preferably 0 to 5% by mass is there.
- the conductive structure-containing film after removing the substrate film from the substrate film-containing conductive structure-containing film of the present invention tends to be excellent in handleability, At the time of production of a laminated glass using a structure-containing film, deformation and breakage of the conductive structure are easily suppressed, and as a result, good electrical conductivity is easily obtained.
- plasticizer examples include the following compounds.
- the plasticizer may be used alone or in combination of two or more.
- Esters of polyvalent aliphatic or aromatic acids For example, dialkyl adipates (e.g. dihexyl adipate, di-2-ethyl butyl adipate, dioctyl adipate, di-2-ethyl hexyl adipate, hexyl cyclohexyl adipate, heptyl adipate, nonyl adipate, diisononyl adipate, heptyl nonyl adipate); adipic acid and alcohols Or esters with alcohols containing ether compounds (eg, di (butoxyethyl) adipate, di (butoxyethoxyethyl) adipate); dialkyl sebacates (eg, dibutyl sebacate); containing sebacic acid and alicyclic or ether compounds Est
- Esters or ethers of polyvalent aliphatic or aromatic alcohols or oligoether glycols with one or more aliphatic or aromatic substituents For example, esters of glycerin, diglycol, triglycol, tetraglycol and the like with a linear or branched aliphatic or alicyclic carboxylic acid can be mentioned.
- diethylene glycol-bis- (2-ethylhexanoate), triethylene glycol-bis- (2-ethylhexanoate), triethylene glycol-bis- (2-ethylbutanoate), tetra-ethylene glycol Ethylene glycol-bis-n-heptanoate, triethylene glycol-bis-n-heptanoate, triethylene glycol-bis-n-hexanoate, tetraethylene glycol dimethyl ether, and dipropylene glycol benzoate can be mentioned. • Phosphate esters of aliphatic or aromatic ester alcohols.
- Examples include tris (2-ethylhexyl) phosphate, triethylphosphate, diphenyl-2-ethylhexyl phosphate, and tricresyl phosphate.
- Polyesters or oligoesters consisting of polyhydric alcohols and polyhydric carboxylic acids.
- the terminal may be a hydroxy group or a carboxyl group, and may be esterified or etherified.
- Polyesters or oligoesters consisting of lactones or hydroxycarboxylic acids.
- the terminal may be a hydroxy group or a carboxyl group, and may be esterified or etherified.
- the content of the ionomer resin in the resin composition (A) is preferably 50% by mass or more, 70% by mass based on the total mass of the resin composition (A).
- the above is more preferable, 80 mass% or more is further preferable, 85 mass% or more is particularly preferable, 90 mass% or more is extremely preferable, 95 mass% or more is most preferable, and 100 mass% may be sufficient.
- the resin composition (A) may contain one type of ionomer resin, the type of ⁇ , ⁇ -unsaturated carboxylic acid, the content ratio of the ⁇ , ⁇ -unsaturated carboxylic acid, and the neutralization Of other copolymerizable monomers represented by types of metal ions, types of .alpha.-olefins, content ratios of .alpha.-olefin structural units, esters of .alpha.,. Beta.-unsaturated carboxylic acids, and the content ratios thereof And so on may contain two or more different ionomer resins.
- the ionomer resin has, for example, a structural unit derived from ethylene and a structural unit derived from an ⁇ , ⁇ -unsaturated carboxylic acid, and at least a part of the ⁇ , ⁇ -unsaturated carboxylic acid is neutralized by a metal ion Resin is mentioned.
- the metal ion include sodium ion and magnesium ion.
- the content ratio of the ⁇ , ⁇ -unsaturated carboxylic acid component is at least 2 mass% Is preferable, 5 mass% or more is more preferable, 30 mass% or less is preferable, and 20 mass% or less is more preferable.
- the content ratio of the structural unit of the ⁇ , ⁇ -unsaturated carboxylic acid described above is the above lower limit value and the above upper limit value for at least one type of ionomer resin It is preferable to be in the range of Examples of the ⁇ , ⁇ -unsaturated carboxylic acid constituting the ionomer resin include acrylic acid, methacrylic acid, maleic acid, monomethyl maleate, monoethyl maleate, maleic anhydride and the like, with acrylic acid and methacrylic acid being particularly preferable. .
- the ionomer resin a resin in which at least a part of the carboxyl group of ethylene-acrylic acid copolymer or ethylene-methacrylic acid copolymer is neutralized with sodium or magnesium ion is particularly preferable.
- the content of the ethylene-vinyl acetate copolymer resin in the resin composition (A) is based on the total mass of the resin composition (A) 50 mass% or more is preferable, 70 mass% or more is more preferable, 80 mass% or more is more preferable, 85 mass% or more is particularly preferable, 90 mass% or more is extremely preferable, 95 mass% or more is most preferable, 100 mass% It may be
- the resin composition (A) may contain one type of ethylene-vinyl acetate copolymer resin, and the content ratio of vinyl acetate structural units, other copolymerizable monomers such as vinyl esters other than vinyl acetate, and carbon Two or more types of ethylene-vinyl acetate copolymer resins may be included, in which one or more of the types such as ⁇ -olefins of several or more and the content ratio
- the proportion of the vinyl acetate monomer to the total of the ethylene monomer and the vinyl acetate monomer is preferably less than 50 mol%, more preferably less than 30 mol%, and less than 20 mol% Is more preferred, and less than 15 mol% is particularly preferred. If the ratio of vinyl acetate monomer to the total of ethylene monomer and vinyl acetate monomer is less than the above upper limit value, for example, less than 50 mol%, mechanical strength and flexibility tend to be expressed in a balanced manner. .
- the ratio of the vinyl acetate monomer to the total of the ethylene monomer and the vinyl acetate monomer may be 1 mol% or more, 3 mol% or more, or 7 mol% or more. Good.
- the ratio of the above-mentioned vinyl acetate monomer of the at least one ethylene vinyl acetate copolymer resin is the upper limit value mentioned above It is preferable to be in the range of and the lower limit value.
- the resin composition (A) comprises water, an ultraviolet absorber, an antioxidant, an adhesion regulator, a brightening agent or a brightening agent, a stabilizer, a pigment, a pigment, a processing aid, organic or inorganic nanoparticles, calcined silica Additives other than plasticizers such as acids and surfactants may be included.
- the resin composition (A) may contain a corrosion inhibitor.
- the content of the corrosion inhibitor in the resin composition (A) is preferably 0.005 to 5% by mass based on the total mass of the resin composition (A).
- the corrosion inhibitor include benzotriazole compounds or benzotriazole compounds having a substituent.
- the resin layer (X) is formed by a method of applying the resin composition (A) on one side of a substrate film or a metal foil.
- the method of coating the resin composition (A) on one side of the substrate film or metal foil is not particularly limited, but the method of melting and applying the resin composition (A), or the solution or dispersion of the resin composition (A) The method of applying the solution is preferred.
- a method of melting and applying the resin composition (A) As a method of melting and applying the resin composition (A), a method of kneading the resin composition (A) uniformly to form a melt, and then extruding the melt on one surface of the substrate film or metal foil, or A known method such as a method of applying the melt with a knife; a method of spray coating the resin composition (A) on one side of a substrate film or a metal foil to melt the same;
- the resin composition (A) As a method of applying a solution or dispersion of the resin composition (A), the resin composition (A) is dissolved or uniformly dispersed in a solvent, and the obtained solution or dispersion is used as a substrate film or metal foil.
- a known method such as a method of coating or spray coating on one side and removing a solvent as necessary may be mentioned.
- the solvent used for dissolving or dispersing the resin composition (A) is not particularly limited.
- alcohols such as methanol, ethanol, propanol, butanol, n-butyl alcohol, t-butyl alcohol, octanol and diacetone alcohol
- Ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, 1,4-dioxane and tetrahydrofuran
- ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone and isophorone
- N, N-dimethyl Amides such as acetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, etc .
- vinegars such as methyl acetate, ethyl acetate, isopropyl a
- Ester methylene chloride, propylene chloride, ethylene chloride, chlorides such as chloroform; dimethyl sulfoxide, acetic acid, terpineol, butyl carbitol, and the like.
- the resin composition (A) contains a polyvinyl acetal resin
- lowers such as ethanol, propanol, butanol, n-butyl alcohol, t-butyl alcohol and the like Alcohol is preferred.
- the resin composition (A) contains an ionomer resin or an ethylene vinyl acetate copolymer resin, toluene, xylene, benzene, trichlene, carbon tetrachloride, mineral spirits, tetrahydrofuran and the like are preferable.
- concentration of the resin composition (A) in the solution or dispersion is not particularly limited, but is preferably 5 to 30% by mass, and more preferably 8 to 20% by mass with respect to the total mass of the solution or dispersion.
- the temperature of the resin composition (A) at the time of extrusion is not particularly limited as long as it is a temperature at which the resin composition (A) melts, for example, when the resin composition (A) contains a polyvinyl acetal resin, extrusion
- the temperature of the resin composition (A) at this time is preferably 150 to 250.degree. C., and more preferably 170 to 230.degree.
- the resin temperature becomes too high, the polyvinyl acetal resin is decomposed to increase the content of volatile substances.
- the temperature is too low, the content of volatile substances increases. In order to remove volatile substances efficiently, it is preferable to remove volatile substances by reducing pressure from the vent port of the extruder.
- the thickness of the resin layer (X) in the step (1) and the step (3) is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, still more preferably 20 ⁇ m or more, and particularly preferably 30 ⁇ m or more.
- the thickness of the resin layer (X) is preferably 350 ⁇ m or less, more preferably 330 ⁇ m or less, more preferably 270 ⁇ m or less, still more preferably 250 ⁇ m or less, particularly preferably 150 ⁇ m or less, and most preferably 100 ⁇ m or less.
- the thickness of the resin layer (X) is equal to or less than the above value, from the resin layer (Y) to the resin layer (X)
- the amount of transferred plasticizer decreases and the decrease in the amount of plasticizer in the resin layer (Y) is suppressed, so the head impact index of the laminated glass for a vehicle using the conductive structure-containing film tends to be small.
- the thickness of the resin layer (X) is measured using a thickness gauge or a laser microscope.
- the resin constituting the substrate film used in the present invention is not particularly limited.
- polyester resin such as polyethylene terephthalate (PET); polyimide resin; triacetyl chloride (TAC), polyethylene (PE), polypropylene (PP), Polyvinyl chloride (PVC) or the like can be used.
- the base film has appropriate adhesiveness with the resin layer (X). Specifically, in the step (2), it does not peel off from the resin layer (X) and is used for producing laminated glass etc. It can be removed by means such as peeling off from the resin layer (X), and it does not cause deformation due to shrinkage etc. even when it is heated or when it comes in contact with various drugs in step (2). preferable.
- the resin constituting the substrate film is preferably a polyester resin or a polyimide resin, and particularly preferably PET.
- the thickness of the base film is preferably 10 to 250 ⁇ m, more preferably 20 to 150 ⁇ m, and particularly preferably 30 to 100 ⁇ m from the viewpoint of cost and strength.
- the metal foil used in the step (3) is not particularly limited as long as it contains a conductive metal, and examples thereof include copper foil and silver foil. Among them, copper foil is preferable.
- One aspect of the production method of the present invention includes the step (4) of laminating a base film on the resin layer (X) after the step (3) of forming the resin layer (X) on one side of a metal foil.
- the method for laminating the base film to the resin layer (X) is not particularly limited, but laminating is carried out using a pressure roll, a heating roll, a press, a vacuum laminator, etc. at a temperature higher than the melting temperature of the resin layer (X).
- Known methods can be mentioned. Among them, a method using a pressure roll which is easily applicable to a highly productive roll-to-roll system is particularly preferable.
- the temperature of the resin layer (X) at pressure bonding is preferably equal to or higher than the glass transition temperature (Tg) of the resin composition (A), more preferably Tg + 30 ° C. or higher, still more preferably Tg + 50 ° C. or higher, Tg + 70. C. or higher is particularly preferred.
- the upper limit of the temperature of the resin layer (X) at the time of pressure bonding is not particularly limited. 200 degrees C or less is preferable, as for the temperature of the resin layer (X) at the time of pressure bonding, 180 degrees C or less is more preferable, and 160 degrees C or less is especially preferable.
- the temperature of the resin layer (X) at the time of pressure bonding is higher than the above lower limit value, the adhesion between the metal foil and the resin layer (X) and the adhesion between the resin layer (X) and the base film are sufficient. If it is lower than the above upper limit value, problems such as thermal decomposition and foaming of the resin layer (X) and a decrease in thickness of the resin layer (X) due to the outflow of the resin composition (A) hardly occur.
- the lower limit of the surface temperature of the heating roll is preferably higher than the temperature mentioned above as the preferable temperature of the resin layer (X) in the method using a pressure bonding roll, It is more preferable that the temperature is higher, and it is particularly preferable that the temperature is higher by 20 ° C. or more than the temperature.
- the preferable aspect of the base film used by process (4) is the same as the preferable aspect of the base film used by process (1) mentioned above.
- the presence of the base film used in the step (4) makes it possible to suppress the occurrence of wrinkles in the step (5) (step of processing a metal foil to form a conductive structure) described later. Further, when the base film used in the step (4) is formed into a roll after the step (5) described later, the side having the conductive structure of the resin layer (X) does not have the conductive structure. It can prevent contact with
- Step (3) and step (4) may be performed simultaneously.
- a method of performing a process (3) and a process (4) simultaneously the method of inserting the melt, solution, or dispersion liquid of a resin composition (A) between a base film and metal foil is mentioned.
- metal is formed after the step (3) of forming the resin layer (X) on one side of the metal foil, and the step (4) of laminating a base film on the resin layer (X). And (5) processing the foil to form a conductive structure.
- a conductive structure there is no restriction
- Step (2)> Another aspect of the production method of the present invention comprises the step (2) of forming a conductive structure on the resin layer (X) after the step (1) of forming the resin layer (X) on one side of a substrate film Including.
- the method of forming the conductive structure on the resin layer (X) but (i) the metal foil is laminated on the resin layer (X), and the conductive structure is etched by the above method.
- a metal layer is formed on the resin layer (X) by vapor deposition or the like, and a metal foil is etched by the above-mentioned method to form a conductive structure;
- a resin layer (X) A method of printing a conductive paste on top to form a conductive structure;
- the methods of (i) and (ii) are preferable from the viewpoint of producing a conductive structure-containing film with a substrate film suitable for producing a laminated glass excellent in forward visibility, and the method of (i) from the viewpoint of production cost Is more preferred.
- the preferable aspect of the metal foil used by the method of (i) is the same as the preferable aspect of the metal foil used by process (3) mentioned above.
- the method for laminating the metal foil in the method (i) is not particularly limited, and known methods for laminating using a pressure roll, a heating roll, a press, a vacuum laminator, etc. at a temperature higher than the temperature at which the resin layer (X) melts. The method of can be applied.
- the preferable temperature of the resin layer (X) at the time of pressure bonding in the method using the pressure bonding roll, and the preferable surface temperature of the heating roll in the method using the heating roll are the same as the temperatures described above as the preferable embodiment of the step (4).
- the thickness of the conductive structure formed in the step (2) and the step (5) is preferably 1 to 30 ⁇ m, more preferably 2 to 20 ⁇ m, from the viewpoint of easily achieving reduction of light reflection and necessary calorific value. More preferably, it is 3 to 15 ⁇ m, particularly preferably 3 to 12 ⁇ m.
- the thickness of the conductive structure is measured using a thickness gauge or a laser microscope.
- the conductive structure is preferably made of copper or silver in terms of etching ease and availability.
- the conductive structure preferably has at least two bus bar structures.
- a method of forming a bus bar structure a method using a bus bar generally used in the art such as a metal foil tape, a metal foil tape with a conductive adhesive, a conductive paste, etc .; etching the metal foil by the above method
- a method of forming a bus bar by leaving a part of a metal foil when forming a conductive structure By connecting feeders to at least two bus bars and connecting each feeder to a power supply, current can be supplied to the conductive structure.
- the conductive structure preferably has a metal fine wire structure between the at least two bus bar structures.
- the metal fine wire structure means a conductive structure having a line width of 1 to 100 ⁇ m.
- the line width of the metal thin wire structure is preferably 1 to 30 ⁇ m, more preferably 2 to 15 ⁇ m, still more preferably 3 to 12 ⁇ m, and particularly preferably 3 to 9 ⁇ m.
- the base film-attached conductive structure-containing film obtained by the production method of the present invention is also one of the present invention.
- An electrically conductive structure-containing film not having a substrate film comprising the step (6) of removing the substrate film from the electrically conductive structure-containing film with a substrate film obtained by the above-mentioned production method (hereinafter simply referred to as "conductive structure
- the method for producing the "containing film” is also one of the present invention.
- the conductive structure containing film obtained by this manufacturing method is also one of this invention.
- the method of manufacturing a laminated glass using the base material film with a conductive structure containing film obtained by the manufacturing method of this invention, and the laminated glass obtained by this manufacturing method are also one of this invention.
- a method for producing laminated glass using a base film-attached conductive structure-containing film for example, (i) at least two conductive structure-containing films obtained by removing the base film from the base film-attached conductive structure-containing film
- a manufacturing method including a step (7) of sandwiching and laminating between glass; (ii) a step of laminating and laminating glass on the side not having a base film of a conductive structure-containing film with a base film to obtain a laminate ( 8) and a process of removing the substrate film from the laminate, and laminating (laminating) the glass on the side not having glass, and laminating (iii) a conductive film-containing film with a substrate film
- Manufacturing method including the step of laminating between at least two sheets of glass;
- the glass is an inorganic glass; such as a methacrylic resin sheet, a polycarbonate resin sheet, a polystyrene resin sheet, a polyester resin sheet such as polyethylene terephthalate, a polycycloolefin resin sheet, etc.
- Organic glass is preferred.
- inorganic glass, methacrylic resin sheet or polycarbonate resin sheet is preferable, and inorganic glass is particularly preferable.
- the inorganic glass is not particularly limited, and examples thereof include float glass, tempered glass, semi-tempered glass, chemically tempered glass, green glass, quartz glass and the like.
- At least one resin layer (Y) may be further sandwiched between at least two sheets of glass. Specifically, in the step (7), at least one resin layer (Y) may be sandwiched between the conductive structure-containing film and the glass, and in the step (8), the conductive structure with a base film At least one resin layer (Y) may be sandwiched between the containing film and the glass and / or between the laminate after removing the base film in the step (9) and the glass.
- the resin layer (Y) preferably contains at least one thermoplastic resin selected from the group consisting of polyvinyl acetal resin, ethylene vinyl acetate copolymer resin and ionomer resin, and contains at least one polyvinyl acetal resin Is more preferred. Further, from the viewpoint of making it difficult to cause adhesion of the resin layer (X) and reflection or refraction of light at the adhesive interface with the resin layer (X), the thermoplastic resin contained in the resin composition (A) It is preferable to contain the same thermoplastic resin.
- the amount of acetyl group of the polyvinyl acetal resin based on the ethylene unit of the polyvinyl acetal main chain is not particularly limited, but preferably 0.1 to 20. It is a mole%, more preferably 0.5 to 3 mole% or 5 to 8 mole%.
- the degree of acetalization of the polyvinyl acetal resin is not particularly limited, but is preferably 40 to 86 mol%, more preferably 45 to 84 mol%, still more preferably 50 to 82 mol%, particularly preferably 60 to 82 mol%, Preferably, it is 68 to 82 mol%.
- the amount of hydroxyl groups of the polyvinyl acetal resin based on the ethylene unit of the polyvinyl acetal main chain is not particularly limited, but preferably 6 to 26% by mass, more preferably 12 to 24% by mass, more preferably 15 to 22% by mass It is preferably 18 to 21% by mass, particularly preferably 6 to 20% by mass, more preferably 8 to 18% by mass, still more preferably 10 to 15% by mass, from the viewpoint of obtaining laminated glass excellent in sound insulation performance. Preferably, it is 11 to 13% by mass.
- the above-mentioned amount of acetyl groups, the degree of acetalization, and the amount of hydroxyl groups have the same meanings as the meanings described in the preceding ⁇ polyvinyl acetal resin> paragraph.
- the amount of acetyl groups, the degree of acetalization and the amount of hydroxyl groups of at least one type of polyvinyl acetal resin are preferably within the above ranges.
- the resin layer (Y) preferably contains a plasticizer.
- the content of the plasticizer in the resin layer (Y) is preferably 16.0% by mass or more, more preferably from the viewpoint of obtaining laminated glass excellent in impact resistance, based on the total mass of the resin layer (Y). Is preferably 16.1 to 36.0% by mass, more preferably 22.0 to 32.0% by mass, particularly preferably 26.0 to 30.0% by mass, and from the viewpoint of obtaining laminated glass excellent in sound insulation performance, The amount is preferably 30% by mass or more, more preferably 30 to 50% by mass, still more preferably 31 to 40% by mass, and particularly preferably 32 to 35% by mass.
- the plasticizer mentioned above in the paragraph of ⁇ plasticizer> is mentioned, for example.
- the method for producing the resin layer (Y) is not particularly limited, and after uniformly kneading the resin composition constituting the resin layer (Y), known methods such as extrusion method, calendar method, press method, casting method, inflation method, etc.
- the film produced by the film forming method can be used.
- a commercially available interlayer film for laminated glass may be used.
- membrane with a base film is not specifically limited, A well-known method is applicable.
- the conductive structure-containing film obtained by removing the base film from the conductive film-containing film with a base film is overlaid on glass and an arbitrary number of resin layers (Y) are placed one on another
- the conductive structure-containing film and the resin layer (Y) are fused on the entire surface or locally of the conductive structure-containing film and the resin layer (Y) by raising the temperature as a pre-pressing step. it can.
- the conductive structure-containing film and an arbitrary number of resin layers (Y) may be bonded in advance, and then laminated by being disposed between at least two sheets of glass and fusion-bonded at a high temperature.
- a method of degassing under reduced pressure by a method such as vacuum bag, vacuum ring, vacuum laminator; nip roll
- a method of degassing using: a method of compression molding under high temperature; and the like For example, a method of degassing under the conditions of about 2 ⁇ 10 4 Pa and 130 to 145 ° C. by a vacuum bag method or a vacuum ring method described in EP 1235683 B1 can be mentioned.
- the vacuum laminator consists of a heatable and vacuumable chamber in which a laminate (laminated glass) is formed in a time of about 20 minutes to about 60 minutes.
- a vacuum of 1 Pa to 3 ⁇ 10 4 Pa and a temperature of 100 ° C. to 200 ° C., in particular 130 ° C. to 160 ° C. are effective.
- no treatment with an autoclave may be performed.
- the treatment with an autoclave is carried out, for example, at a pressure of about 1 ⁇ 10 6 Pa to about 1.5 ⁇ 10 6 Pa and a temperature of about 100 ° C. to about 145 ° C. for about 20 minutes to 2 hours.
- the resin layer (X) and / or the resin layer (Y) are coextruded together with the correspondingly colored polymer melt or at least one of the resin layer (X) and the resin layer (Y) One may have partially different coloration.
- the resin layer (Y) may have a wedge-shaped thickness profile.
- the laminate of the present invention can have a wedge-shaped thickness profile even when the thickness profile of the resin layer (X) is a parallel plane, and a head-up display (HUD) in a windshield for an automobile It can be used for
- the laminated glass of the present invention can be used as laminated glass in buildings or vehicles.
- it can be used for windshields such as trains, trains, cars, ships, aircrafts, etc., rear glass, roof glass, side glass and the like.
- the conductive structure-containing film with a substrate film obtained by the production method of the present invention is, besides laminated glass, a heating member for anti-snow protection and anti-fogging measures such as mirrors, curve mirrors, traffic lights and traffic signs; It can also be used as a heating member for preventing malfunction of a camera, sensor or the like in a window glass for automobile; functional member used for electromagnetic wave transmission / reception, sensor, electromagnetic wave shield, touch panel, crime prevention glass, display etc.
- thermoplastic resin composition (A) The polyvinyl butyral (PVB) resin shown in Table 1 was mixed at a mass ratio described in Table 2 to obtain a thermoplastic resin composition (A).
- the viscosity of a 10% by mass toluene / ethanol 1/1 (mass ratio) solution of a thermoplastic resin composition (A) measured at 20 ° C. and 30 rpm using a Brookfield type (B type) viscometer It was measured. The results are shown in Table 2.
- thermoplastic resin composition (A) -III shown in Table 2 was formed into a film at a die temperature of 220 ° C. using an extruder equipped with a T-die to prepare a polyvinyl butyral resin film.
- the film was adjusted to an average thickness of about 50 ⁇ m in Production Example 1 and to an average thickness of about 52 ⁇ m in Production Example 2.
- Example 1 ⁇ Step (1)> The thermoplastic resin compositions (A) -III shown in Table 2 were dissolved in ethanol to prepare a 12% by mass solution. The resulting solution is applied to a 50 ⁇ m-thick PET film unwound from a roll using a comma-type (a kind of knife coating method) small coating tester, and heated by 50 to 120 ° C. hot air in a drying zone. After removing the solvent (ethanol), it was cut into A4 size and vacuum dried (50 ° C., 12 hours) to form a resin layer (X) on one side of the PET film. The thickness of the resin layer (X) was 32 ⁇ m.
- the conductive structure was formed by immersing in a copper etching solution, and the remaining photoresist layer was removed by a conventional method to obtain a conductive structure-containing film (a) with a base film.
- the conductive structure has a structure in which copper wires having a line width of 7 ⁇ m are arranged in a wavy line at intervals of 500 ⁇ m, and both ends of each wavy line are provided at intervals of 10 cm.
- Step (6), Step (7) The obtained base material film-attached conductive structure-containing film (a) was cut out about 0.5 cm outside (12 cm long, 12 cm wide) from the end of the conductive structure. Subsequently, the PET film was peeled and removed, and the obtained conductive structure-containing film (a ′) was placed on a glass of 15 cm long, 15 cm wide, and 3 mm in thickness. At this time, the conductive structure-containing film (a ′) was disposed such that the surface not having the conductive structure was in contact with the glass, and the conductive structure was in the vicinity of the center of the glass.
- the solution was put in a vacuum bag and decompressed at room temperature using a vacuum pump for 15 minutes, and then heated at 100 ° C. for 60 minutes while being decompressed. After the temperature was lowered, the pressure was returned to normal pressure, and the laminated glass after prelamination was taken out. Then, this was introduced into an autoclave and treated at 140 ° C. and 1.2 MPa for 30 minutes to produce a laminated glass. As a result of observing the state of the conductive structure in the obtained laminated glass using a loupe, no clear deformation or disconnection was found in the conductive structure.
- Example 2 Instead of arranging one interlayer film for automobile windshields of 15 cm long, 15 cm wide and 0.76 mm thickness as a resin layer (Y) in ⁇ Preparation of laminated glass (step (7))> of Example 1 Intermediate film for automobile windshield [15 mm long, 15 cm wide and 0.38 mm thickness as a resin layer (Y) on both surfaces of the conductive structure-containing film (a ′) [polyvinyl butyral resin (hydroxyl group content 20.0 mass% A laminated glass was produced in the same manner as in Example 1 except that the viscosity average polymerization degree 1700 of polyvinyl alcohol used as the raw material and the content of 72% by mass and the content of 3GO of 28% by mass were arranged one by one. As a result of observing the state of the conductive structure in the obtained laminated glass using a loupe, no clear deformation or disconnection was found in the conductive structure.
- Steps (1) and (2) were performed in the same manner as in Example 1 except that the thickness of the resin layer (X) was set to 20 ⁇ m, to obtain a base film-attached conductive structure-containing film (b).
- the base film-attached conductive structure-containing film (b) is cut out about 2 cm from the end of the conductive structure (length 15 cm, width 15 cm) and each bus bar (5 mm width copper wire) at both ends of the conductive structure
- An electrode (a copper foil tape with a conductive adhesive) was pasted onto the) so that the ends of each electrode were sticking out.
- the polyvinyl butyral resin film prepared in Production Example 1 is cut out into 15 cm long and 15 cm wide on a glass of 15 cm long, 15 cm wide, and 3 mm thickness, and stacked, and the electrode obtained above is thereon
- the base film-attached conductive structure film (b) attached was stacked such that the PET film was the outermost layer.
- the solution was put in a vacuum bag and decompressed at room temperature for 15 minutes using a vacuum pump, then heated at 100 ° C. for 60 minutes with the vacuum reduced, and then cooled back to normal pressure.
- Example 4 Instead of the polyvinyl butyral resin film produced in Production Example 1 used in ⁇ Step (8)> of Example 3 and the interlayer for a car windshield of 0.76 mm thickness used in ⁇ Step (9)> Intermediate film for automobile front glass with a thickness of 0.38 mm [Polyvinyl butyral resin (hydroxyl group content 20.0 mass%, viscosity average degree of polymerization of polyvinyl alcohol used as raw material 1700 mass) 72 mass%, 3GO content 28 mass%] A laminated glass was produced in the same manner as in Example 3 except that each was used. As a result of observing the state of the conductive structure in the obtained laminated glass using a loupe, no clear deformation or disconnection was found in the conductive structure.
- Example 5 The pressure was reduced (5 kPa) for 15 minutes at 140 ° C. using a vacuum laminator in ⁇ Step (2)> of Example 1, and the upper chamber was returned to normal pressure and pressurized for 3 minutes instead of adhering, heat set at 140 ° C.
- a body-containing film and a laminated glass were produced. As a result of observing the state of the conductive structure in the obtained laminated glass using a loupe, no clear deformation or disconnection was found in the conductive structure.
- thermoplastic resin composition (A) -IV was used instead of the thermoplastic resin composition (A) -III, and the concentration of the ethanol solution of the thermoplastic resin composition (A) was changed to 12% by mass.
- a base film-attached conductive structure-containing film (d), a conductive structure-containing film, and a laminated glass were produced in the same manner as in Example 1 except that the% by mass was used. As a result of observing the state of the conductive structure in the obtained laminated glass using a loupe, no clear deformation or disconnection was found in the conductive structure.
- thermoplastic resin composition (A) -I was used instead of the thermoplastic resin composition (A) -III, and the concentration of the ethanol solution of the thermoplastic resin composition (A) was changed to 12% by mass.
- a substrate film-attached conductive structure-containing film (e), a conductive structure-containing film, and a laminated glass were produced in the same manner as in Example 1 except that the% by mass was used. As a result of observing the state of the conductive structure in the obtained laminated glass using a loupe, although deformation was partially recognized in the conductive structure, no disconnection was recognized.
- thermoplastic resin composition (A) -V was used instead of the thermoplastic resin composition (A) -III, and the concentration of the ethanol solution of the thermoplastic resin composition (A) was changed to 12% by mass.
- a substrate film-attached conductive structure-containing film (f), a conductive structure-containing film, and a laminated glass were produced in the same manner as in Example 1 except that the% by mass was used. As a result of observing the state of the conductive structure in the obtained laminated glass using a loupe, although deformation was partially recognized in the conductive structure, no disconnection was recognized.
- thermoplastic resin compositions (A) -III shown in Table 2 were dissolved in ethanol to prepare a 12% by mass solution.
- the resulting solution is applied to the blackened surface of a 7 ⁇ m thick copper foil whose one side has been blackened using a comma type (one type of knife coating type) small coating tester, and 50 in the drying zone After the solvent was removed by hot air at ⁇ 120 ° C., the sheet was cut into A4 size and vacuum dried (50 ° C., 12 hours) to form a resin layer (X) on one side of the copper foil.
- the thickness of the resin layer (X) was 31 ⁇ m.
- ⁇ Step (4)> A 50 ⁇ m-thick PET film is stacked on the side of the resin layer (X) obtained in step (3) which does not have a copper foil, and the pressure is reduced (5 kPa) at 140 ° C. for 15 minutes using a vacuum laminator. The pressure was returned to normal pressure and pressure was applied for 3 minutes to bond, to obtain a laminate (G) comprising a laminated structure of copper foil / resin layer (X) / PET film.
- ⁇ Step (5)> After laminating a dry film resist on the copper foil of the obtained laminate (G), an etching resistance pattern was formed using a photolithography method.
- the conductive structure was formed by immersing in a copper etching solution, and then the remaining photoresist layer was removed by a conventional method to obtain a conductive structure-containing film (g) with a base film.
- the conductive structure has a structure in which copper wires having a line width of 7 ⁇ m are arranged in a wavy line at intervals of 500 ⁇ m, and both ends of each wavy line are provided at intervals of 10 cm.
- Comparative Example 1 The 52 ⁇ m thick polyvinyl butyral resin film obtained in Production Example 2 is sandwiched between a 50 ⁇ m thick PET film and a 7 ⁇ m thick copper foil and laminated at 140 ° C. using a vacuum laminator.
- the polyvinyl butyral resin film (H) provided with the base film and copper foil was obtained.
- the polyvinyl butyral resin film (H) was used instead of the base film-attached conductive structure-containing film (c), a base film-attached conductive structure-containing film ( h), a conductive structure-containing film, and a laminated glass were produced.
- a break such that the conductive thin wire was peeled off was observed in a part of the conductive structure.
- thermoplastic resin composition (A) -I shown in Table 2 Relative to 100 parts by mass of the thermoplastic resin composition (A) -I shown in Table 2, 0.15 parts by mass of TINUVIN 326 (manufactured by BASF) as an antioxidant, triethylene glycol as an ultraviolet (UV) absorber 0.04 parts by mass of bis (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate) and 0.03 parts by mass of magnesium acetate tetrahydrate as an adhesion regulator and potassium acetate 0.02 parts by mass was added and mixed.
- TINUVIN 326 manufactured by BASF
- UV absorber 0.04 parts by mass of bis (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate
- magnesium acetate tetrahydrate as an adhesion regulator and potassium acetate 0.02 parts by mass was added and mixed.
- the obtained mixture is extruded onto a blackened surface of a 7 ⁇ m thick, 30 cm wide copper foil which has been blackened on one side and unwound from a roll using an extruder (die setting temperature: 240 ° C.) , And a resin layer (X) was formed on one side of the copper foil.
- the thickness of the resin layer (X) was 35 ⁇ m.
- the mixture is the thermoplastic resin composition (A) in the present invention.
- ⁇ Step (4)> A 50 ⁇ m thick, 30 cm wide PET film is placed on the side of the resin layer (X) obtained in step (3) that does not have a copper foil, and it passes between thermocompression bonding rolls set at 140 ° C. ( The pressure was 0.2 MPa and the speed was 0.5 m / min) to obtain a laminate (I) having a laminate structure of copper foil / resin layer (X) / PET film, and was wound into a roll.
- a conductive structure-containing substrate film is included Film (i) was prepared and wound into a roll.
- thermoplastic resin composition (A) -III is used instead of thermoplastic resin composition (A) -I, and 10 parts by mass of 3GO is further added to 100 parts by mass of thermoplastic resin composition (A) -III
- the conductive structure-containing film with a base film (j), the conductive structure-containing film, and the laminated glass in the same manner as in Example 10 except for the addition and the thickness of the resin layer (X) to 28 ⁇ m. was produced.
- no clear deformation or disconnection was found in the conductive structure.
- thermoplastic resin composition (A) -I shown in Table 2 Relative to 100 parts by mass of the thermoplastic resin composition (A) -I shown in Table 2, 0.15 parts by mass of TINUVIN 326 (manufactured by BASF) as an antioxidant, triethylene glycol bis (3 as a UV absorber) 0.04 parts by weight of (3-t-butyl-4-hydroxy-5-methylphenyl) propionate), 0.03 parts by weight of magnesium acetate tetrahydrate as an adhesion regulator, and 0.02 parts of potassium acetate Parts by mass are added and mixed, and the resulting mixture is applied by extrusion onto a PET film of 50 ⁇ m in thickness and 30 cm in width using an extruder (die setting temperature: 240 ° C.), and resin is applied to one side of the PET film Layer (X) was formed.
- TINUVIN 326 manufactured by BASF
- triethylene glycol bis (3 as a UV absorber) 0.04 parts by weight of (3-t-butyl-4-hydroxy-5-methylphen
- the thickness of the resin layer (X) was 36 ⁇ m.
- Step (2)> On the surface of the resin layer (X) obtained in step (1) which does not have a PET film, place the blackened surface of a copper foil with a thickness of 7 ⁇ m and a width of 30 cm, one side of which is blackened, 140
- the laminated body (K) consisting of a laminated structure of PET film / resin layer (X) / copper foil is made to pass through (pressure: 0.2 MPa, speed 0.5 m / min) between thermocompression bonding rolls set to ° C. It was obtained and wound up in a roll.
- a base film-attached conductive structure-containing film (k), a conductive structure-containing film, and a laminated glass were produced in the same manner as in Example 10 except that the obtained laminate (K) was used.
- the obtained laminate (K) was used.
- Example 13 Relative to 100 parts by mass of the thermoplastic resin composition (A) -I shown in Table 2, 0.15 parts by mass of TINUVIN 326 (manufactured by BASF) as an antioxidant, triethylene glycol bis (3 as a UV absorber) 0.04 parts by weight of (3-t-butyl-4-hydroxy-5-methylphenyl) propionate), 0.03 parts by weight of magnesium acetate tetrahydrate as an adhesion regulator, and 0.02 parts of potassium acetate The parts by mass were added and mixed.
- TINUVIN 326 manufactured by BASF
- the obtained mixture is extruded onto a blackened surface of a 7 ⁇ m thick, 30 cm wide copper foil which has been blackened on one side and unwound from a roll using an extruder (die setting temperature: 240 ° C.)
- the resin layer (X) was formed.
- a 50 ⁇ m-thick PET film is pasted together through a pressure roller so that the PET film is in contact with the resin layer (X) to obtain a laminate (L) comprising a laminated structure of copper foil / resin layer (X) / PET film , Rolled into a roll.
- the thickness of the resin layer (X) was 34 ⁇ m.
- the base film-attached conductive structure-containing film (I), the conductive structure-containing film, and the laminated glass were prepared in the same manner as in Example 10 except that the obtained laminate (L) was used.
- the obtained laminate (L) was used.
- Comparative Example 2 (No base film) A conductive structure-containing film and a laminated glass were produced in the same manner as in Example 10 except that ⁇ Step (4)> was not performed, and that the thickness of the resin layer (X) was 31 ⁇ m. As a result of observing the state of the conductive structure in the obtained laminated glass using a loupe, disconnection was observed in a part of the conductive structure. It is estimated that the wrinkles which arose at the time of the thermocompression bonding of copper foil are the cause.
- Comparative Example 3 No base film; containing plasticizer
- a conductive structure-containing film and a laminated glass were produced in the same manner as in Example 11 except that ⁇ Process (4)> was not performed, and the thickness of the resin layer (X) was 31 ⁇ m.
- the conductive structure-containing film was unwound from the roll, it was mainly due to peeling off of a part of the conductive structure attached to the adjacent resin layer (X).
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Abstract
Description
[1]基材フィルムの片面に、ポリビニルアセタール樹脂、アイオノマー樹脂およびエチレン酢酸ビニル共重合体樹脂からなる群より選ばれる少なくとも1種の熱可塑性樹脂を含む熱可塑性樹脂組成物(A)を塗布して樹脂層(X)を形成する工程(1);および該樹脂層(X)上に導電構造体を形成する工程(2);を含む、基材フィルム付き導電構造体含有フィルムの製造方法。
[2]金属箔の片面に、ポリビニルアセタール樹脂、アイオノマー樹脂およびエチレン酢酸ビニル共重合体樹脂からなる群より選ばれる少なくとも1種の熱可塑性樹脂を含む熱可塑性樹脂組成物(A)を塗布して樹脂層(X)を形成する工程(3);該樹脂層(X)に基材フィルムをラミネートする工程(4);および金属箔を加工して導電構造体を形成する工程(5);を含む、基材フィルム付き導電構造体含有フィルムの製造方法。
[3]前記工程(1)または前記工程(3)において、熱可塑性樹脂組成物(A)を塗布する方法が、熱可塑性樹脂組成物(A)を溶融して塗布する方法によるものである、前記[1]または[2]に記載の基材フィルム付き導電構造体含有フィルムの製造方法。
[4]前記工程(1)または前記工程(3)において、熱可塑性樹脂組成物(A)を塗布する方法が、熱可塑性樹脂組成物(A)の溶液または分散液を塗布する方法によるものである、前記[1]または[2]に記載の基材フィルム付き導電構造体含有フィルムの製造方法。
[5]前記熱可塑性樹脂組成物(A)が、熱可塑性樹脂組成物(A)の総質量に基づいて50質量%以上のポリビニルアセタール樹脂を含む、前記[1]~[4]のいずれかに記載の基材フィルム付き導電構造体含有フィルムの製造方法。
[6]ブルックフィールド型(B型)粘度計を用いて20℃、30rpmで測定された、前記ポリビニルアセタール樹脂の濃度10質量%のトルエン/エタノール=1/1(質量比)溶液の粘度が200mPa・sより大きい、前記[5]に記載の基材フィルム付き導電構造体含有フィルムの製造方法。
[7]前記熱可塑性樹脂組成物(A)が、熱可塑性樹脂組成物(A)の総質量に基づいて0~20質量%の可塑剤を含む、前記[5]または[6]に記載の基材フィルム付き導電構造体含有フィルムの製造方法。
[8]前記熱可塑性樹脂組成物(A)が、熱可塑性樹脂組成物(A)の総質量に基づいて80質量%以上のポリビニルアセタール樹脂を含む、前記[1]~[7]のいずれかに記載の基材フィルム付き導電構造体含有フィルムの製造方法。
[9]前記導電構造体が少なくとも2本のバスバー構造を有する、前記[1]~[8]のいずれかに記載の基材フィルム付き導電構造体含有フィルムの製造方法。
[10]前記導電構造体が少なくとも2本のバスバー構造の間に金属細線構造を有する、前記[9]に記載の基材フィルム付き導電構造体含有フィルムの製造方法。
[11]前記工程(2)または前記工程(5)において、金属箔をエッチングして前記導電構造体を形成する、前記[1]~[10]のいずれかに記載の基材フィルム付き導電構造体含有フィルムの製造方法。
[12]前記[1]~[11]のいずれかに記載の製造方法により得られる基材フィルム付き導電構造体含有フィルム。
[13]前記[1]~[11]のいずれかに記載の製造方法により得られる基材フィルム付き導電構造体含有フィルムから基材フィルムを除去する工程(6)を含む、導電構造体含有フィルムの製造方法。
[14]前記[13]に記載の製造方法により得られる、導電構造体含有フィルム。
[15]前記[13]に記載の製造方法により得られる導電構造体含有フィルムを少なくとも2枚のガラスの間に挟みラミネートする工程(7)を含む、合わせガラスの製造方法。
[16]前記[1]~[11]のいずれかに記載の製造方法により得られる基材フィルム付き導電構造体含有フィルムの基材フィルムを有さない面にガラスを重ねラミネートして積層体を得る工程(8)、および該積層体から基材フィルムを除去し、ガラスを有さない面にさらにガラスを重ねてラミネートする工程(9)を含む、合わせガラスの製造方法。
[17]前記工程(7)において、前記導電構造体含有フィルムとガラスとの間に、少なくとも1層の樹脂層(Y)を挟む、前記[15]に記載の合わせガラスの製造方法。
[18]前記工程(8)において基材フィルム付き導電構造体含有フィルムとガラスとの間に、および/または前記工程(9)において基材フィルムを除去した後の積層体とガラスとの間に、少なくとも1層の樹脂層(Y)を挟む、前記[16]に記載の合わせガラスの製造方法。
[19]前記樹脂層(Y)が、前記熱可塑性樹脂組成物(A)に含まれる熱可塑性樹脂と同一の熱可塑性樹脂を含む、前記[17]または[18]に記載の合わせガラスの製造方法。
[20]前記[15]~[19]のいずれかに記載の製造方法により得られる合わせガラス。
[21]前記[14]に記載の導電構造体含有フィルムを用いた、加熱部材。
本発明のこれらの製造方法により、基材フィルム/樹脂層(X)/導電構造体の積層構成を有する基材フィルム付き導電構造体含有フィルムが製造される。基材フィルム付き導電構造体含有フィルムにおいて、基材フィルムと樹脂層(X)、および樹脂層(X)と導電構造体は、互いに接合または一体化されている。
<樹脂組成物(A)>
工程(1)および工程(3)で用いる樹脂組成物(A)は、ポリビニルアセタール樹脂、アイオノマー樹脂およびエチレン酢酸ビニル共重合体樹脂からなる群より選ばれる少なくとも1種の熱可塑性樹脂を含む。中でも、樹脂組成物(A)がポリビニルアセタール樹脂および/またはアイオノマー樹脂を含むことが好ましく、ポリビニルアセタール樹脂を含むことが好ましい。
樹脂組成物(A)がポリビニルアセタール樹脂を含む場合、樹脂組成物(A)中のポリビニルアセタール樹脂の含有量は、樹脂組成物(A)の総質量に基づいて50質量%以上が好ましく、70質量%以上がより好ましく、80質量%以上がさらに好ましく、85質量%以上が特に好ましく、90質量%以上が極めて好ましく、95質量%以上が最も好ましく、100質量%であってもよい。
ポリビニルアセタール樹脂の好ましい粘度平均重合度は、原料となるポリビニルアルコール系樹脂の上記粘度平均重合度と同一である。樹脂組成物(A)が異なる2種類以上のポリビニルアセタール樹脂を含む場合、少なくとも1種類のポリビニルアセタール樹脂の粘度平均重合度が前記下限値以上かつ前記上限値以下であることが好ましい。
樹脂組成物(A)は、樹脂組成物(A)の総質量に基づいて0~20質量%の可塑剤を含むことが好ましい。樹脂組成物(A)中の可塑剤の含有量はより好ましくは0~19質量%、さらに好ましくは0~15質量%、特に好ましくは0~10質量%、最も好ましくは0~5質量%である。可塑剤の含有量が前記範囲内であると、本発明の基材フィルム付き導電構造体含有フィルムから基材フィルムを除去した後の導電構造体含有フィルムが取扱い性に優れる傾向にあり、該導電構造体含有フィルムを用いた合わせガラスの作製時に導電構造体の変形および断線が抑制されやすく、その結果、良好な通電性が得られやすい。
・多価の脂肪族または芳香族酸のエステル。例えば、ジアルキルアジペート(例えば、ジヘキシルアジペート、ジ-2-エチルブチルアジペート、ジオクチルアジペート、ジ-2-エチルヘキシルアジペート、ヘキシルシクロヘキシルアジペート、ヘプチルアジペート、ノニルアジペート、ジイソノニルアジペート、ヘプチルノニルアジペート);アジピン酸とアルコール若しくはエーテル化合物を含むアルコールとのエステル(例えば、ジ(ブトキシエチル)アジペート、ジ(ブトキシエトキシエチル)アジペート);ジアルキルセバケート(例えば、ジブチルセバケート);セバシン酸と脂環式若しくはエーテル化合物を含むアルコールとのエステル;フタル酸のエステル(例えば、ブチルベンジルフタレート、ビス-2-ブトキシエチルフタレート);および脂環式多価カルボン酸と脂肪族アルコールとのエステル(例えば、1,2-シクロヘキサンジカルボン酸ジイソノニルエステル)が挙げられる。
・多価の脂肪族若しくは芳香族アルコールまたは1つ以上の脂肪族若しくは芳香族置換基を有するオリゴエーテルグリコールのエステルまたはエーテル。例えば、グリセリン、ジグリコール、トリグリコール、テトラグリコール等と、直鎖状若しくは分岐状の脂肪族若しくは脂環式カルボン酸とのエステルが挙げられる。さらに具体的には、ジエチレングリコール-ビス-(2-エチルヘキサノエート)、トリエチレングリコール-ビス-(2-エチルヘキサノエート)、トリエチレングリコール-ビス-(2-エチルブタノエート)、テトラエチレングリコール-ビス-n-ヘプタノエート、トリエチレングリコール-ビス-n-ヘプタノエート、トリエチレングリコール-ビス-n-ヘキサノエート、テトラエチレングリコールジメチルエーテル、およびジプロピレングリコールベンゾエートが挙げられる。
・脂肪族または芳香族のエステルアルコールのリン酸エステル。例えば、トリス(2-エチルヘキシル)ホスフェート、トリエチルホスフェート、ジフェニル-2-エチルヘキシルホスフェート、およびトリクレジルホスフェートが挙げられる。
・クエン酸、コハク酸および/またはフマル酸のエステル。
・多価アルコールと多価カルボン酸とからなるポリエステルまたはオリゴエステル。末端はヒドロキシ基またはカルボキシル基であっても、エステル化若しくはエーテル化されていてもよい。
・ラクトン若しくはヒドロキシカルボン酸からなるポリエステルまたはオリゴエステル。末端はヒドロキシ基またはカルボキシル基であっても、エステル化若しくはエーテル化されていてもよい。
樹脂組成物(A)がアイオノマー樹脂を含む場合、樹脂組成物(A)中のアイオノマー樹脂の含有量は、樹脂組成物(A)の総質量に基づいて50質量%以上が好ましく、70質量%以上がより好ましく、80質量%以上がさらに好ましく、85質量%以上が特に好ましく、90質量%以上が極めて好ましく、95質量%以上が最も好ましく、100質量%であってもよい。樹脂組成物(A)は、1種類のアイオノマー樹脂を含んでいてもよく、α,β-不飽和カルボン酸の種類、α,β-不飽和カルボン酸の構成単位の含有割合、中和のための金属イオンの種類、α-オレフィンの種類、α-オレフィンの構成単位の含有割合、α,β-不飽和カルボン酸のエステルなどに代表されるその他の共重合可能なモノマーの種類およびその含有割合等のうちいずれか1つ以上がそれぞれ異なる2種類以上のアイオノマー樹脂を含んでいてもよい。
樹脂組成物(A)がエチレン酢酸ビニル共重合体樹脂を含む場合、樹脂組成物(A)中のエチレン酢酸ビニル共重合体樹脂の含有量は、樹脂組成物(A)の総質量に基づいて50質量%以上が好ましく、70質量%以上がより好ましく、80質量%以上がさらに好ましく、85質量%以上が特に好ましく、90質量%以上が極めて好ましく、95質量%以上が最も好ましく、100質量%であってもよい。樹脂組成物(A)は、1種類のエチレン酢酸ビニル共重合体樹脂を含んでいてもよく、酢酸ビニル構成単位の含有割合、その他の共重合可能なモノマー、例えば酢酸ビニル以外のビニルエステルや炭素数3以上のα-オレフィンなどの種類およびその含有割合等のうちいずれか1つ以上がそれぞれ異なる2種類以上のエチレン酢酸ビニル共重合体樹脂を含んでいてもよい。
樹脂組成物(A)は、水、紫外線吸収剤、酸化防止剤、接着調整剤、増白剤若しくは蛍光増白剤、安定剤、色素、顔料、加工助剤、有機若しくは無機ナノ粒子、焼成ケイ酸、表面活性剤等の可塑剤以外の添加剤を含んでいてもよい。樹脂層(X)上に形成された導電構造体の腐食を抑制するために、樹脂組成物(A)が腐食防止剤を含有してもよい。樹脂組成物(A)中の腐食防止剤の含有量は、樹脂組成物(A)の総質量に基づいて、好ましくは0.005~5質量%である。腐食防止剤としては、例えばベンゾトリアゾール系化合物または置換基を有するベンゾトリアゾール系化合物が挙げられる。
樹脂層(X)は、樹脂組成物(A)を基材フィルムまたは金属箔の片面に塗布する方法により形成される。かかる方法を採用することにより、樹脂組成物(A)からなるフィルムと基材フィルムまたは金属箔とをラミネートする方法に比べ、樹脂組成物(A)を製膜する工程が不要なため生産性が高く、また樹脂層(X)と基材フィルムとの間および樹脂層(X)と金属箔との間に気泡等の欠陥が生じにくい。樹脂組成物(A)を基材フィルムまたは金属箔の片面にコートする方法は特に限定されないが、樹脂組成物(A)を溶融して塗布する方法、または樹脂組成物(A)の溶液または分散液を塗布する方法が好ましい。
上記工程(1)および上記工程(3)における樹脂層(X)の厚さは好ましくは1μm以上、より好ましくは5μm以上、さらに好ましくは20μm以上、特に好ましくは30μm以上である。樹脂層(X)の厚さが前記値以上であると、樹脂層(X)の収縮または変形に起因する導電構造体の歪等が生じにくい。樹脂層(X)の厚さは好ましくは350μm以下、より好ましくは330μm以下、より好ましくは270μm以下、さらに好ましくは250μm以下、特に好ましくは150μm以下、最も好ましくは100μm以下である。樹脂層(X)の厚さが前記値以下であると、後述する、ポリビニルアセタール樹脂および可塑剤を含む樹脂層(Y)を積層する場合に、樹脂層(Y)から樹脂層(X)への可塑剤移行量が少なくなり、樹脂層(Y)中の可塑剤量の低下が抑制されるため、導電構造体含有フィルムを用いた乗物用合わせガラスの頭部衝撃指数が小さくなりやすい。樹脂層(X)の厚さは、厚み計またはレーザー顕微鏡等を用いて測定される。
本発明に用いられる基材フィルムを構成する樹脂は特に限定されず、例えば、ポリエチレンテレフタレート(PET)などのポリエステル樹脂;ポリイミド樹脂;トリアセチルクロライド(TAC)、ポリエチレン(PE)、ポリプロピレン(PP)、ポリ塩化ビニル(PVC)などが使用できる。上記基材フィルムは樹脂層(X)との適度な接着性を有していること、具体的には、工程(2)においては樹脂層(X)から剥がれず、かつ合わせガラス作製などに使用される際には樹脂層(X)から剥離させるなどの手段により除去可能であり、加熱時や工程(2)における各種薬剤との接触時にも収縮等による変形などを起こさないものであることが好ましい。かかる観点から、基材フィルムを構成する樹脂はポリエステル樹脂、ポリイミド樹脂が好ましく、PETが特に好ましい。基材フィルムの厚さは、コストと強度の観点から、10~250μmが好ましく、20~150μmがより好ましく、30~100μmが特に好ましい。
工程(3)で用いる金属箔は導電性を有する金属を含む限り特に限定されず、例えば銅箔、銀箔が挙げられ、中でも銅箔が好ましい。
本発明の製造方法の一態様は、金属箔の片面に樹脂層(X)を形成する前記工程(3)後、該樹脂層(X)に基材フィルムをラミネートする工程(4)を含む。樹脂層(X)に基材フィルムをラミネートする方法は特に制限されないが、樹脂層(X)が溶融する温度以上の温度で、圧着ロール、加熱ロール、プレス機、真空ラミネーターなどを用いてラミネートする公知の方法が挙げられる。中でも、生産性の高いロール・トゥ・ロール方式に適用しやすい圧着ロールを用いる方法が特に好ましい。圧着ロールを用いる方法において、圧着時の樹脂層(X)の温度は樹脂組成物(A)のガラス転移温度(Tg)以上が好ましく、Tg+30℃以上がより好ましく、Tg+50℃以上がさらに好ましく、Tg+70℃以上が特に好ましい。圧着時の樹脂層(X)の温度の上限値は特に制限されない。圧着時の樹脂層(X)の温度は200℃以下が好ましく、180℃以下がより好ましく、160℃以下が特に好ましい。圧着時の樹脂層(X)の温度が上記下限値より高いと、金属箔と樹脂層(X)との間の接着力および樹脂層(X)と基材フィルムとの間の接着力が十分となりやすく、上記上限値より低いと、樹脂層(X)の熱分解や発泡、および樹脂組成物(A)の流出による樹脂層(X)の厚みの低下などの問題が生じにくい。また、加熱ロールを用いる方法において、加熱ロールの表面温度の下限値は、圧着ロールを用いる方法における樹脂層(X)の好ましい温度として上述した温度よりも高いことが好ましく、かかる温度より10℃以上高いことがより好ましく、かかる温度より20℃以上高いことが特に好ましい。
本発明の製造方法の一態様は、金属箔の片面に樹脂層(X)を形成する前記工程(3)、および該樹脂層(X)に基材フィルムをラミネートする工程(4)後に、金属箔を加工して導電構造体を形成する工程(5)を含む。金属箔を加工して導電構造体を形成する方法に特に制限はないが、例えば金属箔をエッチングして導電構造体を形成する方法が挙げられる。より具体的には、工程(3)および工程(4)により得られた金属箔/樹脂層(X)/基材フィルムからなる積層フィルムの金属箔上にドライフィルムレジストをラミネートした後、フォトリソグラフィの手法を用いてエッチング抵抗パターンを形成し、次いで、エッチング抵抗パターンが付与された積層フィルムを銅エッチング液に浸漬して導電構造体を形成した後、公知の方法により残存するフォトレジスト層を除去することによって導電構造体を形成する方法が挙げられる。上記金属箔をエッチングして導電構造体を形成する方法は、所望の形状の導電構造体を簡便かつ容易に、効率的に形成できる。
本発明の製造方法の別の態様は、基材フィルムの片面に樹脂層(X)を形成する工程(1)後に、該樹脂層(X)上に導電構造体を形成する工程(2)を含む。樹脂層(X)上に導電構造体を形成する方法に特に制限はないが、(i)樹脂層(X)上に金属箔をラミネートし、上述の方法により金属箔をエッチングして導電構造体を形成する方法;(ii)樹脂層(X)上に蒸着等により金属層を形成し、上述の方法により金属箔をエッチングして導電構造体を形成する方法;(iii)樹脂層(X)上に導電ペーストを印刷して導電構造体を形成する方法;(iv)樹脂層(X)上に金属ワイヤーを配置する方法;等が挙げられる。中でも、前方視認性に優れる合わせガラスの作製に適する基材フィルム付き導電構造体含有フィルムを製造する観点から、(i)および(ii)の方法が好ましく、製造コストの観点から(i)の方法がより好ましい。(i)の方法で用いる金属箔の好ましい態様は、前述した工程(3)で用いる金属箔の好ましい態様と同様である。(i)の方法における金属箔をラミネートする方法は特に制限されず、樹脂層(X)が溶融する温度以上の温度で、圧着ロール、加熱ロール、プレス機、真空ラミネーターなどを用いてラミネートする公知の方法を適用できる。圧着ロールを用いる方法における圧着時の樹脂層(X)の好ましい温度、および加熱ロールを用いる方法における加熱ロールの好ましい表面温度は、工程(4)の好ましい態様として上述した温度と同様である。
工程(2)および工程(5)において形成された導電構造体の厚さは、光の反射低減および必要な発熱量が得られやすい観点から、好ましくは1~30μm、より好ましくは2~20μm、さらに好ましくは3~15μm、特に好ましくは3~12μmである。導電構造体の厚さは、厚み計またはレーザー顕微鏡等を用いて測定される。
上述の製造方法により得られる基材フィルム付き導電構造体含有フィルムから基材フィルムを除去する工程(6)を含む、基材フィルムを有さない導電構造体含有フィルム(以下、単に「導電構造体含有フィルム」と称する)の製造方法も本発明のひとつである。また、かかる製造方法により得られる導電構造体含有フィルムも本発明のひとつである。本発明の製造方法により得られる基材フィルム付き導電構造体含有フィルムから基材フィルムを除去する方法に特に制限はなく、基材フィルムと樹脂層(X)との界面で機械的に剥離する方法等が挙げられる。
本発明の製造方法により得られた基材フィルム付き導電構造体含有フィルムを用いて合わせガラスを製造する方法、およびかかる製造方法により得られる合わせガラスも、本発明のひとつである。基材フィルム付き導電構造体含有フィルムを用いた合わせガラスの製造方法としては、例えば(i)基材フィルム付き導電構造体含有フィルムから基材フィルムを除去した導電構造体含有フィルムを少なくとも2枚のガラスの間に挟みラミネートする工程(7)を含む製造方法;(ii)基材フィルム付き導電構造体含有フィルムの基材フィルムを有さない面にガラスを重ねラミネートして積層体を得る工程(8)、および該積層体から基材フィルムを除去し、ガラスを有さない面にさらにガラスを重ねてラミネートする工程(9)を含む製造方法;(iii)基材フィルム付き導電構造体含有フィルムを少なくとも2枚のガラスの間にラミネートする工程を含む製造方法;(iv)基材フィルムとしてPET等の有機ガラスを用い、基材フィルム付き導電構造体含有フィルムの導電構造体を有する面に必要に応じて別の層を介した上でさらにガラスを載せてラミネートする方法;等が挙げられる。中でも、得られる合わせガラスの透明性の観点から(i)の製造方法または(ii)の製造方法が好ましい。
表1に示すポリビニルブチラール(PVB)樹脂を表2に記載の質量比で混合し、熱可塑性樹脂組成物(A)を得た。ブルックフィールド型(B型)粘度計を用いて20℃、30rpmで測定された、熱可塑性樹脂組成物(A)の濃度10質量%のトルエン/エタノール=1/1(質量比)溶液の粘度を測定した。結果を表2に示す。
実施例および比較例で得られた合わせガラスにおける導電構造体の状態を、ルーペで目視観察し、配線の変形および断線の有無を下記基準で評価した。
A 変形および断線は認められなかった。
B 部分的に変形は認められたが、断線は認められなかった。
C 僅かに断線が認められた。
D 一部に重大な断線がみられた。
E 断線が顕著であった。
<ポリビニルブチラール樹脂フィルムの作製>
表2に示した熱可塑性樹脂組成物(A)-IIIを、Tダイを備えた押出機を用いてダイ温度220℃で製膜し、ポリビニルブチラール樹脂フィルムを作製した。当該フィルムを、製造例1では平均厚さ約50μmに調整し、製造例2では平均厚さ約52μmに調整した。
<工程(1)>
表2に示した熱可塑性樹脂組成物(A)-IIIをエタノールに溶解し、12質量%の溶液を調製した。得られた溶液を、コンマ方式(ナイフコート方式の一種)の小型塗工試験機を用いて、ロールから巻き出した厚さ50μmのPETフィルムに塗布し、乾燥ゾーンで50~120℃の熱風により溶媒(エタノール)を除去した後、A4サイズに切り取って、真空乾燥(50℃、12時間)を行い、PETフィルムの片面に樹脂層(X)を形成した。樹脂層(X)の厚さは32μmであった。
<工程(2)>
工程(1)で得られた樹脂層(X)の上に、片面が黒化処理された厚さ7μmの銅箔を、黒化処理面と樹脂層(X)とが接するような向きで重ね、真空ラミネーターを用いて140℃で15分間減圧(5kPa)し、上チャンバーを常圧に戻し3分間加圧して接着し、基材フィルム/樹脂層(X)/銅箔の積層構成からなる積層体(A)を得た。得られた積層体(A)の銅箔上に、ドライフィルムレジストをラミネートした後、フォトリソグラフィの手法を用いてエッチング抵抗パターンを形成した。次に銅エッチング液に浸漬して導電構造体を形成した後、常法により、残存するフォトレジスト層を除去し、基材フィルム付き導電構造体含有フィルム(a)を得た。導電構造体は、線幅7μmの銅線が500μm間隔で波線状に並んだ構造を有し、その各波線の両端が、10cmの間隔で設けられた長さ11cm幅5mmの2本のバスバー構造と接続された構造を有していた。また、導電構造体の断線は見られなかった。
<合わせガラスの作製(工程(6)、工程(7))>
得られた基材フィルム付き導電構造体含有フィルム(a)を、導電構造体の端部から0.5cm程度外側(縦12cm、横12cm)で切り出した。続いてPETフィルムを剥離除去し、得られた導電構造体含有フィルム(a’)を縦15cm、横15cm、厚さ3mmのガラスの上に配置した。このとき、導電構造体含有フィルム(a’)の導電構造体を有さない面がガラスと接する向きで、かつ導電構造体がガラスの中央付近にくるように配置した。次に、導電構造体の両端部にある各々のバスバー(5mm幅銅線)に、電極(導電性粘着剤付き銅箔テープ)を、ガラスから外へ各電極端部がはみ出すように貼り付けた。その上に、樹脂層(Y)としての縦15cm、横15cm、厚さ0.76mmの自動車フロントガラス用(合わせガラス用)中間膜〔ポリビニルブチラール樹脂(水酸基量20.0質量%、原料としたポリビニルアルコールの粘度平均重合度1700)含有量72質量%、トリエチレングリコール-ビス-(2-エチルヘキサノエート)(以下、3GOと称する)含有量28質量%〕1枚を重ね、さらに縦15cm、横15cm、厚さ3mmのガラスを重ねて配置した。これを真空バッグに入れ、真空ポンプを用いて室温で15分間減圧した後、減圧したまま100℃で60分間加熱した。降温後、常圧に戻し、プレラミネート後の合わせガラスを取り出した。その後、これをオートクレーブに投入し、140℃、1.2MPaで30分間処理し、合わせガラスを作製した。得られた合わせガラスにおける導電構造体の状態をルーペを用いて観察した結果、導電構造体に明確な変形や断線は見られなかった。
実施例1の<合わせガラスの作製(工程(7))>において樹脂層(Y)としての縦15cm、横15cm、厚さ0.76mmの自動車フロントガラス用中間膜1枚を配置した代わりに、導電構造体含有フィルム(a’)の両面に、樹脂層(Y)としての縦15cm、横15cm、厚さ0.38mmの自動車フロントガラス用中間膜〔ポリビニルブチラール樹脂(水酸基量20.0質量%、原料としたポリビニルアルコールの粘度平均重合度1700)含有量72質量%、3GO含有量28質量%〕を1枚ずつ配置したこと以外は実施例1と同様にして、合わせガラスを作製した。得られた合わせガラスにおける導電構造体の状態をルーペを用いて観察した結果、導電構造体に明確な変形や断線は見られなかった。
樹脂層(X)の厚さを20μmとしたこと以外は実施例1と同様にして工程(1)および工程(2)を行い、基材フィルム付き導電構造体含有フィルム(b)を得た。
<工程(8)>
基材フィルム付き導電構造体含有フィルム(b)を、導電構造体の端部から2cm程度外側(縦15cm、横15cm)で切り出し、導電構造体の両端部にある各々のバスバー(5mm幅銅線)に、電極(導電性粘着剤付き銅箔テープ)を、外へ各電極端部がはみ出すように貼り付けた。次に、縦15cm、横15cm、厚さ3mmのガラスの上に、製造例1で作製したポリビニルブチラール樹脂フィルムを縦15cm、横15cmに切り出して重ね、その上に、上記で得られた電極を貼り付けた基材フィルム付き導電構造体フィルム(b)を、PETフィルムが最外層となるように重ねた。これを真空バッグに入れ、真空ポンプを用いて室温で15分間減圧にした後、減圧したまま100℃で60分間加熱し、降温後、常圧に戻した。
<工程(9)>
次いで、PETフィルムを剥離除去し、PETフィルムが接着していた面に、樹脂層(Y)としての縦15cm、横15cm、厚さ0.76mmの自動車フロントガラス用中間膜〔ポリビニルブチラール樹脂(水酸基量20.0質量%、原料としたポリビニルアルコールの粘度平均重合度1700)含有量72質量%、3GO含有量28質量%〕1枚を重ね、さらに縦15cm、横15cm、厚さ3mmのガラスを重ねて配置した。これを真空バッグに入れ、真空ポンプを用いて室温で15分間減圧にした後、減圧したまま100℃で60分間加熱した。降温後、常圧に戻し、プレラミネート後の合わせガラスを取り出した。その後、これをオートクレーブに投入し、140℃、1.2MPaで30分間処理し、合わせガラスを作製した。得られた合わせガラスにおける導電構造体の状態をルーペを用いて観察した結果、導電構造体に明確な変形や断線は見られなかった。
実施例3の<工程(8)>において使用した製造例1で作製したポリビニルブチラール樹脂フィルム、および<工程(9)>で使用した厚さ0.76mmの自動車フロントガラス用中間膜の代わりに、厚さ0.38mmの自動車フロントガラス用中間膜〔ポリビニルブチラール樹脂(水酸基量20.0質量%、原料としたポリビニルアルコールの粘度平均重合度1700)含有量72質量%、3GO含有量28質量%〕をそれぞれ用いたこと以外は実施例3と同様にして、合わせガラスを作製した。得られた合わせガラスにおける導電構造体の状態をルーペを用いて観察した結果、導電構造体に明確な変形や断線は見られなかった。
実施例1の<工程(2)>において真空ラミネーターを用いて140℃で15分間減圧(5kPa)し、上チャンバーを常圧に戻し3分間加圧して接着した代わりに、140℃に設定した熱圧着ロールの間を通過(圧力:0.2MPa、速度0.5m/分)させて接着したこと以外は実施例1と同様にして、基材フィルム付き導電構造体含有フィルム(c)、導電構造体含有フィルム、および合わせガラスを作製した。得られた合わせガラスにおける導電構造体の状態をルーペを用いて観察した結果、導電構造体に明確な変形や断線は見られなかった。
熱可塑性樹脂組成物(A)-IIIの代わりに熱可塑性樹脂組成物(A)-IVを用いたこと、および熱可塑性樹脂組成物(A)のエタノール溶液の濃度を12質量%に代えて10質量%としたこと以外は実施例1と同様にして、基材フィルム付き導電構造体含有フィルム(d)、導電構造体含有フィルム、および合わせガラスを作製した。得られた合わせガラスにおける導電構造体の状態をルーペを用いて観察した結果、導電構造体に明確な変形や断線は見られなかった。
熱可塑性樹脂組成物(A)-IIIの代わりに熱可塑性樹脂組成物(A)-Iを用いたこと、および熱可塑性樹脂組成物(A)のエタノール溶液の濃度を12質量%に代えて15質量%としたこと以外は実施例1と同様にして、基材フィルム付き導電構造体含有フィルム(e)、導電構造体含有フィルム、および合わせガラスを作製した。得られた合わせガラスにおける導電構造体の状態をルーペを用いて観察した結果、導電構造体に部分的に変形は認められたものの、断線は認められなかった。
熱可塑性樹脂組成物(A)-IIIの代わりに熱可塑性樹脂組成物(A)-Vを用いたこと、および熱可塑性樹脂組成物(A)のエタノール溶液の濃度を12質量%に代えて8質量%としたこと以外は実施例1と同様にして、基材フィルム付き導電構造体含有フィルム(f)、導電構造体含有フィルム、および合わせガラスを作製した。得られた合わせガラスにおける導電構造体の状態をルーペを用いて観察した結果、導電構造体に部分的に変形は認められたものの、断線は認められなかった。
<工程(3)>
表2に示した熱可塑性樹脂組成物(A)-IIIをエタノールに溶解し、12質量%の溶液を作製した。得られた溶液をコンマ方式(ナイフコート方式の一種)の小型塗工試験機を用いて、片面が黒化処理された厚さ7μmの銅箔の黒化処理面に塗布し、乾燥ゾーンで50~120℃の熱風により溶媒を除去した後、A4サイズに切り取って、真空乾燥(50℃、12時間)を行い、銅箔の片面に樹脂層(X)を形成した。樹脂層(X)の厚さは31μmであった。
<工程(4)>
工程(3)で得られた樹脂層(X)の銅箔を有さない面に、厚さ50μmのPETフィルムを重ね、真空ラミネーターを用いて140℃で15分減圧(5kPa)し、上チャンバーを常圧に戻し3分加圧して接着し、銅箔/樹脂層(X)/PETフィルムの積層構成からなる積層体(G)を得た。
<工程(5)>
得られた積層体(G)の銅箔上に、ドライフィルムレジストをラミネートした後、フォトリソグラフィの手法を用いてエッチング抵抗パターンを形成した。次に銅エッチング液に浸漬して導電構造体を形成した後、常法により、残存するフォトレジスト層を除去し、基材フィルム付き導電構造体含有フィルム(g)を得た。導電構造体は、線幅7μmの銅線が500μm間隔で波線状に並んだ構造を有し、その各波線の両端が、10cmの間隔で設けられた長さ11cm幅5mmの2本のバスバー構造と接続された構造を有していた。また、導電構造体の断線は見られなかった。
次に、実施例1の<合わせガラスの作製(工程(6)、工程(7))>と同様にして、導電構造体含有フィルムおよび合わせガラスを作製した。得られた合わせガラスにおける導電構造体の状態をルーペを用いて観察した結果、導電構造体に明確な変形や断線は見られなかった。
厚さ50μmのPETフィルムと厚さ7μmの銅箔の黒化面の間に、製造例2で得られた厚さ52μmのポリビニルブチラール樹脂フィルムを挟み、真空ラミネーターを用いて140℃でラミネートして、基材フィルムと銅箔を備えたポリビニルブチラール樹脂フィルム(H)を得た。
次に、基材フィルム付き導電構造体含有フィルム(c)の代わりに前記ポリビニルブチラール樹脂フィルム(H)を用いたこと以外は実施例5と同様にして、基材フィルム付き導電構造体含有フィルム(h)、導電構造体含有フィルム、および合わせガラスを作製した。得られた合わせガラス中の導電構造体の状態をルーペを用いて観察した結果、導電構造体の一部に導電細線がはがれたような断線がみられた。
<工程(3)>
100質量部の表2に示した熱可塑性樹脂組成物(A)-Iに対し、酸化防止剤としてのTINUVIN326(BASF製)を0.15質量部、紫外線(UV)吸収剤としてのトリエチレングリコールビス(3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオネート)を0.04質量部、並びに接着調整剤としての酢酸マグネシウム・4水和物0.03質量部および酢酸カリウム0.02質量部を添加して混合した。得られた混合物を、押出機(ダイ設定温度:240℃)を用いて、ロールから巻き出した、片面が黒化処理された厚さ7μm、幅30cmの銅箔の黒化処理面上に押出して塗布し、銅箔の片面に樹脂層(X)を形成した。樹脂層(X)の厚さは35μmであった。
なお、本実施例10では、樹脂層(X)を構成する材料として、表2に示した熱可塑性樹脂組成物(A)-Iに対して、酸化防止剤などの添加剤が添加された混合物を使用した。この場合は当該混合物が、本発明における熱可塑性樹脂組成物(A)となる。後述の実施例11~13および比較例2~3においても同様である。
<工程(4)>
工程(3)で得られた樹脂層(X)の銅箔を有さない面の上に、厚さ50μm、幅30cmのPETフィルムを載せ、140℃に設定した熱圧着ロールの間を通過(圧力:0.2MPa、速度0.5m/分)させて、銅箔/樹脂層(X)/PETフィルムの積層構成からなる積層体(I)を得、ロール状に巻き取った。
A4サイズの積層体(G)の代わりにロールから巻き出した積層体(I)を用いたこと以外は実施例9の<工程(5)>と同様にして、基材フィルム付き導電構造体含有フィルム(i)を作製し、ロール状に巻き取った。基材フィルム付き導電構造体含有フィルム(a)に代えて、ロールから巻き出した基材フィルム付き導電構造体含有フィルム(i)を用いたこと以外は実施例1の<合わせガラスの作製(工程(6)、工程(7))>と同様にして、導電構造体含有フィルム、および合わせガラスを作製した。得られた合わせガラスにおける導電構造体の状態をルーペを用いて観察した結果、導電構造体に部分的に変形が認められたものの、断線は認められなかった。
熱可塑性樹脂組成物(A)-Iの代わりに熱可塑性樹脂組成物(A)-IIIを用い、100質量部の熱可塑性樹脂組成物(A)-IIIに対して10質量部の3GOをさらに添加したこと、および樹脂層(X)の厚さを28μmとしたこと以外は実施例10と同様にして、基材フィルム付き導電構造体含有フィルム(j)、導電構造体含有フィルム、および合わせガラスを作製した。得られた合わせガラスにおける導電構造体の状態をルーペを用いて観察した結果、導電構造体に明確な変形や断線は見られなかった。
<工程(1)>
100質量部の表2に示した熱可塑性樹脂組成物(A)-Iに対し、酸化防止剤としてのTINUVIN326(BASF製)を0.15質量部、UV吸収剤としてのトリエチレングリコールビス(3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオネート)を0.04質量部、並びに接着調整剤としての酢酸マグネシウム・4水和物0.03質量部および酢酸カリウム0.02質量部を添加して混合し、得られた混合物を、押出機(ダイ設定温度:240℃)を用いて、厚さ50μm、幅30cmのPETフィルムに押出して塗布し、PETフィルムの片面に樹脂層(X)を形成した。樹脂層(X)の厚さは36μmであった。
<工程(2)>
工程(1)で得られた樹脂層(X)のPETフィルムを有さない面の上に、片面が黒化処理された厚さ7μm、幅30cmの銅箔の黒化処理面を載せ、140℃に設定した熱圧着ロールの間を通過(圧力:0.2MPa、速度0.5m/分)させて、PETフィルム/樹脂層(X)/銅箔の積層構成からなる積層体(K)を得、ロール状に巻き取った。
得られた積層体(K)を用いたこと以外は実施例10と同様にして、基材フィルム付き導電構造体含有フィルム(k)、導電構造体含有フィルム、および合わせガラスを作製した。得られた合わせガラスにおける導電構造体の状態をルーペを用いて観察した結果、導電構造体に部分的に変形が認められたものの、断線は認められなかった。
100質量部の表2に示した熱可塑性樹脂組成物(A)-Iに対し、酸化防止剤としてのTINUVIN326(BASF製)を0.15質量部、UV吸収剤としてのトリエチレングリコールビス(3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオネート)を0.04質量部、並びに接着調整剤としての酢酸マグネシウム・4水和物0.03質量部および酢酸カリウム0.02質量部を添加して混合した。得られた混合物を、押出機(ダイ設定温度:240℃)を用いて、ロールから巻き出した、片面が黒化処理された厚さ7μm、幅30cmの銅箔の黒化処理面上に押出して塗布し、樹脂層(X)を形成した。PETフィルムが樹脂層(X)に接するように、圧着ロールを通して厚さ50μmのPETフィルムを貼り合わせて、銅箔/樹脂層(X)/PETフィルムの積層構成からなる積層体(L)を得、ロール状に巻き取った。樹脂層(X)の厚さは34μmであった。
得られた積層体(L)を用いたこと以外は実施例10と同様にして、基材フィルム付き導電構造体含有フィルム(l)、導電構造体含有フィルム、および合わせガラスを作製した。得られた合わせガラスにおける導電構造体の状態をルーペを用いて観察した結果、導電構造体に部分的に変形が認められたものの、断線は認められなかった。
<工程(4)>を行わなかったこと、および樹脂層(X)の厚さを31μmとしたこと以外は実施例10と同様にして、導電構造体含有フィルムおよび合わせガラスを作製した。得られた合わせガラスにおける導電構造体の状態をルーペを用いて観察した結果、導電構造体の一部に断線がみられた。銅箔の熱圧着時に生じたシワが原因であると推定される。
<工程(4)>を行わなかったこと、および樹脂層(X)の厚さを31μmとしたこと以外は実施例11と同様にして、導電構造体含有フィルムおよび合わせガラスを作製した。得られた合わせガラスにおける導電構造体の状態をルーペを用いて観察した結果、導電構造体に顕著な断線がみられた。導電構造体含有フィルムをロールから巻き出す際に、隣接する樹脂層(X)に付着していた導電構造体の一部が剥がれ落ちたことが主な原因であった。
Claims (21)
- 基材フィルムの片面に、ポリビニルアセタール樹脂、アイオノマー樹脂およびエチレン酢酸ビニル共重合体樹脂からなる群より選ばれる少なくとも1種の熱可塑性樹脂を含む熱可塑性樹脂組成物(A)を塗布して樹脂層(X)を形成する工程(1);および該樹脂層(X)上に導電構造体を形成する工程(2);を含む、基材フィルム付き導電構造体含有フィルムの製造方法。
- 金属箔の片面に、ポリビニルアセタール樹脂、アイオノマー樹脂およびエチレン酢酸ビニル共重合体樹脂からなる群より選ばれる少なくとも1種の熱可塑性樹脂を含む熱可塑性樹脂組成物(A)を塗布して樹脂層(X)を形成する工程(3);該樹脂層(X)に基材フィルムをラミネートする工程(4);および金属箔を加工して導電構造体を形成する工程(5);を含む、基材フィルム付き導電構造体含有フィルムの製造方法。
- 前記工程(1)または前記工程(3)において、熱可塑性樹脂組成物(A)を塗布する方法が、熱可塑性樹脂組成物(A)を溶融して塗布する方法によるものである、請求項1または2に記載の基材フィルム付き導電構造体含有フィルムの製造方法。
- 前記工程(1)または前記工程(3)において、熱可塑性樹脂組成物(A)を塗布する方法が、熱可塑性樹脂組成物(A)の溶液または分散液を塗布する方法によるものである、請求項1または2に記載の基材フィルム付き導電構造体含有フィルムの製造方法。
- 前記熱可塑性樹脂組成物(A)が、熱可塑性樹脂組成物(A)の総質量に基づいて50質量%以上のポリビニルアセタール樹脂を含む、請求項1~4のいずれかに記載の基材フィルム付き導電構造体含有フィルムの製造方法。
- ブルックフィールド型(B型)粘度計を用いて20℃、30rpmで測定された、前記ポリビニルアセタール樹脂の濃度10質量%のトルエン/エタノール=1/1(質量比)溶液の粘度が200mPa・sより大きい、請求項5に記載の基材フィルム付き導電構造体含有フィルムの製造方法。
- 前記熱可塑性樹脂組成物(A)が、熱可塑性樹脂組成物(A)の総質量に基づいて0~20質量%の可塑剤を含む、請求項5または6に記載の基材フィルム付き導電構造体含有フィルムの製造方法。
- 前記熱可塑性樹脂組成物(A)が、熱可塑性樹脂組成物(A)の総質量に基づいて80質量%以上のポリビニルアセタール樹脂を含む、請求項1~7のいずれかに記載の基材フィルム付き導電構造体含有フィルムの製造方法。
- 前記導電構造体が少なくとも2本のバスバー構造を有する、請求項1~8のいずれかに記載の基材フィルム付き導電構造体含有フィルムの製造方法。
- 前記導電構造体が少なくとも2本のバスバー構造の間に金属細線構造を有する、請求項9に記載の基材フィルム付き導電構造体含有フィルムの製造方法。
- 前記工程(2)または前記工程(5)において、金属箔をエッチングして前記導電構造体を形成する、請求項1~10のいずれかに記載の基材フィルム付き導電構造体含有フィルムの製造方法。
- 請求項1~11のいずれかに記載の製造方法により得られる基材フィルム付き導電構造体含有フィルム。
- 請求項1~11のいずれかに記載の製造方法により得られる基材フィルム付き導電構造体含有フィルムから基材フィルムを除去する工程(6)を含む、導電構造体含有フィルムの製造方法。
- 請求項13に記載の製造方法により得られる、導電構造体含有フィルム。
- 請求項13に記載の製造方法により得られる導電構造体含有フィルムを少なくとも2枚のガラスの間に挟みラミネートする工程(7)を含む、合わせガラスの製造方法。
- 請求項1~11のいずれかに記載の製造方法により得られる基材フィルム付き導電構造体含有フィルムの基材フィルムを有さない面にガラスを重ねラミネートして積層体を得る工程(8)、および該積層体から基材フィルムを除去し、ガラスを有さない面にさらにガラスを重ねてラミネートする工程(9)を含む、合わせガラスの製造方法。
- 前記工程(7)において、前記導電構造体含有フィルムとガラスとの間に、少なくとも1層の樹脂層(Y)を挟む、請求項15に記載の合わせガラスの製造方法。
- 前記工程(8)において基材フィルム付き導電構造体含有フィルムとガラスとの間に、および/または前記工程(9)において基材フィルムを除去した後の積層体とガラスとの間に、少なくとも1層の樹脂層(Y)を挟む、請求項16に記載の合わせガラスの製造方法。
- 前記樹脂層(Y)が、前記熱可塑性樹脂組成物(A)に含まれる熱可塑性樹脂と同一の熱可塑性樹脂を含む、請求項17または請求項18に記載の合わせガラスの製造方法。
- 請求項15~19のいずれかに記載の製造方法により得られる合わせガラス。
- 請求項14に記載の導電構造体含有フィルムを用いた、加熱部材。
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- 2018-07-06 KR KR1020207000254A patent/KR20200027947A/ko not_active Application Discontinuation
- 2018-07-06 CN CN201880042268.8A patent/CN110799469B/zh active Active
- 2018-07-06 EP EP18827811.3A patent/EP3650417A4/en active Pending
- 2018-07-06 WO PCT/JP2018/025684 patent/WO2019009409A1/ja unknown
- 2018-07-06 US US16/628,313 patent/US20200171795A1/en not_active Abandoned
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JPWO2019131948A1 (ja) * | 2017-12-28 | 2021-01-07 | 株式会社クラレ | 回路付きフィルム |
JP7148550B2 (ja) | 2017-12-28 | 2022-10-05 | クラレイ ユーロップ ゲゼルシャフト ミット ベシュレンクテル ハフツング | 回路付きフィルム |
Also Published As
Publication number | Publication date |
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EP3650417A4 (en) | 2021-03-17 |
KR20200027947A (ko) | 2020-03-13 |
US20200171795A1 (en) | 2020-06-04 |
CN110799469A (zh) | 2020-02-14 |
JP7196070B2 (ja) | 2022-12-26 |
EP3650417A1 (en) | 2020-05-13 |
JPWO2019009409A1 (ja) | 2020-04-30 |
CN110799469B (zh) | 2022-08-05 |
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