JP5618080B2 - Etching laminate - Google Patents

Description

  The present invention relates to a laminate for etching treatment in which a metal foil is provided on a substrate via an adhesive layer.

  As a method of providing a circuit or metal mesh pattern on a polyester base material, a metal foil is provided via a polyester resin adhesive layer, a coating film is further provided on the metal foil, and then an etching treatment is performed. A technique for removing the coating film is common.

  In recent years, there is an increasing need for shortening the etching processing time in order to improve productivity. In order to shorten the etching time, it is common to increase the reaction rate by increasing the temperature. However, if the etching temperature is increased to 80 ° C. or higher, accurate etching cannot be performed or the adhesive strength of the adhesive layer is reduced. There was a problem of falling.

  For example, Patent Document 1 discloses a laminate in which an adhesive layer made of a polyester resin having a glass transition temperature of −10 to 20 ° C. and a conductive metal foil are provided on a base material. However, when this laminate was subjected to an etching process at 80 ° C. or higher, there was a problem that the adhesive strength of the adhesive layer was lowered.

JP 2008-124238 A

  The problem to be solved by the present invention is that, in a laminate in which an adhesive layer and a metal foil layer are sequentially provided on a base material, the adhesive layer has an adhesive strength even when etching treatment or removal of the coating film is performed at 80 ° C. or higher. An object of the present invention is to provide an etching treatment laminate capable of accurately forming a metal mesh pattern or circuit without lowering.

  As a result of intensive studies in order to solve such problems, the present inventor has found that the above object can be achieved by a polyester resin composition having a specific composition, and has reached the present invention.

That is, the gist of the present invention is as follows.
(1) A laminate for etching treatment in which a metal foil is provided on a substrate via an adhesive layer, wherein the adhesive layer has a glass transition temperature of more than 20 ° C and less than 65 ° C and a number average molecular weight of less than 10,000. Polyester resin (A), including a polyester resin (I) having a glass transition temperature of 65 ° C. or higher and a number average molecular weight of 10,000 or higher and an isocyanate compound, (A) / (I) is 20/80 to 60/40 (mass ratio) A laminate for etching treatment which is).
(2) The laminate for etching treatment according to (1), wherein the polyester resin (a) has a hydroxyl value of 170 to 720 equivalents / ton.
(3) For etching treatment according to (1), wherein the equivalent ratio of the amount of isocyanate end groups to the total amount of hydroxyl groups of polyester resin (a) and polyester resin (a) is 0.5 to 2.0 times. Laminated body.
(4) An electromagnetic wave shielding laminate obtained by etching the etching treatment laminate according to any one of (1) to (3).

  In the laminate of the present invention, the adhesive layer is excellent in adhesiveness in a high temperature environment and has resistance to an etching treatment agent, so that it can be etched at 80 ° C. or higher, and a metal mesh pattern or The circuit can be formed accurately. Moreover, the laminated body which provided the metal mesh by the etching process can be used as an electromagnetic wave shield of PDP.

The present invention will be described in detail below.
In the laminate of the present invention, a metal foil layer is provided on a substrate via an adhesive layer.

  The resin of the adhesive layer is composed of a polyester resin (A), a polyester resin (A), and an isocyanate compound.

  The polyester resin (A) and the polyester resin (A) are composed mainly of a dicarboxylic acid component and a glycol component.

  Dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, 4,4'-dicarboxybiphenyl, 5-sodium sulfoisophthalic acid, 5-hydroxy-isophthalic acid, oxalic acid, malonic acid, succinic acid , Glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid , Nonadecanedioic acid, eicosanedioic acid, docosanedioic acid, dimer acid, hydrogenated dimer acid, fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid Acid, 1,3-cyclohexanedicarboxylic acid, Examples include 2,5-norbornene dicarboxylic acid.

  As the glycol component, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polytetramethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, tricyclodecanedimethanol, Examples include spiro glycol and dimer diol. Among these, ethylene glycol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, tricyclodecane dimethanol and spiroglycol are preferable.

  The polyester resins (a) and (b) may be copolymerized with a hydroxycarboxylic acid as necessary. Hydroxycarboxylic acids include lactic acid, glycolic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyisobutyric acid, 2-hydroxy-2-methylbutyric acid, 2-hydroxyvaleric acid, 3-hydroxy Valeric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid, 10-hydroxystearic acid, 4- (β-hydroxy) ethoxybenzoic acid, β-propiolactone, β-butyrolactone, γ- Examples include butyrolactone, δ-valerolactone, and ε-caprolactone. When copolymerizing hydroxycarboxylic acid, the copolymerization amount of hydroxycarboxylic acid is preferably 20 mol% or less with respect to the total of all dicarboxylic acid components and all hydroxycarboxylic acid components.

  In addition, the polyester resins (a) and (b) may be copolymerized with a monocarboxylic acid, a monoalcohol, a trifunctional or higher carboxylic acid, or a trifunctional or higher alcohol as long as the amount is small.

  Examples of monocarboxylic acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid, cyclohexane acid, 4-hydroxyphenyl stearic acid, and the like. Examples of the monoalcohol include octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and 2-phenoxyethanol. When copolymerizing a monocarboxylic acid and a monoalcohol, the respective copolymerization amounts are preferably 20 mol% or less in the total dicarboxylic acid component and the total glycol component.

  Examples of the trifunctional or higher carboxylic acid include 1,3,4-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid, pyromellitic acid, trimellitic acid and the like. Include trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, α-methylglucose, mannitol, and sorbitol. When copolymerizing a trifunctional or higher functional carboxylic acid or a trifunctional or higher functional alcohol, the copolymerization amount is preferably 20 mol% or less in the total dicarboxylic acid component and the total glycol component.

  The glass transition temperature of the polyester resin (a) needs to be higher than 20 ° C. and lower than 65 ° C., preferably higher than 20 ° C. and lower than 60 ° C., higher than 20 ° C. and lower than 50 ° C. Further preferred. If the glass transition temperature of the polyester resin (a) is 65 ° C. or higher, the adhesive strength at a high temperature of the adhesive layer decreases, which is not preferable. On the other hand, when the glass transition temperature of the polyester resin (a) is 20 ° C. or lower, accurate etching cannot be performed or the adhesive layer may be hydrolyzed, which is not preferable.

  From the viewpoint of crosslinking, the hydroxyl value of the polyester resin (a) is preferably 170 to 720 equivalent / ton, more preferably 350 to 720 equivalent / ton, and 350 to 540 equivalent / ton. More preferred. By setting the hydroxyl value of the polyester resin (a) to 170 to 720 equivalent / ton, an adhesive layer having sufficient adhesive strength can be obtained.

  The number average molecular weight of the polyester resin (a) needs to be 4,000 to 10,000, preferably 5,000 to 9000, and more preferably 6,000 to 8,000. If the number average molecular weight of the polyester resin (a) is less than 4000, the adhesive strength of the adhesive layer is lowered, which is not preferable. On the other hand, when the number average molecular weight of the polyester resin (a) exceeds 10,000, the hydroxyl value becomes relatively small and the degree of crosslinking becomes low, which is not preferable.

  The glycol component of the polyester resin (a) is preferably a glycol having a branched structure from the viewpoints of solubility and adhesiveness. Examples of the glycol having a branched structure include propylene glycol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-n-butyl-propanediol, 3- Examples thereof include methyl-pentanediol and polypropylene glycol. Among them, propylene glycol and 2-methyl-1,3-propanediol are preferable.

  The copolymerization amount of glycol having a branched structure in all glycol components of the polyester resin (a) is preferably 1 to 70 mol%, more preferably 10 to 65 mol%, and 30 to 60 mol%. More preferably.

  The glass transition temperature of the polyester resin (a) needs to be 65 ° C. or higher, preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and further preferably 90 ° C. When the glass transition temperature of the polyester resin (a) is less than 65 ° C., it is not preferable because accurate etching cannot be performed or the adhesive layer may be hydrolyzed.

  The hydroxyl value of the polyester resin (a) is preferably 450 equivalent / ton or less, and more preferably 170 equivalent / ton or less. By setting the hydroxyl value of the polyester resin (a) to 450 equivalents / ton or less, the number average molecular weight is relatively increased, and an adhesive layer having sufficient adhesive strength can be obtained.

  The number average molecular weight of the polyester resin (a) needs to be 10,000 or more, preferably 15000 to 60000, and more preferably 20000 to 40000. If the number average molecular weight of the polyester resin (a) is less than 10,000, the cohesive force is lowered and the adhesive strength of the adhesive layer is lowered, which is not preferable.

  As the dicarboxylic acid component of the polyester resin (a), it is preferable to copolymerize terephthalic acid and / or isophthalic acid.

  When copolymerizing terephthalic acid to the polyester resin (a), the copolymerization amount of terephthalic acid in all dicarboxylic acid components is preferably 20 mol% or more, and preferably 40 mol% from the viewpoint of adhesive strength. More preferred is 60 mol%.

  When isophthalic acid is copolymerized with the polyester resin (a), the copolymerization amount of isophthalic acid in all dicarboxylic acid components is preferably 20 mol% or more, and preferably 40 mol% from the viewpoint of solubility. More preferred.

  The polyester resin (A) or (I) can be produced by a known method by combining the above monomers. For example, it can be produced by a method comprising an esterification reaction and a polycondensation reaction.

  In the esterification reaction, all monomer components and / or low polymers thereof are reacted by heating and melting under an inert atmosphere. The reaction temperature is preferably 180 to 260 ° C, and the reaction time is preferably 2.5 to 10 hours, more preferably 4 to 6 hours.

  The polycondensation reaction is carried out until a desired molecular weight is reached by adding a catalyst and distilling off the glycol component from the esterified product obtained by the esterification reaction under reduced pressure. The reaction temperature is preferably 220 to 280 ° C. The degree of vacuum is preferably 130 Pa or less. It is preferable to gradually reduce the pressure over 60 to 180 minutes until the atmospheric pressure reaches 130 Pa or less.

Although it does not specifically limit as a polycondensation catalyst, Well-known compounds, such as a zinc acetate, an antimony trioxide, a tetrabutyl titanate, a tetra- n-butyl titanate, n-butylhydroxy oxotin, an octylic acid tin, can be used. It is preferable that the usage-amount of a catalyst shall be 0.1-20 * 10 < ^-4 > mol with respect to 1 mol of carboxylic acid components.

  In order to adjust the hydroxyl value, a polyhydric alcohol can be further added following the polycondensation reaction, and depolymerization can be performed in an inert atmosphere.

  The blending ratio of the polyester resin (A) and the polyester resin (A) needs to be (A) / (I) = 20 / 80-60 / 40 (mass ratio), and 30 / 70-40 / 60. (Mass ratio) is preferable. When the blending ratio of (a) is less than 20% by mass, accurate etching cannot be performed or the adhesive layer may be hydrolyzed, which is not preferable. On the other hand, when the blending ratio of (a) exceeds 60% by mass, the adhesive strength of the adhesive layer is lowered, which is not preferable.

  Examples of the isocyanate compound include, but are not limited to, isocyanates such as hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, and blocked isocyanates thereof.

  The blending ratio of the polyester resin (A), the polyester resin (A) and the isocyanate compound is such that the terminal group amount of the isocyanate compound is 0.5 to the total amount of the hydroxyl group amount of the polyester resin (A) and the hydroxyl group amount of the polyester resin (A). The range is preferably 2.0 times equivalent, and more preferably 1.0 to 1.2 times equivalent. By setting the blending ratio in the range of 0.5 to 2.0 times equivalent, the polyester resin (A) and the polyester resin (I) are efficiently cross-linked via the isocyanate compound, so that the adhesive strength can be increased. . Therefore, even if the etching process is performed at a temperature higher than the glass transition temperature of the polyester resin (A) or the polyester resin (A), the adhesive layer is not dissolved and an accurate etching process can be performed.

  In addition, when mix | blending a polyester resin (A), a polyester resin (I), and an isocyanate compound and forming an adhesive layer, a crosslinking catalyst, a hardening | curing agent, and a curing catalyst can be used as needed.

  Examples of the crosslinking catalyst include tertiary amine catalysts such as N-methylimidazole, 1,4-diazine and diazabicyclo [2.2.2] -octane, and tin-based catalysts such as stannous octoate and dibutyltin dilaurate. . When using a crosslinking catalyst, it is preferable that the compounding quantity shall be 0.3-1.0 mass part with respect to a total of 100 mass parts of polyester resin (A) and polyester resin (I).

  The adhesive layer may contain flame retardants, heat stabilizers, antioxidants, lubricants, pigments, fillers, tackifiers, other resins, acid anhydrides, antistatic agents, foaming agents, and the like. .

  Flame retardants include decabromodiphenyl ether, bis (pentabromophenyl) ethane, tetrabromobisphenol, hexabromocyclododecane, hexabromobenzene and other halides, triphenyl phosphate, tricresyl phosphate, 1,3-phenylenebis ( Phosphorus compounds such as diphenyl phosphate), ammonium polyphosphate, polyphosphate amide, and guanidine phosphate, halogen-containing phosphate esters such as tris (chloroethyl) phosphate and tris (dichloropropyl) phosphate, red phosphorus, triazine, melamine isocyanurate, ethylene dimelamine Nitrogen flame retardants such as tin dioxide, antimony pentoxide, antimony trioxide, inorganic flame retardant aids such as aluminum hydroxide and magnesium hydroxide, silicone powder and the like.

Examples of the heat stabilizer include phosphoric acid and phosphoric acid ester.
Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, and thioether compounds.
Examples of the lubricant include talc, silica, polyethylene wax, paraffin wax and the like.
Examples of the pigment include titanium dioxide, calcium carbonate, and zinc oxide.
Examples of the tackifier include tackifiers.
Examples of other resins include epoxy resins and acrylic resins.

  The method for producing the laminate for etching treatment is not particularly limited. For example, a polyester resin (A), a polyester resin (A), and an isocyanate compound are dissolved in an organic solvent to prepare a resin solution. And a method in which an adhesive layer is provided by drying and a metal foil layer is provided on the adhesive layer.

  The method for preparing the resin solution is not particularly limited, but after dissolving the polyester resins (A) and (I) in an organic solvent, the isocyanate compound may be added and dissolved, or the polyester resin (A), (I) and the isocyanate compound may be dissolved together in an organic solvent. Since the isocyanate compound has high reactivity and may react during dissolution, the former method is more preferable.

  The organic solvent used for preparing the resin solution is not particularly limited, but aromatic solvents such as toluene, xylene, solvent naphtha and solvesso, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, methyl alcohol, ethyl Examples thereof include alcohol solvents such as alcohol, isopropyl alcohol and isobutyl alcohol, ester solvents such as ethyl acetate and normal butyl acetate, and acetate solvents such as cellosolve acetate and methoxyacetate. These may be used alone or in combination of two or more.

  The total solid content concentration of the polyester resins (A) and (I) in the resin solution is preferably 20 to 40% by mass, and more preferably 20 to 30% by mass.

  The solution viscosity of the resin solution is preferably 5000 mPa · s or less, more preferably 4000 mPa · s or less, still more preferably 3000 mPa · s or less, and most preferably 2000 mPa · s or less. When the solution viscosity is 5000 mPa · s or less, the fluidity is high and the handleability is excellent.

  As the substrate, transparent glass, soda glass, semi-tempered glass, tempered glass, polyethylene terephthalate (PET) film, polycarbonate film, polymethyl methacrylate film, polyethylene film, polypropylene film and the like are used. Although it does not specifically limit as thickness of a base material, 20-100 micrometers is preferable.

The adhesive layer can be provided by applying a resin solution on a substrate and drying it.
The method for applying the resin solution is not particularly limited, and examples thereof include a method of applying using a coater. Examples of the coater include a bar coater, a comma coater, a die coater, a roll coater, a reverse roll coater, a gravure coater, a gravure reverse coater, and a flow coater. Although the thickness of an adhesive layer is not specifically limited, 10-30 micrometers is preferable. As drying temperature, 80-120 degreeC is preferable. The adhesive layer may be formed by applying a plurality of times.

  The metal foil layer can be provided by placing a metal foil on the adhesive layer and thermocompression bonding or laminating.

  As the metal foil layer, a metal foil of copper, aluminum, nickel, iron, chromium, titanium or the like is used. Among these, copper and aluminum are preferable from the viewpoint of conductivity, ease of circuit processing, and cost.

  The thermocompression bonding or laminating temperature is preferably 80 to 150 ° C., and the pressure is preferably 100 to 300 kPa.

  The laminate for etching treatment of the present invention can be used for a technique of etching a metal foil to provide a circuit or metal mesh pattern. The etching process is performed, for example, by providing a coating film on the metal foil layer, processing with an etching solution, and subsequently removing the coating film.

  The coating film is a film for protecting the metal foil during the etching process, and is not particularly limited as long as it is a material having resistance to the etching process. Although the thickness of a coating film is not specifically limited, 0.1-10 micrometers is preferable. As a method for forming the coating film, photolithography and flexographic printing are used.

  As an etchant, an aqueous solution of cupric chloride, ferric chloride, and sodium hydroxide is used. The temperature of the etching solution is preferably 80 ° C. or higher. By setting the temperature of the etching solution within this range, the etching processing speed can be made much faster than before.

  A sodium hydroxide aqueous solution is used as a treatment liquid for removing the coating film.

  A resin may be laminated on the laminate provided with a circuit or metal mesh pattern for the purpose of protection. Examples of the resin include acrylic pressure-sensitive adhesives and acrylic resins.

  Laminates with circuit and metal mesh patterns are electromagnetic shielding, printed wiring, circuits such as contactless resonance tags and IC cards, electrolytic capacitor electrodes, current collectors of secondary batteries and electric double layer capacitors, electromagnetic waves It can be used as a shield / electromagnetic wave absorber.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The physical properties were measured by the following method.
(1) Glass transition temperature of polyester resin In accordance with JIS K-7121, using an input-compensated differential scanning calorimeter (Perkin Elmer Diamond DSC, measurement range: 20 to 120 ° C.) in a nitrogen stream, Measurement was performed under the condition of a temperature rising rate of 10 ° C / min.

(2) Composition of polyester resin Using a high resolution nuclear magnetic resonance apparatus (JNM-LA400 manufactured by JEOL Ltd.), ¹ H-NMR analysis was performed to determine the resin composition from the peak intensity of each copolymer component ( Frequency: 400 MHz, solvent: deuterated trifluoroacetic acid, temperature: 25 ° C.). In addition, with respect to a resin containing a constituent monomer in which no assignable / quantifiable peak is observed on the ¹ H-NMR spectrum, it is subjected to methanol decomposition at 230 ° C. for 3 hours in a sealed tube, followed by gas chromatogram analysis for quantitative analysis. I did it.

(3) Hydroxyl value of polyester resin In accordance with JIS K-0070, 3 g of sample was dissolved in 50 ml of pyridine by heating under reflux, acetic anhydride was acetylated solution, and cresol red-thymol blue was used as an indicator of 0.5 N potassium hydroxide. Titration with methanol solution. Using the titrated value, the number of hydroxyl equivalents per ton of sample was calculated.

(4) Number average molecular weight of polyester resin The number average molecular weight of polystyrene conversion was measured on the following conditions using gel permeation chromatography (GPC).
Liquid feeding unit: LC-10ADvp manufactured by Shimadzu Corporation
Ultraviolet-visible spectrophotometer: SPD-6AV manufactured by Shimadzu Corporation, detection wavelength: 254 nm
Column: One Shodex KF-803 and two Shodex KF-804s connected in series Solvent: Tetrahydrofuran Measurement temperature: 40 ° C

(5) Amount of isocyanate end group According to JIS K1603-2007, 3 g of sample was dissolved in 20 ml of dehydrated toluene, 20 ml of 2N di-normal butylamine solution was added and left for 20 minutes after stirring, and then 100 ml of isopropyl alcohol was added. Titration with 1.0N hydrochloric acid solution. The titrated value was used to calculate the equivalent number of isocyanate end groups per ton of sample.

(6) Adhesive strength of adhesive layer The resin solution used for forming the adhesive layer was applied to the non-corona surface of a 75 μm PET sheet using a bar coater, dried at 100 ° C. for 30 seconds, and adhered with a dry thickness of 25 μm. A PET film having a layer formed thereon was prepared.
Subsequently, a PET film having a thickness of 100 μm was stacked on the adhesive layer, and thermocompression bonded for 30 minutes under the conditions of a temperature of 120 ° C. and a pressure of 100 kPa, thereby producing a laminate. The obtained laminate was cut to a width of 25 mm, and a peel strength was measured by performing a 180 ° peel test at 23 ° C. and 60 ° C. using a tensile strength tester (manufactured by Shimadzu Corporation, Autograph AG100B). And the adhesive strength. The adhesive strength at 23 ° C. is practically preferably 10 N / 25 mm or more, more preferably 15 N / 25 mm or more, and further preferably 20 N / 25 mm or more.

(7) Heat resistance of the adhesive layer Using the values of the adhesive strength under the two temperature conditions measured in (6), the retention ratio of the adhesive strength at 60 ° C to the adhesive strength at 23 ° C is calculated and evaluated according to the following criteria: did. Practically 70% or more is preferable.
◎: 90% or more ○: 80% or more and less than 90% △: 70% or more and less than 80% ×: less than 70%

(8) Resistance to Etching Agent A metal mesh pattern (line width: 30 μm, space width: 250 μm) was printed as a coating layer on the metal foil side of the etching treatment laminate using a photolithography method. Subsequently, this printed matter was immersed in an aqueous cupric chloride solution (cupric chloride concentration: 50% by mass) at 80 ° C. to dissolve the copper foil portion corresponding to the non-printing portion. Then, it washed with water, immersed in 80 degreeC sodium hydroxide aqueous solution (sodium hydroxide concentration: 20 mass%), the coating layer was peeled, and the process which forms the pattern of a metal mesh on the metal foil of a laminated body was performed. When the laminate was immersed in a cupric chloride aqueous solution or a sodium hydroxide aqueous solution, the state of the adhesive layer was judged according to the following criteria.
○: The adhesive layer did not peel off.
Δ: Less than 10% of the area of the adhesive layer peeled off.
X: 10% or more of the area of the adhesive layer was peeled off.

(9) Etching results The pattern of the metal mesh formed in (8) is observed with a scanning electron microscope, the actual line width / space width formed in the laminate, and the line width / space width of the target mesh pattern The differences were compared with each other and judged according to the following criteria.
○: The difference between the line width and the space width was 1 μm or less.
Δ: The difference between the line width and the space width was 1 μm or more.

The polyester resins used in Examples and Comparative Examples were prepared as follows.
Polyester resin A
8300 g of terephthalic acid, 8300 g of isophthalic acid, 15800 g of bisphenol A (ethylene oxide adduct), 5300 g of ethylene glycol (terephthalic acid: isophthalic acid: bisphenol A (ethylene oxide adduct): ethylene glycol = 50: 50: 55: 85 (molar ratio) )) Was put into a reaction vessel equipped with a stirring blade, and esterification was performed at 240 ° C. for 5 hours under a pressure of 0.35 MPa while stirring at a rotation speed of 50 rpm. Thereafter, the mixture is transferred to a polycondensation can and 90 g of germanium dioxide (8.8 × 10 ⁻⁴ mol per mol of terephthalic acid) is added as a polymerization catalyst, and the pressure is gradually reduced to 1.3 hPa over 60 minutes. A polycondensation reaction was performed at 245 ° C. After releasing the reduced pressure, 670 g of trimethylolpropane (0.05 mol per mol of terephthalic acid) was added, and a depolymerization reaction was performed at 245 ° C. for 2 hours. Thereafter, powdered polyester resin A was obtained using a crusher.

Polyester resin B
8300 g of terephthalic acid, 8300 g of isophthalic acid, 15800 g of bisphenol A (ethylene oxide adduct), 5300 g of ethylene glycol (terephthalic acid: isophthalic acid: bisphenol A (ethylene oxide adduct): ethylene glycol = 50: 50: 55: 85 (molar ratio) )) Was put into a reaction vessel equipped with a stirring blade, and esterification was performed at 240 ° C. for 5 hours under a pressure of 0.35 MPa while stirring at a rotation speed of 50 rpm. Thereafter, the mixture is transferred to a polycondensation can and 90 g of germanium dioxide (8.8 × 10 ⁻⁴ mol per mol of terephthalic acid) is added as a polymerization catalyst, and the pressure is gradually reduced to 1.3 hPa over 60 minutes. A polycondensation reaction was performed at 245 ° C. Then, the pellet-shaped polyester resin B was obtained using the strand cutter.

Polyester resin C, E, F, G
It was produced in the same manner as the polyester resin A, except that the raw material monomer was changed as shown in Table 1.

Polyester resin D, H
It was produced in the same manner as the polyester resin B except that the raw material monomer was changed as shown in Table 1.

  Table 1 shows the resin charge composition, final resin composition and characteristic values of the polyester resin.

Example 1
Polyester resin A and polyester resin B were added to a mixed solvent of toluene / methyl ethyl ketone 8/2 (mass ratio) so as to have a blending ratio shown in Table 2, and shaken with a paint shaker. Subsequently, 0.9 parts by mass of hexamethylene diisocyanate (isocyanate terminal group amount: 11891 equivalents / ton) (the hydroxyl group amount of polyester resin A and polyester resin B) with respect to 100 parts by mass of polyester resin A and polyester resin B in total. 0.5 times by weight of tin 2-ethylhexanoate as a crosslinking catalyst with respect to the solid content of the resin, and shaken again with a paint shaker for 5 minutes to obtain a resin solution. Was made.
This resin solution was applied to a PET film having a thickness of 25 μm so that the thickness of the adhesive layer after drying was 25 μm, and dried at 100 ° C. for 30 seconds to form an adhesive layer.
Subsequently, on the adhesive layer, a copper foil having a thickness of 50 μm is thermocompression-bonded at 120 ° C. under a pressure of 100 kPa for 30 minutes using a hot press machine manufactured by Hayashi Machinery Co., Ltd. A laminate was obtained.

Examples 2-14, Comparative Examples 1-16
A laminate for etching treatment was produced in the same manner as in Example 1 except that the polyester resin used for the adhesive layer was changed.

  Tables 2 and 3 show the characteristic values of the polyester resin and laminate used for the adhesive layer.

Examples 1 to 10 all had high adhesive strength in a high-temperature environment. Therefore, even when the etching temperature was 80 ° C., the adhesive layer was not dissolved in cupric chloride or sodium hydroxide, and the metal after the etching treatment was used. The mesh pattern was formed accurately.
In Examples 12 and 13, since the equivalent ratio of the isocyanate terminal group amount to the total of the hydroxyl group amount of the polyester resin (a) and the hydroxyl group amount of the polyester resin (a) was not in the range of 0.5 to 2.0 times equivalent, The adhesive layer partially peeled off during etching, leaving room for improvement.
In Example 14, since the hydroxyl value of the polyester resin (a) was not in the range of 170 to 720 equivalents / ton, the adhesive layer partially peeled during etching, leaving room for improvement.

  In Comparative Examples 1-2 and Comparative Examples 7-8, the blending ratio of the polyester resin (A) is small and the blending ratio of the polyester resin (A) is large. Therefore, the adhesive strength of the adhesive layer is low, and the adhesive layer peels off during etching. It was.

  In Comparative Examples 3-6 and Comparative Examples 9-12, the blending ratio of the polyester resin (a) was large and the blending ratio of the polyester resin (a) was small. Therefore, the adhesive strength in a high temperature environment was low, and the etching temperature was 80 ° C. In this case, accurate etching could not be performed.

  In Comparative Example 13, since the glass transition temperatures of the two types of polyester resins used were both 65 ° C. or higher, the adhesive strength in a high temperature environment was low, and when immersed in a cupric chloride aqueous solution or a sodium hydroxide aqueous solution, The adhesive layer was peeled off.

  In Comparative Example 14, since the number average molecular weights of the two kinds of polyester resins used were both less than 10,000, the adhesive strength in a high temperature environment was low, and when the etching temperature was 80 ° C., accurate etching could not be performed. .

  In Comparative Example 15, since the glass transition temperatures of the two types of polyester resins used were both lower than 65 ° C., the adhesive strength in a high temperature environment was low, and accurate etching was not possible when the etching temperature was 80 ° C. It was.

  In Comparative Example 16, the glass transition temperatures of the two types of polyester resins used were both higher than 65 ° C., and the adhesive layer was peeled off when immersed in a cupric chloride aqueous solution or a sodium hydroxide aqueous solution.

Claims (4)

A laminate for etching treatment in which a metal foil is provided on a base material via an adhesive layer, wherein the adhesive layer has a glass transition temperature of more than 20 ° C. and less than 65 ° C. and a number average molecular weight of less than 10,000 polyester resin ( A), including a polyester resin (I) and an isocyanate compound having a glass transition temperature of 65 ° C. or higher and a number average molecular weight of 10,000 or more, and (A) / (I) is 20/80 to 60/40 (mass ratio). Etching laminate. The laminate for etching treatment according to claim 1, wherein the hydroxyl value of the polyester resin (a) is 170 to 720 equivalent / ton. The laminate for etching treatment according to claim 1, wherein the equivalent ratio of the amount of isocyanate end groups to the sum of the amount of hydroxyl groups of the polyester resin (a) and the amount of hydroxyl groups of the polyester resin (a) is 0.5 to 2.0 times. The laminated body for electromagnetic wave shields which etches the laminated body for etching processes in any one of Claims 1-3.