Laminated film and laminate

Abstract

To provide a laminated film having a semi-aromatic polyamide resin film and a primer layer having an excellent adhesive property between metal layers formed by sputtering or electroless plating.SOLUTION: There is provided a laminated film comprising a semi-aromatic polyamide resin film, and a primer layer. The primer layer contains a polyester resin in which a content of aliphatic dicarboxylic acid in acid components is 5 to 60 mol %, and a molar ratio of terephthalic acid to isophthalic acid is 1 / 99 to 70 / 30.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a laminate film and a laminate. [Background technology]

[0002] One example of a wiring board used in electronic devices is a flexible printed circuit board (FPC). Flexible printed circuit boards are produced by using a metal-clad laminate, such as a copper-clad laminate (CCL), in which copper is laminated on an insulating base film, forming copper wiring by, for example, performing a copper etching process, and then laminating a coverlay film to protect the copper wiring. One method for producing a copper-clad laminate is to laminate a resin film with an adhesive layer and copper foil together, followed by thermocompression bonding. However, thermocompression bonding is not sufficient to meet the demand for fine circuit formation that has become increasingly common in recent devices with increasing density.

[0003] Therefore, attempts have been made to produce copper-clad laminates by providing a conductor layer made of metal on a resin film by sputtering or electroless plating, and then performing additional copper electroplating as necessary (for example, Patent Document 1 and Patent Document 2). However, these methods of laminating a metal layer directly on a resin film do not provide sufficient adhesion between the resin film and the metal layer, and there is a problem in that the metal layer is easily peeled off from the resin film during the electroplating process or reflow soldering process.

[0004] Adhesive layers using polyester resins have been proposed for bonding resin films to metals (e.g., Patent Documents 3 and 4). However, the adhesive layers described in Patent Documents 3 and 4 have insufficient adhesive performance between the resin film and a metal layer formed by sputtering or electroless plating. Furthermore, the heat resistance and plating solution resistance of the adhesive layer are also insufficient. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2020-012156 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-212143 [Patent Document 3] Japanese Patent Application Publication No. 9-286968 [Patent Document 4] Japanese Patent Application Laid-Open No. 2012-214558 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention solves the above-mentioned problems and aims to provide a laminated film having a semi-aromatic polyamide resin film and a primer layer that has excellent adhesion between metal layers formed by sputtering or electroless plating and excellent resistance to plating solutions.

[0007] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above object can be achieved, thereby completing the present invention. That is, the gist of the present invention is as follows.

[0008] (1) A laminated film in which a primer layer is laminated on a film made of a semi-aromatic polyamide resin, and the primer layer contains a polyester resin in which the content of aliphatic dicarboxylic acids among the acid components is 5 to 60 mol % and the molar ratio of terephthalic acid / isophthalic acid is 1 / 99 to 70 / 30. (2) A laminated film of (1) that satisfies the following conditions when the following peel resistance test is conducted on a 0.1 μm thick copper layer formed on a primer layer by sputtering or electroless plating. [Peeling resistance test] Cross-cut test conforming to JIS K5600-5-6. [conditions] The peeling state of the copper layer is either Class 0, Class 1, or Class 2. (3) The laminated film of (1) or (2), which contains a primer layer characterized in that the weight-average molecular weight of the polyester resin is 20,000 to 100,000. (4) The laminate film according to any one of (1) to (3), wherein the primer layer contains inorganic particles and / or organic particles. (5) A laminate in which a metal layer is laminated on the primer layer of the laminate film of any one of (1) to (4). [Effects of the Invention]

[0009] According to the present invention, a laminate film can be obtained that has excellent adhesion between a resin film and a metal layer formed by sputtering or electroless plating, and excellent resistance to plating solutions. Furthermore, the laminate film of the present invention also has excellent heat resistance and blocking resistance when rolled. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention will be described in detail below. The laminated film of the present invention has a primer layer on a film made of a semi-aromatic polyamide resin. The primer layer contains a polyester resin in which the content of aliphatic dicarboxylic acid among the carboxylic acid components is 5 to 60 mol % and the molar ratio of terephthalic acid / isophthalic acid is 1 / 99 to 70 / 30.

[0011] The polyester resin contained in the primer layer is a resin consisting of an acid component containing an aliphatic dicarboxylic acid, terephthalic acid (hereinafter sometimes abbreviated as TPA), and isophthalic acid (hereinafter sometimes abbreviated as IPA), and a polyol component.

[0012] Examples of aliphatic dicarboxylic acids constituting the polyester resin contained in the primer layer of the present invention include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, pimelic acid, suberic acid, azelaic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedicarboxylic acid, docosanedicarboxylic acid, fumaric acid, maleic acid, and itaconic acid. These acid components may also be derivatives such as anhydrides, esters, and acid chlorides. Among the aliphatic dicarboxylic acids, adipic acid or sebacic acid is preferred from the viewpoint of adhesion between the primer layer and the metal layer. Examples of acid components other than TPA, IPA, and aliphatic dicarboxylic acids include, but are not limited to, alicyclic dicarboxylic acids such as 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, perhydronaphthalenedicarboxylic acid, dimer acid, and cyclobutenedicarboxylic acid, and aromatic dicarboxylic acids such as orthophthalic acid, naphthalenedicarboxylic acid, and 5-sodium-sulfoisophthalic acid. These acid components may also be derivatives such as anhydrides, esters, and acid chlorides.

[0013] The content of aliphatic dicarboxylic acid in the acid component must be 5 to 60 mol%, preferably 10 to 50 mol%, more preferably 15 to 45 mol%, particularly preferably 20 to 45 mol%, and most preferably 30 to 45 mol%. If the content of aliphatic dicarboxylic acid in the acid component is less than 5 mol%, the adhesion between the primer layer and the metal layer and the plating solution resistance will be poor. If the content of aliphatic dicarboxylic acid in the acid component exceeds 60%, the resulting laminate film will have poor heat resistance, and further, when the resulting laminate film is wound into a roll and stored, blocking will easily occur, resulting in poor blocking resistance.

[0014] The TPA / IPA (molar ratio) in the acid component must be 1 / 99 to 70 / 30, preferably 2 / 98 to 70 / 30, more preferably 3 / 97 to 65 / 35, even more preferably 5 / 95 to 65 / 35, and most preferably 20 / 80 to 65 / 35. If the TPA / IPA (molar ratio) in the acid component is outside of 1 / 99 and the TPA content is low, the heat resistance of the resulting primer layer will be poor. If the TPA / IPA (molar ratio) in the polyester resin is outside of 70 / 30 and the TPA content is high, not only will the adhesion between the primer layer and the metal layer be poor, but plating resistance will also be poor.

[0015] Examples of the polyol component constituting the polyester resin contained in the primer layer of the present invention include polyester polyols, polyether polyols, polycarbonate polyols, polyolefin polyols, acrylic polyols, monomeric polyol components (e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4- Examples of polyols include pentanediol, 2-methyl-2-propyl-1,3-propanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-butyl-2-hexyl-1,3-propanediol, cyclohexanediol, bishydroxymethylcyclohexane, dimethanolbenzene, bishydroxyethoxybenzene, alkyldialkanolamine, etc., and alkylene oxide adducts of bisphenols. A plurality of these polyols may be used. Among these, from the viewpoint of adhesion between the primer layer and the metal layer, the polyol component is preferably ethylene glycol, diethylene glycol, neopentyl glycol, 1,6-hexanediol, or an alkylene oxide adduct of bisphenols.

[0016] The polyester resin of the present invention may contain structural units derived from polymerizable components other than the above-mentioned acid component and polyol. Examples of such polymerizable components include hydroxycarboxylic acids such as lactic acid, oxirane, glycolic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxyisobutyric acid, 2-hydroxy-2-methylbutyric acid, 2-hydroxyvaleric acid, 3-hydroxyvaleric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid, 10-hydroxystearic acid, and 4-(β-hydroxy)ethoxybenzoic acid; β-propiolactone, β-butyrolactone, and γ-butyrolactone. Examples of the monocarboxylic acid include aliphatic lactones such as lactone, δ-valerolactone, and ε-caprolactone; monocarboxylic acids such as lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, benzoic acid, p-tert-butylbenzoic acid, cyclohexanoic acid, and 4-hydroxyphenylstearic acid; and monoalcohols such as octyl alcohol, decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, and 2-phenoxyethanol.

[0017] The weight-average molecular weight of the polyester resin is not particularly limited, but is preferably 20,000 to 100,000, more preferably 25,000 to 90,000, even more preferably 30,000 to 90,000, particularly preferably 50,000 to 90,000, and most preferably 60,000 to 85,000. If the weight-average molecular weight of the polyester resin is less than 20,000, not only will the resulting primer layer tend to have poor plating solution resistance, but blocking will also be more likely to occur when the resulting laminate film is wound into a roll and stored. If the weight-average molecular weight of the polyester resin is 100,000 or more, the resulting primer layer may have poor adhesion between the resin film and the metal layer formed by sputtering or electroless plating.

[0018] The acid value of the polyester resin is not particularly limited, but is preferably 1 to 20 mgKOH / g, more preferably 1.5 to 10 mgKOH / g, and particularly preferably 2 to 5 mgKOH / g. If the acid value is less than 1 mgKOH / g, the adhesion between the primer layer and the metal layer tends to be poor. On the other hand, if the acid value exceeds 20 mgKOH / g, the resulting primer layer tends to have poor resistance to plating solutions.

[0019] In the present invention, the primer layer may contain a crosslinking agent. Examples of crosslinking agents include epoxy compounds, oxazoline compounds, carbodiimide compounds, isocyanate compounds, organic acid hydrazide compounds, and aziridine compounds. These compounds may be used alone or in combination of two or more. These compounds react with functional groups, such as carboxyl groups, hydroxyl groups, and amino groups, contained in the polyester resin to form multiple covalent bonds. When similar functional groups are contained in the semi-aromatic polyamide film, the compounds react with these functional groups to form multiple covalent bonds.

[0020] The epoxy compound is not particularly limited, and for example, epoxy compounds containing bisphenol A diglycidyl ether, modified bisphenol A diglycidyl ether, novolac glycidyl ether, glycerin polyglycidyl ether, polyglycerin polyglycidyl ether, etc. can be used. Commercially available epoxy compounds include the Denacol series (EX-313, EX-614B, EX-321, EX-512, EX-1610, etc.) manufactured by Nagase ChemteX Corporation, Adeka Resin EM-0517, EM-0526, EM-11-50B, EM-051R manufactured by Adeka Corporation, and SR-GSG and SR-4GSL manufactured by Sakamoto Pharmaceutical Co., Ltd.

[0021] The oxazoline compound is not particularly limited as long as it has two or more oxazoline groups in the molecule. Examples include compounds having an oxazoline group, such as 2,2'-bis(2-oxazoline), 2,2'-ethylene-bis(4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis(2-oxazoline), and bis(2-oxazolinylcyclohexane) sulfide, as well as oxazoline group-containing polymers. One or more of these can be used. Among these, oxazoline group-containing polymers are preferred for their ease of handling. The oxazoline group-containing polymer can be obtained by polymerizing an addition-polymerizable oxazoline such as 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, or 2-isopropenyl-2-oxazoline. If necessary, other monomers may be copolymerized. The polymerization method for the oxazoline group-containing polymer is not particularly limited, and various known polymerization methods can be used.

[0022] Commercially available oxazoline group-containing polymers include the Epocross series manufactured by Nippon Shokubai Co., Ltd., specifically the water-soluble types "WS-300," "WS-500," and "WS-700," and the solid type "RPS-1005."

[0023] The carbodiimide compound is not particularly limited as long as it has at least two carbodiimide groups in the molecule. Examples include compounds having carbodiimide groups such as p-phenylene-bis(2,6-xylylcarbodiimide), tetramethylene-bis(t-butylcarbodiimide), and cyclohexane-1,4-bis(methylene-t-butylcarbodiimide), and polycarbodiimide, which is a polymer having carbodiimide groups. One or more of these can be used. Among these, polycarbodiimide is preferred because of its ease of handling.

[0024] The method for producing polycarbodiimide is not particularly limited. Polycarbodiimide can be produced, for example, by a condensation reaction of an isocyanate compound accompanied by the removal of carbon dioxide. The isocyanate compound is also not limited, and may be any of aliphatic isocyanate, alicyclic isocyanate, and aromatic isocyanate. The isocyanate compound may be copolymerized with a polyfunctional liquid rubber, polyalkylenediol, or the like, as needed.

[0025] Commercially available polycarbodiimide products include the Carbodilite series manufactured by Nisshinbo Corporation, including water-soluble types "SV-02," "V-02," "V-02-L2," and "V-04," emulsion types "E-02," "E-03A," and "E-04," organic solution types "V-01," "V-03," "V-07," and "V-09," and solvent-free type "V-05."

[0026] The isocyanate compound is not particularly limited as long as it has at least two isocyanate groups in the molecule. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane 2,4'- or 4,4'-diisocyanate, polymethylene polyphenyl diisocyanate, tolidine diisocyanate, 1,4-diisocyanatobutane, hexamethylene diisocyanate, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- or 1,4-diisocyanatocyclohexanone, Examples of diisocyanates include hexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, 4,4'-diisocyanatodicyclohexylmethane, hexahydrotoluene 2,4- or 2,6-diisocyanate, perhydro-2,4'- or 4,4'-diphenylmethane diisocyanate, naphthalene 1,5-diisocyanate, xylylene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and tetramethylxylylene diisocyanate, as well as derivatives thereof. Among isocyanate compounds, aqueous (water-soluble or water-dispersible) ones are preferred.

[0027] Commercially available isocyanate compounds include Bayhydur 3100 and Desmodur DN manufactured by Sumika Covestro Urethane Co., Ltd., Basonate HW-100 manufactured by BASF, and blocked isocyanates BI200 and BI220 manufactured by Baxenden.

[0028] The organic acid hydrazide compound is not particularly limited, and examples thereof include sebacic acid dihydrazide, isophthalic acid dihydrazide, adipic acid dihydrazide, and malonic acid dihydrazide. Among the above organic acid hydrazides, commercially available ones include, for example, organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd. and organic acid hydrazides manufactured by Ajinomoto Fine-Techno Co., Ltd. Examples of the organic acid hydrazides manufactured by Otsuka Chemical Co., Ltd. include SDH, ADH, and MDH. Examples of the organic acid hydrazides manufactured by Ajinomoto Fine-Techno Co., Inc. include Amicure VDH, Amicure VDH-J, Amicure UDH, and Amicure UDH-J.

[0029] In the present invention, the content of the crosslinking agent is preferably 5 to 80 parts by mass, more preferably 15 to 70 parts by mass, and most preferably 40 to 70 parts by mass, based on 100 parts by mass of the polyester resin. If the content of the crosslinking agent is less than 5 parts by mass, the resulting primer layer is likely to have insufficient plating solution resistance and heat resistance, and blocking is likely to occur when the resulting laminate film is wound into a roll and stored. If the content of the crosslinking agent is more than 80 parts by mass, the plating solution resistance and heat resistance tend to be poor, and the adhesion of the metal layer to the resulting primer layer tends to be reduced.

[0030] In the present invention, the primer layer may contain various additives, such as antioxidants, heat stabilizers, weather stabilizers, ultraviolet absorbers, pigments, dyes, inorganic or organic fine particles, fillers, antistatic agents, wetting agents, etc., within ranges that do not impair the effects of the present invention.

[0031] In particular, in a preferred embodiment of the present invention, the primer layer preferably contains inorganic and / or organic particles from the viewpoints of preventing blocking, providing easy lubrication, and preventing scratches due to contact with rolls or the like during processing.

[0032] Examples of inorganic particles include silica particles, alumina particles, zirconia particles, tin oxide particles, titanium oxide particles, zinc oxide particles, niobium oxide particles, neodymium oxide particles, lanthanum oxide particles, cerium oxide particles, magnesium oxide particles, and calcium carbonate particles.

[0033] Examples of organic particles include polystyrene particles, cross-linked polystyrene particles, acrylic particles, cross-linked acrylic particles, polyethylene particles, polyamide particles, benzoguanamine-formaldehyde resin particles, melamine-formaldehyde resin particles, and fluororesin particles.

[0034] Among the above-mentioned particles, silica particles, crosslinked polystyrene particles, and crosslinked acrylic particles are preferred from the viewpoint of easy lubricity.

[0035] The primary particle diameter of the organic and / or inorganic particles is preferably 0.001 to 10 μm, more preferably 0.01 to 4 μm, even more preferably 0.02 to 1.5 μm, and particularly preferably 0.03 to 0.9 μm. If the primary particle diameter is less than 0.001 μm, it may be difficult to achieve sufficient slipperiness and blocking resistance. If the primary particle diameter of the particles exceeds 10 μm, there is a risk that the particles will fall off from the primer layer depending on the thickness of the primer layer.

[0036] The particle content in the primer layer of the present invention is preferably 0.05 to 30 parts by mass, more preferably 0.2 to 20 parts by mass, even more preferably 0.6 to 14 parts by mass, particularly preferably 1 to 8 parts by mass, and most preferably 1 to 5 parts by mass, based on 100 parts by mass of the polyester resin. If the particle content is less than 0.05 parts by mass, blocking is likely to occur when the resulting laminate film is wound into a roll and stored. If the particle content exceeds 30 parts by mass, the resulting primer layer tends to have poor adhesion between the resin film and the metal layer formed by sputtering or electroless plating.

[0037] The amount of the primer layer in the laminated film of the present invention (mass per unit area) is 0.01 to 7 g / m 2 It is preferable that the density is 0.03 to 3 g / m 2 More preferably, it is 0.06 to 1 g / m 2It is more preferable that the thickness of the primer layer is 0.05 to 0.5 μm. If the amount or thickness of the primer layer is small, not only will sufficient adhesion between the resin film and the metal layer formed by sputtering or electroless plating not be obtained, but the fine particles contained in the primer layer may fall off. If the amount or thickness of the primer layer is large, blocking may easily occur when the resulting laminated film is wound into a roll and stored.

[0038] The laminated film of the present invention uses a film made of a semi-aromatic polyamide resin as the substrate film, which allows for a laminated film that is superior in heat resistance and adhesion to a metal layer compared to films made of other resins. The thickness of the semi-aromatic polyamide resin film is not particularly limited, but is preferably 0.5 to 500 μm, more preferably 2 to 300 μm, even more preferably 5 to 200 μm, and particularly preferably 10 to 120 μm. If the thickness of the semi-aromatic polyamide resin film is less than 0.5 μm, not only is it difficult to produce, but the film may also become weak and difficult to handle. On the other hand, if the thickness of the semi-aromatic polyamide resin film exceeds 500 μm, it is not preferable from the viewpoint of cost.

[0039] The dicarboxylic acid component constituting the semi-aromatic polyamide resin preferably contains terephthalic acid as a main component, and examples of the dicarboxylic acid component other than terephthalic acid include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, and octadecanedioic acid, and aromatic dicarboxylic acids such as 1,4-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,2-naphthalenedicarboxylic acid, and isophthalic acid. The proportion of terephthalic acid in the dicarboxylic acid component is preferably 60 to 100 mol %.

[0040] The diamine component constituting the semi-aromatic polyamide resin preferably contains as a main component an aliphatic diamine having 4 to 15 carbon atoms, and examples of the aliphatic diamine having 4 to 15 carbon atoms include 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octadecanediamine, 4-methyl-1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, etc. These may be used alone or in combination of two or more.

[0041] From the viewpoint of bending resistance, the semi-aromatic polyamide resin is preferably a semi-aromatic polyamide resin comprising a dicarboxylic acid component consisting solely of terephthalic acid (100 mol % terephthalic acid) and a diamine component containing 1,9-nonanediamine and 2-methyl-1,8-octanediamine in a total amount of 60 to 100 mol % in the diamine component, or a semi-aromatic polyamide resin comprising a dicarboxylic acid component consisting solely of terephthalic acid (100 mol % terephthalic acid) and a diamine component containing 1,10-decanediamine.

[0042] The semi-aromatic polyamide resin may be copolymerized with lactams such as ε-caprolactam, ζ-enantholactam, η-capryllactam, ω-laurolactam, etc., within the scope of the present invention.

[0043] The semi-aromatic polyamide resin can be produced by any known method, such as solution polymerization or interfacial polymerization using an acid chloride component and a diamine component as raw materials. Alternatively, a prepolymer can be produced using a dicarboxylic acid component and a diamine component as raw materials, and the prepolymer can be polymerized by melt polymerization or solid-state polymerization.

[0044] Furthermore, a terminal-capping agent may be used, if necessary, together with the diamine component, dicarboxylic acid component, and polymerization catalyst to produce the semi-aromatic polyamide resin. From the viewpoint of suppressing thermal decomposition and suppressing an increase in molecular weight, the terminal-capping agent is not particularly limited as long as it is a monofunctional compound that is reactive with the amino group or carboxyl group at the terminal of the semi-aromatic polyamide, and examples thereof include monocarboxylic acids, monoamines, acid anhydrides, monoisocyanates, monohalides, monoesters, and monoalcohols.

[0045] Commercially available semi-aromatic polyamide resins can be suitably used, such as "Genesta (registered trademark)" manufactured by Kuraray Co., Ltd., "Xecot (registered trademark)" manufactured by Unitika Ltd., "Reny (registered trademark)" manufactured by Mitsubishi Engineering Plastics Corporation, "Arlen (registered trademark)" manufactured by Mitsui Chemicals, Inc., and "Ultramid (registered trademark)" manufactured by BASF.

[0046] The semi-aromatic polyamide resin film may contain known additives such as antioxidants, stabilizers, UV absorbers, pigments, dyes, antistatic agents, plasticizers, antioxidants, inorganic or organic particles, fillers, and crosslinking agents, as long as the effects of the present invention are not impaired.

[0047] The semi-aromatic polyamide resin film of the present invention may be a composite film having a laminated structure of two or more layers, such as a composite film in which no particles are contained in the inner layer but a very small amount of particles are contained in the surface layer, or a composite film in which different or the same resins are used for the inner and surface layers.

[0048] In addition, the semi-aromatic polyamide resin film may be subjected to a surface pretreatment such as corona treatment, plasma treatment, ozone treatment, chemical treatment, or solvent treatment in consideration of adhesion to the primer layer.

[0049] (Laminated film manufacturing method) The laminated film of the present invention can be obtained, for example, by applying a liquid containing the above-mentioned polyester resin, a crosslinking agent, and, if necessary, any additives (hereinafter, sometimes referred to as a "primer composition") to the above-mentioned semi-aromatic polyamide resin film and drying it, but the production method is not limited to this. Specifically, examples include a method (inline method) in which a primer composition is applied to a semi-aromatic polyamide resin film before biaxial stretching, followed by stretching and heat treatment, and a method (offline method) in which a primer composition is applied to a resin film and dried without biaxially stretching the resin film, and either method can be used.

[0050] The primer composition of the present invention preferably contains a medium that can be evaporated and removed by drying. While the medium is not particularly limited, a medium with a boiling point of 120°C or less is preferred from the viewpoint of drying efficiency. Examples of mediums with a boiling point of 120°C or less include water, toluene, acetone, 2-butanone (methyl ethyl ketone), methyl isobutyl ketone, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, methyl butyrate, dimethyl carbonate, pentane, hexane, heptane, cyclohexane, 1,4-dioxane, tetrahydrofuran, acetonitrile, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, pyridine, and triethylamine. These mediums may be used alone or in combination.

[0051] The solids concentration in the primer composition of the present invention is preferably 0.5 to 30% by mass, more preferably 1 to 20% by mass, even more preferably 2 to 10% by mass, and particularly preferably 3 to 8% by mass. If the solids concentration is less than 0.5% by mass, drying for a longer period of time or at a higher temperature is required to volatilize the medium, which is undesirable from the viewpoint of workability. If the solids concentration exceeds 30% by mass, the blocking resistance of the resulting primer layer tends to decrease.

[0052] The laminate of the present invention is obtained by laminating a metal layer on the primer layer of the laminate film of the present invention. The metal material constituting the metal layer is not particularly limited, and examples thereof include copper, nickel, aluminum, silver, tin, lead, chromium, gold, magnesium, nickel, iron, zinc, zirconium, titanium, etc. These metals may be used alone or as an alloy of two or more metals. Among these, from the viewpoints of conductivity and cost, it is preferable to use copper or an alloy containing copper.

[0053] The method for laminating a metal layer on the primer layer of the laminated film of the present invention is not particularly limited, and examples thereof include lamination using a metal foil, sputtering, and electroless plating. From the viewpoint of ease of controlling the film thickness, sputtering or electroless plating is preferred.

[0054] When a metal layer is laminated on the primer layer of the laminate film of the present invention by sputtering or electroless plating, the metal layer can be made even thicker by electroplating the metal layer. The metal laminated by sputtering or electroless plating and the metal applied by electroplating may be different metals.

[0055] The use of the laminate of the present invention is not particularly limited, but it can be suitably used as the following materials or films: electronic substrate materials such as flexible printed circuit boards, high heat dissipation substrates, antenna substrates, LED mounting substrates, organic EL substrates, flexible flat cables, flexible antennas, solar cell substrates, and speaker diaphragms; packaging materials for pharmaceuticals; packaging materials for foods such as retort foods; packaging materials for electronic components such as semiconductor packages; electrical insulating materials for motors, transformers, cables, electric wires, multilayer printed circuit boards, and the like; dielectric materials for capacitors, etc.; magnetic tape materials such as cassette tapes, magnetic tapes for data storage in digital data storage, and video tapes; protective materials for liquid crystal panels, glass, digital signage, and other display devices; coverlay films for flexible printed circuit boards, heat-resistant protective films such as heat-resistant masking tape; heat-resistant adhesive films such as heat-resistant barcode labels and various industrial process tapes; heat-resistant reflectors; heat-resistant release films; thermally conductive films; films for semiconductor processes such as dicing tape, dicing tape integrated die attach film (dicing-die attach film), dicing tape integrated die bonding film (dicing-die bonding film), dicing tape integrated wafer backside protection film, and backgliding film; molding and decoration materials such as in-mold molding, film insert molding, vacuum forming, and pressure forming; shock-absorbing materials such as tube coating, wire coating, shock-absorbing film, and sealing film; photographic film; agricultural materials; medical materials; civil engineering and construction materials; filtration membranes; household and industrial materials; and films for textile materials. [Example]

[0056] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. Measurements and evaluations of various values ​​in the examples were carried out as follows.

[0057] 1. Evaluation Method (1) Composition of polyester resin The polyester resin was dissolved in a mixed solvent of deuterated hexafluoroisopropanol and deuterated chloroform in a volume ratio of 1 / 20, and 1H-NMR was measured using a JEOL LA-400 NMR apparatus. The intensity was determined from the integrated intensity of the proton peaks of each copolymerization component in the resulting chart.

[0058] (2) Weight average molecular weight of polyester resin The polyester resin was dissolved in dimethylacetamide to prepare a dimethylacetamide solution with a concentration of 0.14% by mass. The dimethylacetamide solution was injected into a GPC apparatus (Tosoh Corporation, product name "HLC-8220" (column: TskgelGMH-XL x 2)) to measure the weight-average molecular weight of the polyester resin in terms of standard polystyrene.

[0059] (3) Adhesion of the metal layer to the primer layer (peel resistance test) An aqueous primer composition was applied to a resin film described below, and the film was heated for 15 seconds in a hot air dryer set at 240°C to form a primer layer. The resulting laminated film was then placed in a sputtering deposition apparatus, the pressure inside the apparatus was reduced, argon gas was introduced, and sputtering was performed using copper as the target. The discharge power and sputtering time required for sputtering were appropriately adjusted to form a 0.1 μm-thick copper layer on the primer layer of the laminated film. A cross-cut test was performed on this copper layer in accordance with JIS K5600-5-6, and the peeling state of the copper layer was visually evaluated using a scale of 0 to 5. In the present invention, it is preferable that the material falls into any one of categories 0, 1 and 2. Category 0: The edges of the cut are completely smooth and there is no peeling on any of the grids. Category 1: Small peeling of the coating at the intersection of the cuts. The affected area of ​​the cross-cuts does not significantly exceed 5%. Category 2: The coating is flaking along the edges of the cuts and / or at the intersections. The cross-cut area is clearly more than 5% affected but not more than 15%. Category 3: The coating has partially or completely peeled off significantly along the edges of the cuts and / or partially or completely peeled off in various areas of the mesh. The cross-cut area is clearly more than 15% affected but not more than 35%. Category 4: The coating is partially or completely torn off in large areas along the edges of the cuts and / or partially or completely torn off in several sections. Not more than 35% of the cross-cut area is affected. Category 5: Any degree of peeling that cannot be classified as Category 4.

[0060] (4) Resistance of the primer layer to plating solution In a 3,000 mL glass graduated cylinder, 150 g of copper(II) sulfate pentahydrate (special reagent grade, manufactured by Nacalai Tesque), 1,200 g of ion-exchanged water, 380 g of sulfuric acid (special reagent grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 0.275 g of hydrochloric acid (special reagent grade, concentration 35-37%, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 2 g of Lucent Copper A (manufactured by Meltex Corporation), 2 g of Lucent Copper S (manufactured by Meltex Corporation), and 8 g of Lucent Copper SC (manufactured by Meltex Corporation) were added in this order and stirred with a glass rod until the mixture was uniform. Subsequently, ion-exchanged water was poured into the same graduated cylinder and the volume was diluted to 2,000 mL. The mixture was further stirred with a glass rod and used as the plating solution in the experiment. The aqueous primer composition was poured into a Teflon (registered trademark) container and heated at 50°C for 48 hours and then at 150°C for 1 minute to obtain a coating film with a thickness of 0.5 mm. This coating film was separated from the Teflon (registered trademark) container and cut into five square test pieces with sides of 2 cm. The total weight of these five test pieces was measured and recorded. Five of the above test pieces were placed in a 100 mL polyethylene bottle, which was then filled with plating solution and sealed. The bottle was shaken at a rate of 60 cycles / min for three days in a shaker equipped with a water bath set at 50°C. All test pieces were then removed from the plating solution, thoroughly washed with water, and heated in a hot air dryer set at 60°C for 15 hours to completely remove the water. The total weight of the five test pieces was then measured, and the weight loss rate due to immersion in the plating solution was calculated using the following formula. From a practical standpoint, a score of △ or higher is preferable. Weight loss rate (%) = 100 x (total weight before immersion in plating solution - total weight before immersion in plating solution) / total weight before immersion in plating solution ○: Weight reduction rate>96% △:96%≧Weight reduction rate>90% ×:90%≧weight reduction rate

[0061] (5) Blocking resistance of primer layer An aqueous primer composition was applied to a resin film described below and heated for 15 seconds in a hot air dryer set at 240°C to form a primer layer. This laminated film was cut into squares with sides of 5 cm, and 20 identical sheets were stacked with the primer layer facing up. A 10 kg load was placed on top of the stack and heated in a hot air dryer set at 60°C for 24 hours. The load was then removed from the laminated film and it was cooled to room temperature. The adhesion between the primer layer surface and the resin film surface was examined to evaluate blocking resistance. From a practical standpoint, a rating of △ or higher is preferable. ◎: Can be peeled off without any resistance. ◯: Weak resistance was felt when peeling off, and a peeling sound was heard, but no whitening was observed on the primer layer after peeling. △: Weak resistance was felt when peeling off, a peeling sound was heard, and whitening of the primer layer was observed after peeling off. ×: Strong resistance was felt when peeling off, and whitening was observed on the primer layer after peeling off.

[0062] (6) Adhesion strength between the resin film and the metal layer The copper layer-containing laminate prepared in (3) was electroplated with the plating solution prepared in (4) to form a 5 μm-thick copper layer. The laminate was then thoroughly rinsed with water, the water droplets were wiped off, and the laminate was air-dried at room temperature for 3 days. The adhesive strength between the copper layer and the resin layer of this laminate was measured in a thermostatic chamber at 23°C using a tensile tester (Shimadzu Corporation, Autograph AGS-100B) at a peel angle of 90° and a peel rate of 50 mm / min. For practical purposes, a peel strength of 6 N / cm or more is preferred, 8 N / cm or more is more preferred, and 9.5 N / cm or more is particularly preferred.

[0063] (7) Solder heat resistance (heat resistance) A 2.5cm x 2.5cm sample of the laminate with the copper layer prepared in (6) was dried at 120°C for 30 minutes and then immersed in a molten solder bath at 260°C for 1 minute to evaluate the solder heat resistance according to the following criteria. From a practical standpoint, a rating of △ or better is preferable. 〇: No swelling △: Slight swelling ×: Large swelling

[0064] 2.Material The following resins were used as the resin film and the resin film itself. (1) Semi-aromatic polyamide resin 1343 g of 1,9-nonanediamine (NDA), 237 g of 2-methyl-1,8-octanediamine (MODA), 1627 g of terephthalic acid (TPA) (average particle size 80 mm) (NMDA:MODA:TPA = 85:15:99, molar ratio), 48.2 g of benzoic acid (BA) (4.0 mol % with respect to the total number of moles of dicarboxylic acid components and diamine components), 3.2 g of phosphorous acid (PA) (0.1 mass % with respect to the total amount of dicarboxylic acid components and diamine components), and 1100 g of water were placed in a reactor, and the atmosphere was replaced with nitrogen. The above raw materials were stirred at 80°C for 0.5 hours at 28 revolutions per minute, then heated to 230°C and heated at 230°C for 3 hours. After cooling, the reaction product was removed. The reaction product was pulverized and then heated in a dryer under a nitrogen stream at 220°C for 5 hours to undergo solid-state polymerization. The solid-phase polymer was melt-kneaded at a cylinder temperature of 320°C, extruded into strands, cooled, and cut into pellets to prepare semi-aromatic polyamide resin.

[0065] (2) Polyester resin Manufacturing Example 1 60.8 g (36.6 mol%) of terephthalic acid, 37.2 g (22.4 mol%) of isophthalic acid, 82.9 g (41 mol%) of sebacic acid, 57.7 g (93 mol%) of ethylene glycol, and 104.4 g (32 mol%) of an ethylene oxide adduct of bisphenol A were charged into a reactor, and the atmosphere in the system was replaced with nitrogen. Then, while stirring these raw materials at 1000 rpm, the reactor was heated to 250°C and melted. After the temperature in the reactor reached 250°C, the esterification reaction was allowed to proceed for 3 hours. After 3 hours, 0.2 g of tetrabutyl titanate was added as a polymerization catalyst, and the system was depressurized. After the system reached a high vacuum (pressure: 20 Pa), the polymerization reaction was allowed to proceed for an additional 3 hours, yielding polyester resin P-1.

[0066] Manufacturing Examples 2-12 Polyester resins P-2 to P-12 were produced in the same manner as in Production Example 1, except that the amounts of the monomers used were changed as shown in Table 1.

[0067] [Table 1]

[0068] (3) Crosslinking agent Isocyanate compound: Toyo Morton, CAT-10L Epoxy compound: Nagase ChemteX Corporation, "EX-614B" Aziridine compound: Nippon Shokubai Co., Ltd., "PZ-33"

[0069] (4) Particles Nissan Chemical Industries, Ltd., "MEK-ST-ZL" (organosilica sol, particle size 80 nm)

[0070] Example 1 Polyester resin P-1, an isocyanate compound, particles, and methyl ethyl ketone were mixed to obtain the composition shown in Table 2, to prepare a primer composition having a solids concentration of 5.6%. The semi-aromatic polyamide resin was melted in a single-screw extruder with a cylinder temperature of 320°C and a screw diameter of 50 mm, filtered using a sintered metal fiber filter (NF-10, manufactured by Nippon Seisen Co., Ltd., absolute particle size 30 μm), and then extruded into a film from a T-die heated to 320°C to obtain a molten film. The molten material was placed on a cooling roll at 50°C by electrostatic application and cooled to obtain a substantially unoriented unstretched film. The unstretched film was longitudinally stretched at 130°C at a stretching ratio of 3.0, and then the above-mentioned primer composition was applied using a gravure coater so that the amount of the primer layer after drying and stretching was 0.25 g / m 2 The film was preheated at 130°C for 2 seconds, and then introduced into a tenter-type stretching machine, where it was transversely stretched at a ratio of 3.3 while both ends of the longitudinally stretched film were held with clips. The stretching conditions were a preheating zone temperature of 120°C, a stretching zone temperature of 130°C, and a transverse stretching strain rate of 2760% / min. After stretching, the film was heat-set at 270° C. in the same tenter and then relaxed by 5% in the width direction to obtain a biaxially stretched laminated film having a thickness of 25 μm.

[0071] [Table 2]

[0072] (Examples 2 to 20, Comparative Examples 1 to 6) The same procedure as in Example 1 was carried out to obtain easily adhesive films, except that the composition, solid content concentration and substrate of the primer composition were changed as shown in Tables 2 and 3, respectively. The evaluation results are shown in Tables 2 and 3. In Example 21, N-methylpyrrolidone (NMP) was used as the solvent instead of methyl ethyl ketone.

[0073] [Table 3]

[0074] The laminated films obtained in the examples had excellent adhesion between the resin film and the metal layer formed by sputtering or electroless plating, and excellent resistance to plating solutions, as well as excellent heat resistance and blocking resistance when rolled.

[0075] The laminated film obtained in Comparative Example 1 had an insufficient content of aliphatic dicarboxylic acid among the acid components in the polyester resin contained in the primer layer, and therefore had poor adhesion between the primer layer and the metal layer, poor resistance to plating solution, and poor adhesion between the resin film and the metal layer.

[0076] The laminated film obtained in Comparative Example 2 was inferior in blocking resistance and heat resistance because the polyester resin contained in the primer layer contained an excessive amount of aliphatic dicarboxylic acid among the acid components.

[0077] The laminated film obtained in Comparative Example 3 had poor heat resistance because the molar ratio of TPA / IPA among the acid components in the polyester resin contained in the primer layer was outside the range of the present invention and the amount of TPA was low.

[0078] The laminated film obtained in Comparative Example 4 had poor plating solution resistance because the molar ratio of TPA / IPA among the acid components in the polyester resin contained in the primer layer was outside the range of the present invention and contained a large amount of TPA.

[0079] The laminated films obtained in Comparative Examples 5 and 6 were inferior in adhesion between the resin film and the metal layer and in heat resistance because films made of resins other than semi-aromatic polyamide resin were used.

Claims

1. A primer layer is laminated on a film made of a semi-aromatic polyamide resin, The primer layer contains a polyester resin in which the content of aliphatic dicarboxylic acids among acid components is 5 to 60 mol % and the molar ratio of terephthalic acid / isophthalic acid is 1 / 99 to 70 / 30.

2. 2. The laminate film according to claim 1, which satisfies the following conditions when the following peel resistance test is performed on a 0.1 μm thick copper layer formed on a primer layer by sputtering or electroless plating. [Peel resistance test] Cross-cut test conforming to JIS K5600-5-6. [conditions] The peeling state of the copper layer is either Class 0, Class 1 or Class 2.

3. 3. The laminate film according to claim 1, which contains a primer layer characterized in that the weight average molecular weight of the polyester resin is 20,000 to 100,000.

4. 3. The laminate film according to claim 1, wherein the primer layer contains inorganic particles and / or organic particles.

5. A laminate comprising the laminate film according to claim 1 or 2 and a metal layer laminated on the primer layer.

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