Aqueous surface treatment agent, method for producing copper-based material having surface treatment layer, copper-based material, and laminate

Abstract

The purpose of the present invention is to provide: an aqueous surface treatment agent for forming a surface treatment layer having excellent adhesion and heat resistance; a method for producing a copper-based material having a surface treatment layer; a copper-based material; and a laminate. This aqueous surface treatment agent contains a copolymer (A) of a polyphenylene ether resin having a hydroxyl group at one terminal and / or both terminals of the molecule and a silane compound having an acyloxyalkyl group, a hydrolysate of the copolymer (A), or a condensate of the copolymer (A) and the hydrolysate. The copper-based material according to the present invention has a surface treatment layer formed from the water-based surface treatment agent on the surface of the copper-based material or on the surface of the copper-based material. The laminate according to the present invention has a resin film layer containing polyphenylene ether on the surface-treated layer of the copper-based material.

Description

Technical Field

[0001] The present invention relates to a water-based surface treatment agent, a method for producing a copper-based material having a surface treatment layer, the copper-based material, and a laminate. Background Art

[0002] Copper-clad laminates formed by laminating a resin substrate and a copper-based material substrate are used in the manufacture of printed circuit boards, for example. For example, Patent Document 1 discloses a technique in which a surface-treated copper foil having a roughening treatment layer, a heat-resistant treatment layer, and a chromate treatment layer is treated with a silane coupling agent to form a silane coupling agent layer, thereby improving adhesion and corrosion resistance.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: International Publication No. 2024 / 116475. Summary of the Invention

[0006] Problems to be solved by the invention

[0007] In recent years, with the further high-speed communication, the high-frequency of electrical signals has continued to develop, and a high-frequency printed circuit board capable of coping with the above situation is needed. In the high-frequency region, it is ideal to use a resin material with excellent dielectric properties (relative dielectric constant and dielectric loss tangent are low), but due to weak electrostatic interaction with copper foil, there is a tendency for low adhesion. In addition, with the integration of printed circuit boards, heat resistance is required.

[0008] An object of the present invention is to provide a water-based surface treatment agent for forming a surface treatment layer having excellent adhesion and heat resistance, a method for producing a copper-based material having a surface treatment layer, a copper-based material, and a laminate.

[0009] Solutions for solving problems

[0010] The present inventors have conducted intensive studies to solve the above problems and have found that the above problems can be solved by including a surface-treated layer comprising a polyphenylene ether resin modified with a silane compound having a predetermined acyloxyalkyl group, thereby completing the present invention.

[0011] That is, the present invention relates to the following items.

[0012] <1> A water-based surface treatment agent comprising a copolymer (A) of a polyphenylene ether resin having a hydroxyl group at one and / or both molecular terminals and a silane compound having an acyloxyalkyl group, a hydrolyzate thereof, or a condensate thereof.

[0013] <2> The water-based surface treatment agent according to <1> above, wherein

[0014] The above-mentioned copolymer (A) comprises:

[0015] At least one structural unit U1 selected from the following formula (1) and the following formula (2); and

[0016] The structural unit U2 represented by the following formula (3) is

[0017] The molar ratio of U2 to U1 (U2 / U1) is 0.5 or more and 20 or less,

[0018] [Chemical Formula 1]

[0019]

[0020]

[0021]

[0022] In formula (1), X represents a divalent linking group obtained by removing the two phenolic hydroxyl groups from a compound having two phenolic hydroxyl groups, R1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, y represents an integer from 1 to 4, p and q are the average value of the number of repeating units and each independently represents an integer in the range of 1 to 100, in formula (2), r represents an integer in the range of 1 to 100, in formula (3), R2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, L represents a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, and G represents a saturated or unsaturated straight-chain or branched-chain acyloxy group having 1 to 10 carbon atoms.

[0023] <3> The water-based surface treatment agent according to <1> or <2> above, wherein

[0024] The above-mentioned water-based surface treatment agent also includes:

[0025] a metal compound (B) containing at least one metal element selected from zirconium, titanium and trivalent chromium; and

[0026] Compounds containing fluorine (C).

[0027] <4> The water-based surface treatment agent according to <3> above, wherein the mass ratio (AM / BM) of the solid content mass (AM) derived from the copolymer (A) to the metal element-equivalent mass (BM) of the metal compound (B) is 1.0 or more and 35 or less.

[0028] The mass ratio (AM / CM) of the solid content mass (AM) derived from the copolymer (A) to the fluorine element equivalent mass (CM) of the fluorine element-containing compound (C) is 1 or more and 350 or less.

[0029] <5> The water-based surface treatment agent according to <4> above, further comprising a compound (D) containing a vanadium element.

[0030] <6> The water-based surface treatment agent according to <5> above, wherein the mass ratio (AM / DM) of the solid content mass (AM) derived from the copolymer (A) to the vanadium-converted mass (DM) of the vanadium-containing compound (D) is 20 or more and 100 or less.

[0031] <7> A method for manufacturing a copper material having a surface treatment layer, comprising:

[0032] a step of bringing the aqueous surface treatment agent described in any one of <1> to <6> into contact with the surface of the copper-based material or on the surface thereof; and

[0033] After the contacting step, a drying step is performed.

[0034] <8> A copper-based material having a surface-treated layer formed with the aqueous surface-treating agent according to any one of <1> to <6> above on the surface of the copper-based material or on the surface of the copper-based material.

[0035] <9> The copper-based material according to <8>, wherein the coating weight per surface of the surface treatment layer is 2 mg / m 2 More than 500 mg / m 2 the following.

[0036] <10> A laminate comprising a resin film layer containing polyphenylene ether on the surface treatment layer of the copper-based material according to <8> or <9>.

[0037] Effects of the Invention

[0038] According to the present invention, a water-based surface treatment agent for forming a surface treatment layer having excellent adhesion and heat resistance, a method for producing a copper-based material having a surface treatment layer (film), a copper-based material, and a laminate can be provided, wherein the surface treatment agent contains a silane-modified polyphenylene ether resin having an acyloxyalkyl group. DETAILED DESCRIPTION

[0039] Hereinafter, specific embodiments will be shown and the present invention will be described in detail.

[0040] <Copolymer (A)>

[0041] The aqueous surface treatment agent of this embodiment comprises a copolymer (hereinafter referred to as "copolymer (A)") obtained by copolymerizing a polyphenylene ether resin having hydroxyl groups at one and / or both molecular ends with a predetermined silane compound having an acyloxyalkyl group. The aqueous surface treatment agent comprising copolymer (A) can form a surface treatment layer having excellent adhesion to difficult-to-bond resins such as polyphenylene ether resin (PPE resin) and PTFE resin, as well as copper-based materials, and excellent heat resistance.

[0042] (Polyphenylene ether resin having hydroxyl groups at one terminal and / or both terminals of the molecule)

[0043] The copolymer (A) contains at least one structural unit U1 selected from the group consisting of the following formula (1) and the following formula (2), and a structural unit U2 represented by the following formula (3).

[0044] [Chemical Formula 2]

[0045]

[0046]

[0047]

[0048] Examples of the combination of structural units in the copolymer (A) include a combination of structural units of formula (1) and formula (3); a combination of structural units of formula (2) and formula (3); and a combination of structural units of formula (1), formula (2), and formula (3). However, in the copolymer (A), there is a partial structure in which at least one structural unit of formula (3) is adjacent to a structural unit of formula (1) or formula (2). In other words, the copolymer (A) has at least one partial structure formed by a substitution reaction between a phenolic hydroxyl group of a polyphenylene ether resin having a hydroxyl group at one and / or both molecular ends and an OR2 group on a Si atom of a silane compound having an acyloxyalkyl group.

[0049] Copolymer (A) may be composed solely of a combination of the above-mentioned structural units or a combination of other structural units. When copolymer (A) is composed solely of structural units of formula (1) and / or formula (2) and formula (3), examples thereof include: (i) a copolymer having formula (3) added to the terminal portion of the structural units of formula (1) and / or formula (2); (ii) a copolymer having a repeating structure in which structural units of formula (1) and / or formula (2) are linked via formula (3); (iii) a copolymer in which formula (1) and formula (3), formula (2) and formula (3) are alternately polymerized, and formula (1), formula (2) and formula (3) are alternately polymerized; and (iv) a copolymer in which formula (1) and / or formula (2) and formula (3) are graft-polymerized. Furthermore, among (i) to (iv), there may be a partial structure in which structural units of formula (3) are linked via silanol bonds.

[0050] In formula (1), X represents a divalent linking group obtained by removing the two phenolic hydroxyl groups from a compound having two phenolic hydroxyl groups, R1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, y represents an integer from 1 to 4, and p and q are the average values ​​of the number of repeating units and each independently represents an integer in the range of 1 to 100.

[0051] In formula (2), r is an integer in the range of 1 to 100.

[0052] In formula (3), R2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, L represents a linear or branched alkyl group having 1 to 10 carbon atoms, and G represents a saturated or unsaturated linear or branched acyloxy group having 1 to 10 carbon atoms.

[0053] In order to improve properties such as adhesion and heat resistance, the copolymer (A) may contain structural units other than those of formulae (1) to (3). When the copolymer (A) contains structural units other than those of formulae (1) to (3), examples thereof include: (v) copolymers obtained by further adding other structural units to the above-mentioned (i); (vi) copolymers obtained by further adding other structural units to the above-mentioned (ii); (vii) copolymers obtained by alternately polymerizing the above-mentioned (iii) with other structural units; (viii) copolymers obtained by further adding other structural units to the above-mentioned (iv).

[0054] The molar ratio (U2 / U1) of the structural unit U2 to the structural unit U1 in the copolymer (A) of this embodiment is preferably in the range of 0.5 to 20, more preferably in the range of 1 to 18. When the molar ratio U2 / U1 is within the above numerical range, the initial adhesion is excellent.

[0055] The weight average molecular weight of the copolymer (A) of this embodiment is usually in the range of 1000 to 100000, preferably in the range of 2000 to 50000. The weight average molecular weight value in this specification is a value measured by GPC (gel permeation chromatography) and is converted into polystyrene.

[0056] <Method for producing copolymer (A)>

[0057] The copolymer (A) of the present invention can be produced by the following method: a compound having a structural unit represented by formula (1) (hereinafter referred to as "compound (a1)") and / or a compound having a structural unit represented by formula (2) (hereinafter referred to as "compound (a2)"), and a compound capable of forming a structural unit represented by formula (3) (hereinafter referred to as "compound (a3)") are mixed in an organic solvent, and further a compound having a structural unit other than compound (a1) and compound (a2) is mixed as needed, and a polymerization reaction is carried out at a prescribed temperature. In addition, a reaction catalyst (hereinafter also referred to as "compound (a4)") can be further mixed as needed to carry out the reaction. The reaction temperature is not particularly limited, and is generally within the range of 60°C or more and 120°C or less, preferably within the range of 80°C or more and 100°C or less. The reaction time is not particularly limited, and is generally within the range of 10 minutes or more and 24 hours or less, and preferably within the range of 30 minutes or more and 12 hours or less.

[0058] Examples of the compound (a1) include compounds represented by formula (4). That is, the compound represented by formula (4) is a polyphenylene ether resin having hydroxyl groups at both molecular terminals.

[0059] [Chemical Formula 3]

[0060]

[0061] In formula (4), X represents a divalent linking group obtained by removing the two phenolic hydroxyl groups from a compound having two phenolic hydroxyl groups. Specific examples of the compound having two phenolic hydroxyl groups include bisphenol A, tetramethylbisphenol A, bisphenol F, and 4,4'-biphenylenediol.

[0062] In formula (4), R1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0063] In formula (4), y represents an integer of 1 to 4.

[0064] In formula (4), p and q are average values ​​of the number of repeating units and each independently represents an integer in the range of 1 to 100.

[0065] Compound (a1) may be a synthetic product or a commercially available product. Compounds having a number average molecular weight of generally several thousand to several hundred thousand are commercially available. As a raw material for the copolymer (A) of the present invention, compounds having a number average molecular weight of 200 to 100,000 are preferred, and compounds having a number average molecular weight of 500 to 10,000 are more preferred. Specific examples of commercially available compounds (a1) include Noryl SA90 (number average molecular weight 1,700) manufactured by SABIC, but are not limited thereto. The molecular weight in this specification refers to a value calculated in terms of polystyrene based on the results of gel permeation chromatography (GPC).

[0066] Examples of the compound (a2) include compounds represented by formula (5). That is, the compound represented by formula (5) is a polyphenylene ether resin having a hydroxyl group at one terminal of the molecule.

[0067] [Chemical Formula 4]

[0068]

[0069] In formula (5), r is an average value of the number of repeating units and represents an integer in the range of 1 to 100.

[0070] Compound (a2) may be a synthetic product or a commercially available product. Compounds having a number average molecular weight of generally several thousand to several hundred thousand are commercially available. As a raw material for the copolymer (A) of the present invention, compounds having a number average molecular weight of 200 to 100,000 are preferred, and compounds having a number average molecular weight of 500 to 10,000 are more preferred. Specific examples of commercially available compounds (a2) include Noryl SA120 (number average molecular weight 2400) manufactured by SABIC, but are not limited thereto.

[0071] Examples of the compound (a3) ​​include compounds represented by formula (6).

[0072] [Chemical Formula 5]

[0073]

[0074] In formula (6), R2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, L represents a linear or branched alkyl group having 1 to 10 carbon atoms, and G represents a saturated or unsaturated linear or branched acyloxy group having 1 to 10 carbon atoms.

[0075] The copolymer (A) is formed by a substitution reaction between the terminal phenolic hydroxyl group of the compound (a1) and / or the compound (a2) and the OR2 group on the Si atom of the silane compound having an acyloxyalkyl group. That is, the copolymer (A) is a polyphenylene ether resin modified with a silane having an acyloxyalkyl group. In the copolymer (A) used in the present invention, the compound (a3) ​​capable of forming the structural unit represented by formula (3) is not particularly limited as long as it is a compound represented by formula (6), and preferably the carbon chain in G has an unsaturated acyloxy group. As the substance having an acyloxyalkyl group, for example, 3-(trimethoxysilyl)propyl acetate, (trimethoxysilyl)methyl (meth)acrylate, (trimethoxysilyl)ethyl (meth)acrylate, 3-(trimethoxysilyl)propyl (meth)acrylate, 8-(trimethoxysilyl)octyl (meth)acrylate, (triethoxysilyl)methyl (meth)acrylate, (triethoxysilyl)ethyl (meth)acrylate, 3-(triethoxysilyl)propyl (meth)acrylate, 8-(triethoxysilyl)octyl (meth)acrylate, etc. can be used, but the present invention is not limited to these.

[0076] As an organic solvent, there is no particular limitation as long as it can dissolve compounds (a1) to (a3), and examples thereof include alcoholic solvents, glycol ether-based solvents, ketone-based solvents, and amide-based solvents. Alcoholic solvents include methanol, ethanol, propanol, 2-propanol, and butanol; glycol ether-based solvents include ethylene glycol ethyl ether, ethylene glycol n-butyl ether, diethylene glycol ethyl ether, and propylene glycol methyl ether; ketone-based solvents include methyl ethyl ketone and methyl isobutyl ketone; and amide-based solvents include dimethylformamide, dimethylacetamide, and N-methyl-2-pyrrolidone. These organic solvents may be used alone or in combination of two or more.

[0077] From the viewpoint of adhesiveness, the copolymer (A) is preferably formed using a compound (a3) ​​having a carbon-carbon unsaturated bond in G.

[0078] The reaction catalyst is not particularly limited as long as it is a catalyst that promotes the polymerization reaction. Tertiary amines, organometallic carboxylates, titanates, etc. can be used. Examples of tertiary amines include dimethylbenzylamine, triethylamine, and tributylamine. Examples of organometallic carboxylates include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctoate, tin(II) acetate, lead naphthenate, zinc octoate, and cobalt naphthenate. Examples of titanates include titanium tetraethoxide, titanium tetraisopropoxide, and titanium tetrabutoxide. These reaction catalysts can be used alone or in combination of two or more.

[0079] Whether the copolymer (A) produced as described above contains the structural units represented by formula (1), formula (2), formula (3), etc. can be confirmed by measuring the Si-O-Ar (Ar represents an aromatic group)-derived wavelength at 1070 cm-1 using an infrared spectrophotometer by the ATR method. -1 ~1100cm -1 to the peak.

[0080] <Water-based surface treatment agent>

[0081] The water-based surface treatment agent of the present embodiment comprises the copolymer (A) or its hydrolyzate or its condensate. The water-based surface treatment agent of the present embodiment forms a surface treatment layer having excellent adhesion to resin and heat resistance on the copper foil.

[0082] The aqueous surface treatment agent of this embodiment preferably comprises a metal compound (B) containing at least one metal element selected from zirconium, titanium, and trivalent chromium (hereinafter referred to as "compound (B)") and a compound (C) containing a fluorine element (hereinafter referred to as "compound (C)"). The surface treatment layer formed with the aqueous surface treatment agent containing compound (B) and compound (C) exhibits excellent initial adhesion.

[0083] As the compound containing zirconium, as long as it contains zirconium as an element, there is no particular limitation, and it can be any of an inorganic zirconium compound and an organic zirconium compound. As the inorganic zirconium compound, for example, zirconyl sulfate, zirconyl nitrate, zirconyl nitrate, zirconyl chloride, zirconium chloride, zirconium oxide sol, zirconium oxide, hexafluorozirconic acid, etc. can be mentioned, but are not limited to these. In addition, as the organic zirconium compound, for example, zirconium lactate, zirconium tetraisopropoxide, zirconium acetylacetonate, n-propyl zirconate, n-butyl zirconate, zirconium tetraacetylacetonate, etc. can be mentioned, but are not limited to these. These compounds can be used alone or in combination in the preparation of the aqueous surface treatment agent.

[0084] As a compound containing titanium, there is no particular limitation as long as it contains titanium as an element, and it can be any of an inorganic titanium compound and an organic titanium compound. As an inorganic titanium compound, for example, titanium oxysulfate, titanium oxynitrate, titanium nitrate, titanium oxychloride, titanium chloride, titanium dioxide sol, titanium oxide, hexafluorotitanic acid, etc. can be mentioned, but it is not limited to these. In addition, as an organic titanium compound, for example, potassium titanium oxalate, titanium lactate, tetraisopropyl titanate, tetra-n-butyl titanate, butyl titanate dimer, titanium acetylacetonate, diisopropyl diacetylacetonate titanium, diisopropoxy bis(acetylacetonate) titanium, etc. can be mentioned, but it is not limited to these. These compounds can be used alone or in combination in the preparation of the aqueous surface treatment agent.

[0085] The compound containing trivalent chromium is not particularly limited as long as it contains trivalent chromium as an element, and may be any of an inorganic trivalent chromium compound and an organic trivalent chromium compound. Examples of inorganic trivalent chromium compounds include, but are not limited to, chromium acetate, chromium hydroxide, chromium trichloride, chromium sulfate, chromium nitrate, and chromium fluoride. Examples of organic trivalent chromium compounds include, but are not limited to, chromium (III) acetate and chromium (III) acetylacetonate. These compounds may be used alone or in combination in the preparation of a water-based surface treatment agent.

[0086] Compound (C) is not particularly limited as long as it is a compound that can supply fluorine ions when combined with an aqueous surface treatment agent. The compound containing fluorine element is hydrofluoric acid, an inorganic fluoride salt, a fluoride of a metal, a complex of hydrofluoric acid and a metal, and examples thereof include hexafluorozirconic acid, hexafluorotitanic acid, hexafluorohafnic acid, hydrofluoric acid, ammonium fluoride, ammonium bifluoride, germanium fluoride, sodium fluoride, potassium fluoride, potassium bifluoride, ferric fluoride, fluorosilicic acid, sodium fluoride, sodium bifluoride, but are not limited to these. Various compounds containing fluorine element can be combined with only one or more of two or more.

[0087] A compound containing zirconium and fluorine, such as hexafluorozirconic acid, can serve as a supply source of zirconium and fluorine, and a compound containing titanium and fluorine, such as hexafluorotitanic acid, can serve as a supply source of titanium and fluorine.

[0088] In the water-based surface treatment agent of this embodiment, the mass ratio (AM / BM) of the solid content mass (AM) from the copolymer (A) in the water-based surface treatment agent to the metal element converted mass (BM) of the above-mentioned metal compound (B) is preferably greater than 1.0 and less than 35, and more preferably greater than 5.0 and less than 30.

[0089] In addition, in the water-based surface treatment agent of this embodiment, the mass ratio (AM / CM) of the solid content mass (AM) from the copolymer (A) to the fluorine element converted mass (CM) of the above-mentioned fluorine element-containing compound is preferably greater than 1 and less than 350, and more preferably greater than 10 and less than 300.

[0090] When the AM / BM and AM / CM of the water-based surface treatment agent are within the above numerical ranges, the surface treatment layer formed with the water-based surface treatment agent has excellent initial adhesion.

[0091] The aqueous surface treatment agent of the present embodiment preferably contains a compound (D) containing a vanadium element (hereinafter referred to as "compound (D)"). The surface treatment layer formed by the aqueous surface treatment agent containing compound (D) has excellent heat resistance.

[0092] Compound (D) is not particularly limited as long as it can supply vanadium-containing ions when added to an aqueous surface treatment agent. The vanadium-containing compound may be either an inorganic vanadium compound or an organic vanadium compound. Examples of inorganic vanadium compounds include, but are not limited to, sodium vanadate, potassium vanadate, ammonium metavanadate, vanadium sulfate, and vanadium pentoxide. Examples of organic vanadium compounds include, but are not limited to, vanadyl acetylacetonate. The various vanadium-containing compounds may be added alone or in combination of two or more.

[0093] In the water-based surface treatment agent of the present embodiment, the mass ratio (AM / DM) of the solid content mass (AM) derived from the copolymer (A) to the vanadium element-converted mass (DM) of the vanadium element-containing compound (D) is preferably 20 to 100, more preferably 30 to 80. When the mass ratio (AM / DM) is within the above numerical range, a surface treatment layer having even better heat resistance can be formed.

[0094] The pH of the aqueous surface treatment agent of this embodiment is not particularly limited, but is preferably 1 to 6, more preferably 2 to 5. When the pH is within the above numerical range, the surface treatment film formed by the aqueous surface treatment agent tends to have excellent adhesion.

[0095] The water-based surface treatment agent of the present embodiment may contain various additives as needed. As additives, for example, surfactants, defoamers, leveling agents, crosslinking agents, pH regulators, thickeners, antioxidants, antibacterial and antifungal agents, colorants, etc. can be cited, but are not limited to these. By adding these additives to the water-based surface treatment agent, the storage and drying properties of the water-based surface treatment agent can be improved, or the operability of the surface treatment layer using the water-based surface treatment agent in the manufacture can be improved, or the smoothness and stability of the manufactured surface treatment layer can be improved. These additives can be added within the scope of not damaging the effect of the present invention, and the content of the additives relative to the mass of the water-based surface treatment agent can be at most a few percent by mass.

[0096] <Copper-based material with surface treatment layer and method for producing the same>

[0097] The method for manufacturing a copper-based material having a surface treatment layer according to this embodiment (hereinafter referred to as the "manufacturing method") includes: a contacting step (first step) of bringing the aqueous surface treatment agent into contact with the surface or on the surface of the copper-based material; and a drying step (second step) of drying the aqueous surface treatment agent after the contacting step.

[0098] Examples of contact methods in the first step include, but are not limited to, dipping, coating, spraying, and flow coating. The contact temperature and time are not particularly limited, but are generally within the range of 5°C to 50°C and within the range of 0.1 seconds to 1 hour.

[0099] The copper-based material is not particularly limited as long as the entire or a portion of the surface of the material contains copper or a copper alloy, and any material may be formed of at least copper or a copper alloy. Examples of the copper or copper alloy include electrolytic copper foil and rolled copper foil.

[0100] The manufacturing method of this embodiment may also include a degreasing process for the surface of the material before the first process. Degreasing can be performed using a known method using an appropriate degreasing agent according to the material. Examples of degreasing agents include, but are not limited to, known acidic degreasing agents, alkaline degreasing agents, and solvent degreasing agents. Degreasing methods are not particularly limited, and examples include brush cleaning, spray cleaning (spray cleaning), and dip cleaning.

[0101] The manufacturing method of this embodiment may perform a water washing step for washing the surface of the material after the degreasing step and before the first step, or may perform an acid washing step or an alkali washing step after the water washing step, or may perform the water washing step and the acid washing step or the alkali washing step repeatedly before the first step. The acid washing step and the alkali washing step may be applied by known methods.

[0102] The above-mentioned manufacturing method can produce a copper-based material having a surface treatment layer containing the copolymer (A) on the surface. The amount of the surface treatment layer is not particularly limited, but is usually 2 mg / m2 per side. 2 More than 500 mg / m 2 The following range, preferably 5 mg / m 2 More than 200 mg / m 2 The following range.

[0103] A base layer may be provided between the copper-based material and the surface treatment layer comprising the copolymer (A).

[0104] <Laminate having a resin film layer and method for producing the same>

[0105] The method for producing a laminate having a resin film layer according to this embodiment (hereinafter referred to simply as "laminate production method") includes the step of bonding a resin film layer containing polyphenylene ether to the surface treated layer of the copper-based material having the surface treated layer.

[0106] As the bonding method in the bonding step, a commonly used bonding method may be used, and for example, a thermocompression bonding method may be mentioned.

[0107] A laminate having a resin film layer is suitable for a copper-clad laminate because, for example, the resin film layer is excellent in adhesion to a copper-based material and heat resistance.

[0108] Example

[0109] The water-based surface treatment agent of the present invention will be described with reference to Examples and Comparative Examples. However, the present invention is not limited to the following Examples.

[0110] <<Copolymer (A)>>

[0111] <Synthesis example 1>

[0112] As shown in Table 1, 85 g of a1-1 (0.05 mol), 5 times the mass of a1-1 in toluene, and 5 times the mass of a1-1 in ethanol were added to a reaction container equipped with a stirrer, a dropping funnel, and a thermometer, and heated to 80°C while stirring under a nitrogen environment. Then, 0.1 mol of a silane compound a3-1 having an acyloxyalkyl group and 0.001 mol of a catalyst a4-1 were added dropwise in such a way that the reaction temperature was maintained in the range of 80°C to 100°C. After reacting at 80°C to 100°C for 8 hours, 5 times the mass of a1-1 in deionized water was added. Then, water and residual solvent were distilled off to obtain a copolymer A1 with a solid content concentration of 40%. The infrared absorption spectrum of the obtained copolymer A1 is at 1070 cm -1 ~1100cm -1 Has a peak.

[0113] Copolymers A2 to A5 were obtained by the same method as in Synthesis Example 1 using the prescribed amounts (feed amount: mole) of the components shown in Table 1. The infrared absorption spectra of copolymers A2 to A5 were obtained at 1070 cm -1 ~1100cm -1 Has a peak.

[0114] [Table 1]

[0115]

[0116] Each symbol in Table 1 represents the following components.

[0117] <Polyphenylene ether resin having a terminal hydroxyl group: compound a1 / compound a2>

[0118] a1-1: Noryl SA90 (number average molecular weight 1700, made by SABIC Contract Co., Ltd.)

[0119] a2-1: Noryl SA120 (number average molecular weight 2400, manufactured by SABIC Corporation)

[0120] <Silane compound having an acyloxyalkyl group: a3>

[0121] a3-1: (Triethoxysilyl) methyl acrylate

[0122] a3-2: 3-(Trimethoxysilyl)propyl methacrylate

[0123] a3-3: 3-(Trimethoxysilyl)propyl acetate

[0124] Catalyst: a4

[0125] a4-1: Dibutyltin dilaurate

[0126] a4-2: Titanium tetraisopropoxide

[0127] <<Water-based surface treatment agent>>

[0128] <Examples 1 to 25 and Comparative Examples 1 to 5>

[0129] As shown in Table 2, a copolymer (A), a metal compound (B) containing at least one metal element selected from zirconium, titanium and trivalent chromium, a compound (C) containing a fluorine element, and a compound (D) containing a vanadium element were added to deionized water to prepare Examples 1 to 25 and Comparative Examples 1 to 5.

[0130] In each example, the solid content concentration of the aqueous surface treatment agent was adjusted by varying the amount of deionized water added to obtain the film amounts shown in Table 2. The pH of the aqueous surface treatment agent was adjusted using nitric acid and aqueous ammonia.

[0131] <Comparative Example 6>

[0132] Comparative Example 6 was prepared using A0a in which a1-1, which is an unmodified PPO resin, was added to a toluene solvent.

[0133] <Comparative Example 7>

[0134] Comparative Example 7 was prepared using A0b obtained by mixing 0.05 mol of a1-1, which is an unmodified PPO resin, and 0.1 mol of a3-1, a silane compound having an acyloxyalkyl group, in a toluene solvent.

[0135] In Comparative Examples 6 and 7, the solid content concentration was adjusted by changing the blending amount of toluene.

[0136] Each symbol in Table 2 represents the following compound.

[0137] <Compound B>

[0138] B1: Hexafluorozirconic acid

[0139] B2: Zirconium(IV) acetylacetonate

[0140] B3: Hexafluorotitanic acid

[0141] B4: Chromium fluoride

[0142] <Compound C>

[0143] C1: Hydrofluoric acid

[0144] C2: Tetrafluoroboric acid

[0145] <Compound D>

[0146] D1: Ammonium metavanadate

[0147] D2: Vanadium Sulfate

[0148] [Table 2]

[0149]

[0150] <<Manufacturing of copper materials with surface treatment layers>>

[0151] <Copper materials>

[0152] As the metal material, electrolytic copper foil for PCB (glossy surface, thickness: 12 μm, Rz ≤ 1 μm) was used.

[0153] <Pretreatment>

[0154] As an alkaline degreasing agent, Fine Cleaner FC-315S (manufactured by Japan Parkersei Co., Ltd.) was diluted in deionized water to 20 g / L and immersed at 60°C for 1 minute to degrease the surface of the copper material. After degreasing, the surface of the copper material was rinsed with water by immersing it in ion exchange water at 25°C for 1 minute. After rinsing, the surface of the copper material was pickled by immersing it in 10% sulfuric acid at 25°C for 1 minute. After pickling, the surface of the copper material was rinsed with water by immersing it in ion exchange water at 25°C for 1 minute.

[0155] Surface treatment

[0156] After the pretreatment, the copper material was coated with the water-based surface treatment agent of Example 1 using a #3 SUS Meyer rod. The copper material was then dried in a hot air oven at the ambient temperature shown in Table 2 for 5 minutes to obtain a copper material having the film weight shown in Table 2.

[0157] <<Manufacturing of Laminated Body>>

[0158] A resin film layer containing polyphenylene ether (resin content 68%, containing epoxy, vinyl, and acid anhydride groups as resin functional groups and containing silica as filler) was arranged on the surface treated layer of the copper foil having the surface treated layer obtained in Example 1. The film was laminated using a Morton CVA725 vacuum laminator at a temperature of 190°C and a pressure of 70 kgf / cm 2 Vacuum lamination was performed for 150 minutes under the conditions of , thereby obtaining the laminate 1 of Example 1.

[0159] The same method as the method for producing the laminate 1 was used, except that the copper-based material having a surface-treated layer obtained in Example 1 was replaced by the copper-based materials of Examples 2 to 25 and Comparative Examples 1 to 7, and the same vacuum lamination process was performed to obtain laminates 2 to 25 of Examples 2 to 25 and laminates 26 to 32 of Comparative Examples 1 to 7.

[0160] <<Evaluation Test>>

[0161] Various evaluation tests were performed using the laminated bodies of Examples 1 to 25 and Comparative Examples 1 to 7.

[0162] <Initial Adhesion> The initial adhesion of each laminate was measured using a tensile tester in accordance with IPC-TM-650 and evaluated according to the following evaluation criteria.

[0163] (Evaluation Criteria)

[0164] 5: 0.6N / mm or more

[0165] 4: 0.5N / mm or more and less than 0.6N / mm

[0166] 3: 0.4N / mm or more and less than 0.5N / mm

[0167] 2: 0.3N / mm or more and less than 0.4N / mm

[0168] 1: less than 0.3N / mm

[0169] Adhesion after solder float test

[0170] After floating the various laminates in a solder bath at 288° C. for 180 seconds, the adhesion was evaluated using the same test method and evaluation criteria as those for the initial adhesion described above.

[0171] (Evaluation Criteria)

[0172] 5: 0.6N / mm or more

[0173] 4: 0.5N / mm or more and less than 0.6N / mm

[0174] 3: 0.4N / mm or more and less than 0.5N / mm

[0175] 2: 0.3N / mm or more and less than 0.4N / mm

[0176] 1: less than 0.3N / mm

[0177] Heat resistance

[0178] Each laminate was floated on 288°C solder according to IPC TM-650 2.4.13 evaluation rules, and the time required for separation between the resin layer and the copper foil was measured. Evaluation was performed according to the following evaluation criteria.

[0179] (Evaluation Criteria)

[0180] 5: The time required to peel the resin layer and the copper foil is more than 400 seconds

[0181] 4: The time required to peel the resin layer and the copper foil is 300 seconds or more and less than 400 seconds

[0182] 3: The time required to peel the resin layer and the copper foil is 200 seconds or more and less than 300 seconds

[0183] 2: The time required to peel the resin layer and the copper foil is 100 seconds or more and less than 200 seconds

[0184] 1: The time required to peel the resin layer and the copper foil is less than 100 seconds

[0185] Table 3 shows the evaluation results of each test.

[0186] [Table 3]

[0187]

[0188] Furthermore, while the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

[0189] According to the present invention, a water-based surface treatment agent for forming a surface treatment layer having excellent adhesion and heat resistance, a method for producing a copper-based material having a surface treatment layer (film), a copper-based material, and a laminate can be provided, wherein the surface treatment agent contains a silane-modified polyphenylene ether resin having an acyloxyalkyl group.

Claims

1. A water-based surface treatment agent comprising a copolymer (A) of a polyphenylene ether resin having a hydroxyl group at one terminal and / or both terminals of the molecule and a silane compound having an acyloxyalkyl group, a hydrolyzate thereof, or a condensate thereof.

2. The water-based surface treatment agent according to claim 1, wherein The copolymer (A) comprises: At least one structural unit U1 selected from the following formula (1) and the following formula (2); and The structural unit U2 represented by the following formula (3) is The molar ratio of U2 to U1 (U2 / U1) is 0.5 or more and 20 or less, In formula (1), X represents a divalent linking group obtained by removing the two phenolic hydroxyl groups from a compound having two phenolic hydroxyl groups, R1 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, y represents an integer from 1 to 4, p and q are the average value of the number of repeating units and each independently represents an integer in the range of 1 to 100, in formula (2), r represents an integer in the range of 1 to 100, in formula (3), R2 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, L represents a straight-chain or branched-chain alkyl group having 1 to 10 carbon atoms, and G represents a saturated or unsaturated straight-chain or branched-chain acyloxy group having 1 to 10 carbon atoms.

3. The water-based surface treatment agent according to claim 1 or 2, wherein The water-based surface treatment agent further comprises: a metal compound (B) containing at least one metal element selected from zirconium, titanium and trivalent chromium; and Compounds containing fluorine (C).

4. The water-based surface treatment agent according to claim 3, wherein The mass ratio (AM / BM) of the solid content mass (AM) derived from the copolymer (A) to the metal element equivalent mass (BM) of the metal compound (B) is 1.0 or more and 35 or less, The mass ratio (AM / CM) of the solid content mass (AM) derived from the copolymer (A) to the fluorine element equivalent mass (CM) of the fluorine element-containing compound (C) is 1 or more and 350 or less.

5. The water-based surface treatment agent according to claim 4, wherein The water-based surface treatment agent further includes a compound (D) containing vanadium.

6. The water-based surface treatment agent according to claim 5, wherein The mass ratio (AM / DM) of the solid content mass (AM) derived from the copolymer (A) to the vanadium element-equivalent mass (DM) of the vanadium element-containing compound (D) is 20 or more and 100 or less.

7. A method for manufacturing a copper material having a surface treatment layer, comprising: A step of bringing the aqueous surface treatment agent according to any one of claims 1 to 6 into contact with the surface or on the surface of the copper-based material; as well as After the contacting step, a drying step of drying is performed. 8 . A copper-based material having a surface treatment layer formed with the water-based surface treatment agent according to claim 1 or on the surface of the copper-based material.

9. The copper-based material according to claim 8, wherein: The adhesion amount of each side of the surface treatment layer is 2 mg / m 2 More than 500 mg / m 2 the following. 10 . A laminate comprising a resin film layer containing polyphenylene ether on the surface treatment layer of the copper-based material according to claim 8 or 9 .

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