JP5385625B2 - Two-layer flexible copper-clad laminate and method for producing the same - Google Patents

Description

  The present invention relates to a two-layer flexible copper-clad laminate and a method for producing the same, and more specifically, using an acidic copper plating bath composition, copper is thickly plated on a resin film surface to provide a smooth and glossy appearance. In addition, the present invention relates to a two-layer flexible copper-clad laminate (two-layer FCCL) that is excellent in peel resistance and easily finely patterned.

  In addition, the present invention provides a method for producing a two-layer flexible copper-clad laminate having such a two-layer FCCL using an acidic copper plating bath composition and the electroplating step being a one-step wet plating method. Related.

  In recent years, electronic devices such as mobile phones, personal computers, videos, game machines, etc. have been used with higher density and smaller size of components, and printed circuit boards on which they are mounted require higher density of circuits to be mounted. In fact, through-holes and blind via holes used for interlayer connection of at least one side of the substrate or a multilayer substrate tend to have a smaller diameter and a higher aspect.

  In addition, these mounting circuits are conventionally connected between each circuit layer by a conductive metal deposited in a minute hole such as a blind via hole or a through hole provided in a laminated board. The layers are connected by a blind via hole plating method for forming a conductive metal film on the inner side surface and bottom surface of the blind via hole. On the other hand, the through holes are generally connected between the respective layers of the substrate by a through hole plating method in which a conductive metal film is uniformly formed on the inner surface of the through hole.

  In connection with such substrates, polyimide resin films are, for example, electronic components such as printed wiring boards (PWB), flexible printed wiring boards (FPC), automatic tape bonding (TAB) tapes, and chip-on-film (COF) tapes. Widely used as an insulating substrate material. In addition, such PWB, FPC, TAB tape, and COF tape use a metal-coated polyimide film base material in which copper is mainly coated as a metal conductor layer on at least one surface of a polyimide resin film.

  Further, for processing (or manufacturing) such a metal-coated polyimide film substrate, conventionally, for example, 1) a three-layer copper polyimide base obtained by bonding a polyimide film and a copper foil via an adhesive. And 2) a two-layer copper polyimide base material obtained by directly forming a copper layer on a polyimide film. Further, the latter two-layer copper polyimide base material [= Flexible Copper Clad Laminate (two-layer FCCL)], a casting method for forming a polyimide film on a copper foil, and copper foil and polyimide There are a laminating method in which a film is thermocompression bonded with thermoplastic polyimide, and a sputtering / plating method (metallizing method) in which a conductor layer is formed by electroplating after forming a seed layer by sputtering. There are pros and cons in terms of properties and fine patterns. Among them, it is said that the two-layer FCCL by sputtering / plating method (metallization method) is particularly advantageous for fine patterning.

  Therefore, for example, in Patent Document 1, with the reduction in size and thickness of portable electronic devices, even smaller TAB tapes and COF tapes are made smaller and thinner, that is, higher in density. In order to cope with the technical trend of further narrowing of the wiring pitch, after the matte copper plating in the range of 0.5 to 2 μm is applied on the conductive polyimide film, the thickness of the copper plating layer becomes 20 μm or less. Thus, a two-layer plating base material (or substrate) subjected to bright copper plating is described.

  In this way, the two-layer plating base material that is focused on that the copper layer thickness can be made thin and the thickness can be freely controlled is a flexible copper layer having a thickness of 10 μm or less and polyimide Since the bonding interface with the film is flat, it is also said to be a substrate suitable for forming a fine pattern. However, since finer fine patterning is required in recent years, when manufacturing electronic parts such as PWB, FPC, TAB tape, C0F tape using such a two-layer plating substrate, In particular, it causes uneven exposure and uneven etching, so that the surface of the two-layer plated substrate is required to be smoother.

  In addition, the sputtering / plating method (metallization method) that is already advantageous for fine patterning as described above is usually (1) as a pretreatment, a polyimide resin film surface is subjected to plasma treatment and metallization by sputtering under vacuum. The device becomes a large scale due to processing and the like. In addition, (2) since wet processing by plating is performed after dry processing such as plasma processing and sputtering processing, continuation of the manufacturing process is difficult, and productivity tends to be low and cost is increased. Also, (3) blistering after electrolytic copper plating and swelling due to heat treatment (also referred to as baking) are likely to occur, and there is adhesion between “polyimide-electroless nickel plating” and “electroless nickel plating-electrocopper plating”. It tends to decrease partially.

  Therefore, in Patent Document 2, in order to deal with these problems, it is easy to make continuous treatment with a process mainly including wet treatment without performing plasma treatment or sputtering treatment, and deterioration of insulation resistance or migration is performed. There has been proposed a method for surface metallization of a polyimide resin material that has good plating deposition stability without being promoted, and can ensure smoothness and adhesion between the polyimide resin film and the metal regardless of the type of polyimide resin.

  That is, the surface metallization method includes a surface treatment step of a polyimide resin material having a carbonyl group in the molecule as a pretreatment of the polyimide resin material, particularly using an aprotic polar solvent such as dimethylformamide, and surface oxidation. A polyimide resin that includes a treatment step and a treatment step with an alkaline aqueous solution, and the thick copper plating treatment after the electroless nickel plating treatment is performed by performing an alkaline electroless copper plating treatment or an alkaline electrolytic copper plating treatment to obtain a two-layer FCCL. This is a surface metallization method of a material.

  In Patent Document 3, at least one surface of a polyimide film frequently used as PWB, FPC, TAB, and COF is surface-modified with oxygen plasma, and then Ni, Cr, Ni—Cr alloy or the like is sputtered. A two-layer FCCL formed by forming a conductive metal seed layer, applying a sputtered copper layer, performing primary copper plating, and then depositing copper by electrolytic copper plating or electroless copper plating, It exhibits a heat-resistant adhesion equal to or better than that of a three-layer substrate (400 N / m or more), and the cause is that the pretreatment with oxygen plasma gives moderate roughness and chemical alteration to the polyimide resin surface. It is stated that.

JP 2007-23344 A Japanese Patent Laid-Open No. 2007-262481 JP 2008-78276 A

  Under such circumstances, the present inventors have been paying attention to these technical fields including the above-mentioned Patent Documents 1 to 3, and performing an acidic copper plating process on various substrate surfaces used in this field. Under the background of research, for the new plating that exhibits excellent plating appearance such as blind via hole and through hole inside and corner corner plating, and plating surface leveling, and also supports substrate defects A leveling agent is proposed. In addition, based on these results, by using an acidic copper plating bath composition containing this leveling agent as a component, a substrate having micropores such as through holes and blind via holes, or a conductive metal such as copper is coated. A patent application (Japanese Patent Application No. 2006-243651) has already been filed as a method for copper plating of a substrate that can apply copper plating to a resin film with high reliability (see Japanese Patent Application Laid-Open No. 2008-63624).

  In other words, by using an acidic copper plating bath, a substrate with minute holes such as through holes and blind via holes, or a resin film whose surface is coated with a conductive metal such as copper is more reliable than conventional products. It was possible to perform copper plating treatment.

  Therefore, the object of the present invention has been related to various electronic devices in recent years, and the density and miniaturization of components used have progressed, and the mounting circuit provided on a printed circuit board or the like on which the components are mounted has further increased in density. Under the circumstances where there is a demand for further reduction in diameter and trend toward higher aspect, a newly developed acidic copper plating bath composition is used to wet the thickness of resin film such as polyimide film without using primary copper plating. A two-layer flexible copper-clad laminated base material (two-layer FCCL) plated and plated has a smooth and glossy appearance, and the copper plating layer has excellent peeling resistance and is easily made into a fine pattern. It is to provide a coated resin film substrate.

  Another object of the present invention is to use such a two-layer FCCL with the newly developed acidic copper plating bath composition, the entire process being a wet process, and the copper coating process in one step. It is providing the manufacturing method of the metal coating resin film base material which can be thickness-plated.

  As a result of intensive studies to achieve the above object, the present inventors have found a copolymer of “diallyldialkylammonium alkylsulfate”-“(meth) acrylamides”-“sulfur dioxide” which is a leveling agent for plating. In the acidic copper plating bath composition as one component, when the resin film on which the conductive Ni metal film seed layer has been formed in advance is thick copper plated without using the primary copper plating, the two-layer flexible The present inventors have found that the copper clad laminate (two-layer FCCL) has a smooth glossy appearance and that the peel resistance of the obtained copper plating layer is remarkably improved, thereby completing the present invention.

That is, according to the present invention, a seed layer having a coating thickness of 10 to 300 nm of Ni or an alloy thereof is formed in advance by an electroless plating method on the surface of the resin film substrate that has been hydrophilically modified as a pretreatment,
The seed layer is plated with a thickness in the range of 0.05 to 50 μm of copper plating without using a primary copper plating which is a strike copper plating, using an acidic copper plating bath composition. A two-layer flexible copper-clad laminate substrate is provided.

Further, according to the present invention, the resin film substrate on which Ni or its alloy coating seed layer having a coating thickness in the range of 10 to 300 nm is applied, the newly developed acidic copper plating bath composition used, and the two layers obtained The copper plating layer of the flexible copper-clad laminate (two-layer FCCL) is smooth, glossy, and peel-resistant.
(1) It is possible to provide a two-layer flexible copper-clad laminate in which the resin film substrate used is a polyimide film to which a nickel seed layer of electroless plating conductive metal is applied as a seed layer.
(2) Acid copper plating bath composition is (A) copper ion component, (B) organic acid and / or inorganic acid component, (C) chlorine ion component, (D) organic polymer component, (E) Brightener component And (F) a two-layer flexible copper-clad laminate composed of a copolymer component of diallyldialkylammonium alkyl sulfate as a leveling agent for plating, (meth) acrylamides and sulfur dioxide.

  Further, according to the present invention, a two-layer flexible copper-clad laminate substrate (two-layer FCCL) that exhibits the above-described effects is formed using a newly developed acidic copper plating bath composition, A two-layer flexible copper-clad laminate (2) characterized in that the entire process including the step of thickly plating the copper conductive layer on the seed layer is a wet process, and the all-coppering process is a one-step process. A method for producing the layer FCCL) is provided.

That is,
A step of forming a conductive metal seed layer such as Ni or an alloy thereof in advance by electroless plating on the surface of the resin film substrate subjected to hydrophilic surface modification;
In the acidic copper plating bath composition, the process comprises wet electroplating in a one-step process without using primary copper plating as strike copper plating, and depositing a copper conductive layer on the seed layer. It is a manufacturing method of a 2 layer flexible copper clad laminated base material.

In addition, in connection with the method for producing such a two-layer flexible copper-clad laminate, in the present invention,
(1): A method for producing a two-layer flexible copper-clad laminate substrate in which the conductive metal as the seed layer is either Ni or an alloy thereof can be provided.
(2): The manufacturing method of the two-layer flexible copper clad laminated base material whose said resin film board | substrate used is the polyimide film plated with electroless nickel can be provided.
(3): The acidic copper plating bath composition used is (A) a copper ion component, (B) an organic acid and / or an inorganic acid component, (C) a chlorine ion component, (D) an organic polymer component, (E A two-layer flexible copper-clad laminate comprising a brightener component and (F) a copolymer component of diallyldialkylammonium alkyl sulfate, (meth) acrylamides and sulfur dioxide as a leveling agent for plating. A manufacturing method can be provided.
(4) In addition, (D) the organic polymer component is at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, prolunic surfactant, tetronic surfactant, polyethylene glycol / glyceryl ether, polyethylene glycol / dialkyl ether The manufacturing method of the 2 layer flexible copper clad laminated base material which is can be provided.
(5) Moreover, the manufacturing method of the 2 layer flexible copper clad laminated base material whose (E) Brightener component is at least 1 sort (s) chosen from a sulfoalkyl sulfonate, an organic disulfide compound, and a dithiocarbamic acid derivative can be provided. .

  According to the present invention, a two-layer flexible copper-clad laminate is obtained by subjecting a seed layer of a resin film coated with a conductive metal to a secondary copper plating that is a thick plating without using a primary copper plating that is a strike copper plating. The base material utilizes the characteristics of the acidic copper plating bath composition used, and the thick copper plating layer has a smooth, glossy appearance, excellent peel resistance, and is easily formed into a fine pattern. A flexible copper clad laminate substrate could be provided.

  Further, according to the present invention, the characteristics such as the acidic copper plating bath composition used are utilized, and all processes such as seed layer formation and thick plating of the copper conductive layer are wet processes. A two-layer flexible copper-clad laminate (two-layer FCCL) that exhibits such a smooth, glossy appearance, excellent peel resistance, and whose copper-coated surface is easy to be fine-patterned, is a simple one-step process. It was possible to provide a method for manufacturing a two-layer FCCL that can be manufactured with a simple apparatus, low lining cost, and obviously high reliability and high productivity.

  Hereinafter, embodiments of the two-layer flexible copper-clad laminate and the method for producing the same according to the present invention will be described in more detail.

<Acid copper plating bath composition used in the present invention>
As already explained, the acidic copper plating bath composition used in the present invention comprises (A) a copper ion component, (B) an organic acid and / or an inorganic acid component, (C) a chlorine ion component, and (D) an organic polymer. And (E) a brightener component, and (F) a copolymer component of diallyldialkylammonium alkyl sulfate, a (meth) acrylamide and sulfur dioxide, which is a leveling agent for plating. .

  The (A) copper ion component is not particularly limited as long as it is generally a copper compound that dissolves in an acidic solution. In the present invention, for example, copper sulfate (pentahydrate is preferred), copper oxide, copper chloride, copper carbonate, copper pyrophosphate, copper methanesulfonate, copper propanesulfonate, etc., propanolsulfonic acid Examples thereof include copper alkanol sulfonates such as copper, copper acetates, copper citrates, and organic acid coppers such as copper tartrate and salts thereof. Any one of these copper compounds or a combination of any two or more can be used as appropriate.

  Moreover, the concentration of the copper ion of the (A) copper ion component is preferably 10 to 75 g / L, more preferably 15 to 65 g / L in the acidic copper plating bath composition. In particular, when the acidic copper plating bath composition is used for through-hole plating and resin film plating, it is 15 to 30 g / L as copper ions, and when used for blind via-hole plating, it is at a concentration of 25 to 65 g / L as copper ions. Preferably it is. Moreover, when using a copper sulfate pentahydrate as a copper ion source, the density | concentration in an acidic copper plating bath composition becomes like this. Preferably it is 40-300 g / L. Moreover, when using for a through hole and a metal sputter film, Preferably it is 60-120 g / L, When using for a blind via hole, Preferably it is 100-250 g / L.

  In addition, the organic acid and / or inorganic acid component (B) is not particularly limited as long as it can dissolve copper, and is suitably used as appropriate. In the present invention, preferred examples of the organic acid or inorganic acid include, for example, sulfuric acid as the inorganic acid, alkane sulfonic acids such as methane sulfonic acid and propane sulfonic acid, and alkanol sulfone such as propanol sulfonic acid as the organic acid. Examples thereof include organic acids such as acids, citric acid, tartaric acid, and formic acid. Any one of these organic acids and inorganic acids or a combination of any two or more can be suitably used.

  The concentration of the (B) organic acid and / or inorganic acid component in the acidic copper plating bath composition is preferably 30 to 300 g / L, more preferably 50 to 250 g / L. It is. In particular, when used for through-hole plating and resin film plating, it is preferably 150 to 250 g / L, and when used for blind via-hole plating, it is preferably 50 to 150 g / L. Moreover, when this acid component is a sulfuric acid, it is suitable that the density | concentration in an acidic copper plating bath composition becomes like this. Preferably it is 30-300 g / L. Further, it is preferably 150 to 250 g / L for through holes and metal sputtered films, and preferably 50 to 150 g / L for blind via holes.

  The acidic copper plating bath composition used in the present invention preferably contains (C) a chlorine ion component at a concentration of 20 to 100 mg / L as a chlorine ion, particularly 30 to 70 mg / L. It is suitable to contain.

  The organic polymer component (D) acts as a wetting agent that improves the wettability of the plating solution. In the present invention, for example, polyethylene glycol, polypropylene glycol, pluronic surfactant, tetronic type A surfactant, polyethylene glycol / glyceryl ether, polyethylene glycol / dialkyl ether, and the like can be suitably exemplified. Here, polyethylene glycol having a degree of oxyethylene polymerization in the range of 10 to 500 and polypropylene glycol having a degree of oxypropylene polymerization in the range of 1 to 20 are suitably used.

  In addition, examples of the pluronic surfactant include, for example, the general formula (I)

［式中、ａおよびｃは、それぞれ１〜３０の数、ｂは１〜１００の数を示す］
で表される化合物を、テトロニック型界面活性剤としては、例えば一般式（ＶＩＩ）

[Wherein, a and c each represent a number of 1 to 30, and b represents a number of 1 to 100]
As the tetronic surfactant, for example, a compound represented by the general formula (VII)

［式中、ｄは１〜２００の数、ｅは１〜４０の数を示す］
で表される化合物を挙げることができる。

[Wherein, d is a number from 1 to 200, and e is a number from 1 to 40]
The compound represented by these can be mentioned.

［式中、ｆ、ｇおよびｈは、それぞれ１〜２００の数を示す］
で表される化合物を挙げることができ、ポリエチレングリコール・ジアルキルエーテルとしては、例えば一般式（ＩＸ） Furthermore, as polyethylene glycol glyceryl ether, for example, general formula (VIII)

[Wherein f, g and h each represent a number of 1 to 200]
As the polyethylene glycol dialkyl ether, for example, the general formula (IX)

［式中、Ｒ^７およびＲ^８は、それぞれ独立に水素原子または炭素数１〜５のアルキル基、ｉは２〜２００の数を示す］
で表される化合物を挙げることができる。

[Wherein, R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and i represents a number of 2 to 200]
The compound represented by these can be mentioned.

  In the present invention, as the (D) organic polymer component, any one of these polymer components may be used alone or in combination of any two or more, and these (D) organic polymer components may be suitably used. The concentration of the polymer component in the acidic copper plating bath composition is preferably 100 to 20000 mg / L, and particularly preferably in the range of 1000 to 10000 mg / L.

  Moreover, this (E) Brightener component has the effect | action which makes the crystal arrangement of a plating layer uniform. In the present invention, for example, mercaptoalkyl sulfonates, organic disulfide compounds, dithiocarbamic acid derivatives and the like can be mentioned.

［式中、Ｌ^１は炭素数１〜１８の飽和または不飽和のアルキレン基、Ｍはアルカリ金属を示す］
で表される化合物を挙げることができる。 Here, as the mercaptoalkylsulfonate, for example, the general formula (X)

[Wherein L ¹ represents a saturated or unsaturated alkylene group having 1 to 18 carbon atoms, and M represents an alkali metal]
The compound represented by these can be mentioned.

[式中、Ｌ^２およびＬ^３は、それぞれ独立に炭素数１〜１８の飽和叉は不飽和のアルキレン基、Ｘ^１およびＸ^２は、それぞれ独立に硫酸塩基またはリン酸塩基を示す］
で表される化合物を挙げることができる。 Moreover, as an organic disulfide compound, for example, general formula (XI)

[Wherein, L ² and L ³ each independently represent a saturated or unsaturated alkylene group having 1 to 18 carbon atoms, and X ¹ and X ² each independently represent a sulfate group or a phosphate group]
The compound represented by these can be mentioned.

［式中、Ｒ^９およびＲ^１０は、それぞれ独立に水素原子叉は炭素数１〜３のアルキル基、Ｌ^４は炭素数３〜６のアルキレン基、Ｘ^３は硫酸塩基叉はリン酸塩基を示す］
で表される化合物を挙げることができる。 Examples of the dithiocarbamic acid derivative include, for example, the general formula (XII)

[Wherein R ⁹ and R ¹⁰ are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, L ⁴ is an alkylene group having 3 to 6 carbon atoms, X ³ is a sulfate group or a phosphate group. Show]
The compound represented by these can be mentioned.

  In the present invention, any one of these (E) Brightener components may be used singly or in combination of any two or more. The concentration of the (E) Brightener component is preferably 0.02 to 200 mg / L, more preferably 0.2 to 5.0 mg / L in the acidic copper plating bath composition. Is preferred.

［式中、Ｒ^１、Ｒ^２は、それぞれ独立にメチル基、エチル基叉はヒドロキシエチル基で、Ｒ^１、Ｒ^２が共にヒドロキシル基ではなく、Ｒ^３はメチル基またはエチル基である］
で表される構造単位を有するジアリルジアルキルアンモニウムアルキルサルフェイトと、一般式（ＸＩＶ） The leveling agent for plating (F) is represented by the general formula (XIII)

[Wherein, R ¹ and R ² are each independently a methyl group, an ethyl group or a hydroxyethyl group, R ¹ and R ² are not hydroxyl groups, and R ³ is a methyl group or an ethyl group]
Diallyldialkylammonium alkyl sulfate having a structural unit represented by the general formula (XIV)

［式中、Ｒ^４は水素原子またはメチル基であり、Ｒ^５、Ｒ^６は、それぞれ独立に、水素原子、もしくは水酸基を有してもよい炭素数１〜４のアルキル基、または一緒になって環内にエーテル結合を含んでもよい炭素数２〜７のアルキレン基である］
で表わされる構造単位を有する（メタ）アクリルアミド類と、
一般式（ＸＶ）

[Wherein, R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, or a combination thereof. And an alkylene group having 2 to 7 carbon atoms which may contain an ether bond in the ring.
(Meth) acrylamides having a structural unit represented by:
General formula (XV)

で表される構造単位を有する二酸化イオウとの共重合体である。

It is a copolymer with sulfur dioxide having a structural unit represented by

  As these copolymers, in the present invention, for example, as diallyldialkylammonium alkylsulfate, diallyldimethylammonium methylsulfate, diallylethylmethylammonium methylsulfate, diallyldiethylammonium methylsulfate, diallyl (hydroxyethyl) methyl Ammonium methyl sulfate, diallyl ethyl (hydroxyethyl) ammonium methyl sulfate, diallyl dimethyl ammonium ammonium sulfate, diallyl ethyl methyl ammonium ethyl sulfate, diallyl diethyl ammonium ammonium sulfate, diallyl (hydroxyethyl) methyl ammonium ethyl sulfate, diallyl Ethyl (hydroxyethyl) ammonium ethyl sulfate It can be cited as appropriate suitably. In this case, hydroxyethyl is preferably 2-hydroxyethyl.

In the present invention,
(1) In these copolymers, (meth) acrylamides subjected to the reaction are acrylamides when R ⁴ is a hydrogen atom, while methacrylamides are used when R ⁴ is a methyl group. Become.
(2) R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, or together may contain an ether bond. It is an alkylene group of formula 2-7.
(3) When R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, R ⁵ and R ⁶ are each independently a hydrogen atom, The alkyl group having 1 to 2 carbon atoms and the 2-hydroxyalkyl group having 2 to 3 carbon atoms are preferable.

  Therefore, examples of (meth) acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxypropyl) acrylamide, and N, N-dimethylacrylamide. N-methyl-N-ethylacrylamide, N, N-diethylacrylamide, N-methyl-N- (2-hydroxyethyl) acrylamide, N-methyl-N- (2-hydroxypropyl) acrylamide, N-ethyl-N -(2-hydroxyethyl) acrylamide, N-ethyl-N- (2-hydroxypropyl) acrylamide, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N- (2-hydroxyethyl) methacrylamide, N -(2-hydroxypropyl) Methacrylamide, N, N-dimethylmethacrylamide, N-methyl-N-ethylmethacrylamide, N, N-diethylmethacrylamide, N-methyl-N- (2-hydroxypropyl) methacrylamide, N-ethyl-N- (2-hydroxypropyl) methacrylamide and the like can be mentioned.

When R ⁵ and R ⁶ are combined to form an alkylene group having 2 to 7 carbon atoms which may contain an ether bond, the amino group part of (meth) acrylamide may be a morpholino group, piperidino group or pyrrolidino group. preferable.

  In this case, examples of (meth) acrylamides include acroylmorpholine, acroylpiperidine, acroylpyrrolidine, methacryloylmorpholine, methacryloylpiperidine, and methacryloylpyrrolidine.

  Further, these copolymers in the present invention are, for example, diallylethylmethylammonium methylsulfate copolymer, a copolymer of diallylethylmethylammonium methylsulfate, acrylamide and sulfur dioxide, diallylethylmethylammonium. Copolymer of methylsulfate, N-methylacrylamide and sulfur dioxide, diallylethylmethylammonium methylsulfate, copolymer of N-ethylacrylamide and sulfur dioxide, diallylethylmethylammonium methylsulfate and N, N- Copolymer of dimethylacrylamide and sulfur dioxide, copolymer of diallylethylmethylammonium methylsulfate, N-methyl-N-ethylacrylamide and sulfur dioxide, diallylethylmethylan Copolymer of nium methylsulfate, N, N-diethylacrylamide and sulfur dioxide, copolymer of diallylethylmethylammonium methylsulfate, N- (2-hydroxyethyl) acrylamide and sulfur dioxide, diallylethylmethylammonium A copolymer of methylsulfate, N- (2-hydroxypropyl) acrylamide and sulfur dioxide, a copolymer of diallylethylmethylammonium methylsulfate, N-methyl- (2-hydroxyethyl) acrylamide and sulfur dioxide, A copolymer of diallylethylmethylammonium methylsulfate, N-methyl- (2-hydroxypropyl) acrylamide and sulfur dioxide, diallylethylmethylammonium methylsulfate and N-ethyl- (2-hydride) Copolymers of xyethyl) acrylamide and sulfur dioxide, copolymers of diallylethylmethylammonium methylsulfate and N-ethyl- (2-hydroxypropyl) acrylamide and sulfur dioxide, diallylethylmethylammonium methylsulfate and acroyl Copolymer of morpholine and sulfur dioxide, copolymer of diallylethylmethylammonium methylsulfate and acroylpiperidine and sulfur dioxide, copolymer of diallylethylmethylammonium methylsulfate, acroylpyrrolidine and sulfur dioxide A copolymer of diallylethylmethylammonium methylsulfate, methacrylamide and sulfur dioxide, diallylethylmethylammonium methylsulfate and N-methylmethacrylamide Copolymers with sulfur oxide, copolymers of diallylethylmethylammonium methylsulfate, N-ethylmethacrylamide and sulfur dioxide, diallylethylmethylammonium methylsulfate, N, N-dimethylmethacrylamide and sulfur dioxide Copolymer, copolymer of diallylethylmethylammonium methylsulfate, N-methyl-N-ethylmethacrylamide and sulfur dioxide, copolymer of diallylethylmethylammonium methylsulfate, N, N-diethylmethacrylamide and sulfur dioxide Polymer, copolymer of diallylethylmethylammonium methylsulfate, N- (2-hydroxyethyl) methacrylamide and sulfur dioxide, diallylethylmethylammonium methylsulfate and N- (2-hydroxyl) Propyl) copolymer of methacrylamide and sulfur dioxide, diallylethylmethylammonium methylsulfate and N-methyl- (2-hydroxyethyl) methacrylamide and sulfur dioxide, diallylethylmethylammonium methylsulfate A copolymer of N-methyl- (2-hydroxypropyl) methacrylamide and sulfur dioxide, a copolymer of diallylethylmethylammonium methylsulfate, N-ethyl- (2-hydroxyethyl) methacrylamide and sulfur dioxide, A copolymer of diallylethylmethylammonium methylsulfate, N-ethyl- (2-hydroxypropyl) methacrylamide and sulfur dioxide, diallylethylmethylammonium methylsulfate, methacryloylmorpholine, Copolymers with sulfur fluoride, copolymers of diallylethylmethylammonium methylsulfate, methacroylpiperidine and sulfur dioxide, copolymers of diallylethylmethylammonium methylsulfate, methacroylpyrrolidine and sulfur dioxide, etc. be able to.

  In addition, in the dialylethylmethylammonium methylsulfate copolymer exemplified above, diallyldimethylammonium methylsulfate, diallyldiethylammonium methylsulfate, diallyl instead of the monomer diallylethylmethylammonium methylsulfate (Hydroxyethyl) methylammonium methylsulfate, diallylethyl (hydroxyethyl) ammonium methylsulfate, diallyldimethylammonium ethylsulfate, diallylethylmethylammonium ethylsulfate, diallyldiethylammonium ethylsulfate, diallyl (hydroxyethyl) methylammonium Ethyl sulfate, diallyl ethyl (hydroxyethyl) ammonium ethyl sal Well as the copolymer was Eito, together, it may be mentioned.

  In these copolymers, the monomer molar ratio of diallyldialkylammonium alkylsulfate / (meth) acrylamides / sulfur dioxide is usually 1 / (0.001 to 100 from the viewpoint of the stability of the resulting copolymer. ) / (0.001-1), preferably 1 / (0.005-10) / (0.005-1), more preferably 1 / (0.01-10) / (0.01- 1), particularly preferably 1 / (0.05-5) / (0.05-1), most preferably 1 / (0.08-3) / (0.05-1).

  The molecular weight of the copolymer of the present invention is a weight average molecular weight in terms of polyethylene glycol as measured by gel permeation chromatography (GPC), and is usually 300 to 50,000, preferably 500 to 25,000, more preferably 800 to 10. , 000.

  Although there is no restriction | limiting in particular in the manufacturing method of these copolymers, For example, a desired copolymer can be manufactured efficiently by the method shown below.

［式中、Ｒ^１、Ｒ^２、Ｒ^３は、それぞれ前記と同じである。］
で表されるジアリルジアルキルアンモニウムアルキルサルフェイトと、一般式（ＸＶＩＩ
） That is, in the polar solvent, the general formula (XVI)

[Wherein, R ¹ , R ² and R ³ are the same as defined above. ]
A diallyldialkylammonium alkyl sulfate represented by the general formula (XVII)
)

［式中、Ｒ^４、Ｒ^５、Ｒ^６は、それぞれ前記と同じである。］
で表される（メタ）アクリルアミド類と、二酸化イオウとを共重合させることにより、本発明で用いる共重合体が得られる。

[Wherein, R ⁴ , R ⁵ and R ⁶ are the same as defined above. ]
The copolymer used by this invention is obtained by copolymerizing (meth) acrylamides represented by these and sulfur dioxide.

  Thus, examples of diallyldialkylammonium alkylsulfate monomers used in the present invention include diallyldimethylammonium methylsulfate, diallylethylmethylammonium methylsulfate, diallyldiethylammonium methylsulfate, diallyl (hydroxyethyl) methylammonium methylsulfate. Diallylethyl (hydroxyethyl) ammonium methyl sulfate, diallyldimethylammonium ethyl sulfate, diallylethylmethylammonium ethyl sulfate, diallyl diethylammonium ethyl sulfate, diallyl (hydroxyethyl) methylammonium ethyl sulfate, diallylethyl (hydroxyethyl) ) Ammonium ethyl sulfate etc. Among them, suitably used suitably. The hydroxyethyl group of these monomers is preferably 2-hydroxyethyl.

  Moreover, the monomer of the diallyldialkylammonium alkyl sulfate used here can be suitably manufactured, for example, by alkylation reaction of diallylalkylamine and dialkylsulfuric acid.

That is,
(1) Diallyldimethylammonium methylsulfate, diallylethylmethylammonium methylsulfate, diallyl (hydroxyethyl) methylammonium methylsulfate are prepared by adding dimethyl sulfate to diallylmethylamine, diallylethylamine, diallyl (hydroxyethyl) amine, respectively. It can be produced by a methylation reaction.
(2) In addition, diallyl diethylammonium ethyl sulfate, diallylethylmethylammonium ethyl sulfate, diallylethyl (hydroxyethyl) ammonium ethyl sulfate, respectively, diallylethylamine, diallylmethylamine, diallyl (hydroxyethyl) amine, diethyl It can be produced by an ethylation reaction in which sulfuric acid is added and reacted.

Further, in relation to (meth) acrylamides used as monomers, in the above general formula (XVII), when R ⁴ is a hydrogen atom, it becomes an acrylamide, whereas when R ⁴ is a methyl group, it becomes a methacrylamide. . R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, or a carbon number which may contain an ether bond together. 2 to 7 alkylene groups. When R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms that may have a hydroxyl group, preferably R ⁵ and R ⁶ are each independently a hydrogen atom, The alkyl group having 1 to 2 carbon atoms and the 2-hydroxyalkyl group having 2 to 3 carbon atoms are preferable.

  In this case, (meth) acrylamides include acrylamide, N-methylacrylamide, N-ethylacrylamide, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxypropyl) acrylamide, N, N-dimethylacrylamide, N-methyl-N-ethylacrylamide, N, N-diethylacrylamide, N-methyl-N- (2-hydroxyethyl) acrylamide, N-methyl-N- (2-hydroxypropyl) acrylamide, N-ethyl-N- (2-hydroxyethyl) acrylamide, N-ethyl-N- (2-hydroxypropyl) acrylamide, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N- (2-hydroxyethyl) methacrylamide, N- (2-hydroxypropyl) metac Rilamide, N, N-dimethylmethacrylamide, N-methyl-N-ethylmethacrylamide, N, N-diethylmethacrylamide, N-methyl-N- (2-hydroxyethyl) methacrylamide, N-methyl-N- ( 2-hydroxypropyl) methacrylamide, N-ethyl-N- (2-hydroxyethyl) methacrylamide, N-ethyl-N- (2-hydroxypropyl) methacrylamide and the like.

In the case where R ⁵ and R ⁶ are combined to form an alkylene group having 2 to 7 carbon atoms which may contain an ether bond, the amino group portion of (meth) acrylamide is preferably a morpholino group, piperidino group or pyrrolidino group. Is preferred. In this case, examples of (meth) acrylamide include acroylmorpholine, acroylpiperidine, acroylpyrrolidine, methacryloylmorpholine, methacryloylpiperidine, and methacryloylpyrrolidine.

  Therefore, when producing these copolymers, polar solvents used are diallyldialkylammonium alkyl sulfates, (meth) acrylamides, and solvents that dissolve sulfur dioxide. For example, water, methyl Alcohol, ethyl alcohol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide and the like can be mentioned. In the present invention, any one of these solvents or a mixture of two or more of them can be suitably used.

  In addition, as a polymerization catalyst used for the radical copolymerization reaction for producing these copolymers, any polymer capable of polymerizing diallyldialkylammonium alkyl sulfate, (meth) acrylamides and sulfur dioxide can be used. Although there is no particular limitation, organic peroxides such as tert-butyl hydroperoxide and cumene hydroperoxide, aliphatic azo compounds such as 2,2′-azobisisobutyronitrile, ammonium persulfate, persulfate Inorganic peroxides such as potassium, and nitrates such as ammonium nitrate and potassium nitrate. Moreover, the gas containing oxygen, such as air, a radiation, an ultraviolet-ray, and visible light are also mentioned.

  In order to produce these copolymers, the charged monomer molar ratio of diallyldialkylammonium alkylsulfate / (meth) acrylamides / sulfur dioxide is usually 1 / (from the viewpoint of the stability of the resulting copolymer. 0.001-100) / (0.001-1), preferably 1 / (0.005-10) / (0.005-1), and more preferably 1 / (0.01-10). /(0.01-1), particularly preferably 1 / (0.05-5) / (0.05-1), most preferably 1 / (0.08-3) / (0.05- 1).

  In order to produce these copolymers, the polymerization catalyst is usually added to a polar solvent solution containing the diallyldialkylammonium alkyl sulfate, (meth) acrylamides, and sulfur dioxide, and the reaction mixture is heated at room temperature or under heating conditions. The copolymerization is carried out by appropriately adding a stirring operation. The polymerization temperature is preferably -100 ° C to 80 ° C. The polymerization time is preferably 1 to 100 hours. Moreover, after completion | finish of reaction, this copolymer can also be reprecipitated and collect | recovered by adding the solvent which does not dissolve copolymers, such as alcohol and acetone.

  From the above, the copolymer of “diallyldialkylammonium alkyl sulfate”-“(meth) acrylamides”-“sulfur dioxide” obtained in this way is used as a leveling agent for plating to provide a convex surface on the surface of the object to be plated. It is excellent in the action of adsorbing to the part and suppressing the plating deposition of the convex part. In addition, this copolymer is a component of the acidic copper plating bath composition used in the present invention. Any of the plating appearances such as the inside of blind via holes and through-holes, the cornering with plating and the leveling property of the plating surface can be used. In addition, it exhibits characteristics such as being able to cope with substrate defects. In addition, by using such an acidic copper plating bath composition, copper plating can be applied with high reliability to substrates having minute holes such as through-holes and blind via holes, or resin films whose surfaces are coated with a metal such as copper. Processing can be performed.

  In the present invention, the concentration of the leveling agent component for plating (F) constituting the acidic copper plating bath composition is preferably 10 to 1200 mg / L, particularly preferably 50, in the acidic copper plating bath composition. It is suitably used suitably within a concentration range of ˜500 mg / L.

<Polyimide resin film substrate used in the present invention>
As already explained in detail, the technology area is increasingly thinner, more dense, smaller and lighter in relation to electronic devices such as mobile phones, personal computers, TVs, videos, music players, digital cameras, and game consoles. In fact, various parts used in these electronic devices are also tending to have higher density and smaller size. In addition, polyimide resin films, for example, printed wiring boards (PWB), flexible printed wiring boards (FPC), automatic tape bonding (TAB) tapes, and chip-on-film (COF) tapes are involved in the substrate materials on which they are mounted. It is widely used as an insulating substrate material for electronic parts.

  Therefore, the polyimide resin film used in the present invention is usually an aromatic polyimide in which aromatic compounds are directly linked by an imide bond, and has a conjugated structure of aromatics via the imide bond. Due to the strong imide bond, it has the highest thermal, mechanical and chemical properties in the polymer, and in the present invention, as seen in the examples described later, trade names manufactured by Toray DuPont: A polyimide resin film of Kapton 100-EN was used.

<Two-layer flexible copper-clad laminate and manufacturing method thereof according to the present invention>
Therefore, in the present invention, using a polyimide resin film material, a two-layer flexible copper-clad laminate substrate (two-layer FCCL) is used in advance using the acidic copper plating bath composition described above, and Ni or an alloy thereof in advance. Unlike the conventional copper plating method, the entire process of thick plating the copper conductive layer on the seed layer, including the formation of a conductive metal seed layer, is different from the conventional copper plating method. A method for producing a two-layer flexible copper-clad laminate (two-layer FCCL) characterized in that the all-coppering step is one step will be described below.

According to the present invention,
(1): A pretreatment step is performed in which a polyimide resin film surface that is flexible, heat resistant, and excellent in chemical resistance is subjected to surface modification to make it hydrophilic. The surface modification method is different from the conventional atmospheric pressure plasma treatment, corona treatment, and ion irradiation treatment under vacuum, and a polyamic acid modified layer is formed on the surface by an alkali wet modification method. Next, after a Pd ion is adsorbed on the surface with a palladium (Pd) -based catalyst, a reduction treatment is performed to obtain a hydrophilic surface modified layer obtained by [adsorbed Pd ion] → [reduction metallization].

  That is, a series of mutation behaviors by this alkaline wet reforming method is usually that when a polyimide resin is treated with an alkaline aqueous solution, a part of its surface is hydrolyzed and a part of the imide ring is cleaved, resulting in an amide group and a carboxyl group. Generate a group. Since the generated carboxyl group is easy to exchange cation ions, metal ions can be adsorbed.

(2): Conductive metal plating such as Ni or an alloy thereof is applied in advance to the resin film surface thus modified with hydrophilicity by an electroless plating method to form a conductive metal seed layer. . As the Ni alloy, Ni-P, it includes Ni- B of any alloy. Usually, a seed layer having a thickness of 40 to 3000 mm is formed by sputtering using Ni—Cr or the like, but in the present invention, by an FCCL electroless plating method manufactured by Ebara Eugelite, A seed layer of electroless Ni or alloy plating thereof having a layer thickness of 10 to 300 nm was formed.

(3): Next, in the acidic copper plating bath composition according to the present invention, wet electroplating is performed without using the primary copper plating as strike copper plating, and the resin film seed layer is freely formed in one step. The copper conductive layer was thickly plated while controlling the layer thickness to produce a two-layer flexible copper-clad laminate having a copper coating thickness in the range of 0.05 to 50 μm according to the present invention.

  Moreover, in the method of performing a copper plating process on a resin film material having a metal film formed on the surface, for example, on the surface of a resin film such as polyimide or polyester having a thickness of about 12 to 50 μm, conventionally, by vacuum deposition, sputtering, or the like. In contrast to the seed layer formed by dry-coating a metal such as copper, nickel and chromium having a thickness of about 4 to 3000 nm, a “nickel-chromium” alloy, etc., in the present invention, the FCCL as described above is used. What is necessary is just to form the electroconductive nickel seed layer of about 10-300 nm by the wet electroless nickel plating process by the electroless nickel plating method.

Thus, the conditions which perform copper plating with the acidic copper plating bath composition in this invention on the resin film in which the metal film was formed in the surface may be the conditions of normal copper sulfate plating. That is, plating may be performed for about 0.1 to 250 minutes at a liquid temperature of about 23 to 27 ° C. and an average cathode current density of about 1 to 3 A / dm ² . The plating thickness at this time is about 0.05 to 50 μm. In general, it is preferable to perform copper plating under liquid agitation such as aeration.

  Also, in the conventional metallization method, especially when a resin film coated with a very thin metal is plated in a conventional acidic copper plating bath in a process such as vacuum deposition or sputtering, the plating thickness is less than 10 μm. The leveling effect of the additive was not exhibited, and there was a problem that a glossy appearance was not obtained with a rough surface state with many irregularities on the surface, but in the `` acidic copper plating bath composition '' used in the present invention, Even with such a thin plating thickness (about 3 to 5 μm thickness), the surface is in a very fine crystal state, and a highly reliable and smooth bright copper plating surface can be obtained. Needless to say, even if the plating thickness is thicker than this, a good gloss appearance can be obtained.

  From the above, the method for producing a two-layer flexible copper-clad laminate (two-layer FCCL) according to the present invention is a conventional method that is low in productivity because the apparatus is expensive, the running cost is high, and a vacuum process is required. Compared with the two-layer FCCL manufacturing method by metallization method (sputtering / plating method) in particular, all processes including the formation of seed layer by electroless Ni plating that is obviously cheap and in-line can be performed by a wet method (all wet method). Process), and the obtained two-layer flexible copper-clad laminate can be said to be a method for producing a two-layer FCCL characterized by being able to cope with fine patterning as appropriate.

  Moreover, as already explained, (A) copper ion component, (B) organic acid and / or inorganic acid component, (C) chlorine ion component, (D) organic polymer component, (E) used in the present invention. An acidic copper plating bath composition comprising a brightener component and (F) a copolymer component of diallyldialkylammonium alkyl sulfate as a leveling agent for plating, (meth) acrylamides, and sulfur dioxide is the present invention. It is also a feature of the present invention that it can be suitably and suitably provided as a plating treatment agent for the production of a two-layer flexible copper-clad laminate base material.

  Furthermore, by using such an acidic copper plating bath composition as a plating treatment agent for producing a two-layer flexible copper-clad laminate according to the present invention, a resin film in which a seed layer of a conductive metal film is formed in advance. An example described later is a two-layer flexible copper-clad laminate base material (two-layer FCCL) produced by thick copper plating on the surface without using primary copper plating, and exhibits a smooth gloss appearance. As is clear from the above, it is a feature of the present invention that the peel resistance of the obtained copper plating layer is remarkably improved.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

Example 1
(1) [Diallylethylmethylammonium ethyl sulfate], [acrylamide], and [sulfur dioxide], which are leveling agents for plating (F), which are components of “acidic copper plating bath composition-1” used in the present invention. The terpolymer component was prepared as follows.

  Into a 1 liter four-necked round bottom separable flask equipped with a stirrer, a thermometer, and a Dimroth type reflux condenser, 167.1 g (1.5 mol) of diallylmethylamine was charged and 232.5 g of diethyl sulfate ( 1.5 mol) was slowly added dropwise while maintaining the temperature at 20 to 50 ° C., and the mixture was reacted at 50 ° C. for 24 hours. Then, 212.9 g of water was added, and a “diallylethylmethylammonium ethyl sulfate monomer aqueous solution having a concentration of 65% by mass was added. Was prepared.

  Next, water for adjusting the monomer concentration to 60% by mass was added to the 65% by mass diallylethylmethylammonium ethyl sulfate monomer (abbreviated as DAEMAES monomer) aqueous solution (monomer content 1.5 mol). While cooling and stirring with ice water, sulfur dioxide was dissolved in an amount equivalent to DAEMAES monomer by adding 13.3 g (0.19 mol) of acrylamide. Then, while maintaining the obtained mixture of DAEMAES monomer, acrylamide and sulfur dioxide at 60 ° C., 71.3 g of ammonium persulfate (APS) aqueous solution having a concentration of 28.5% by mass (4.0% by mass based on the total monomers) ) Was added in portions and copolymerized for 48 hours to give a molar ratio of [diallylethylmethylammonium ethyl sulfate]: [acrylamide]: [sulfur dioxide] = 8: 1: 8. An aqueous leveling agent solution for plating (F) which is “ternary copolymer-1” of methylammonium ethyl sulfate, acrylamide and sulfur dioxide was obtained.

Subsequently, a part of the obtained solution was reprecipitated with acetone, and the obtained white solid was filtered off and dried in vacuum at 50 ° C. for 48 hours. From the IR spectrum of the obtained white powdery terpolymer, -SO ₂ to 1320 cm ^-1 and 1130 cm ^-1 - absorption due to amide absorption and 1680 cm ^-1 attributable to sulfate in 1220 cm ^-1 Thus, it is supported that it is a terpolymer of diallylethylmethylammonium ethyl sulfate, acrylamide and sulfur dioxide (molar ratio 8: 1: 8).

  Moreover, the weight average molecular weight (Mw) of this ternary copolymer was 1500 as measured by the following method, and the polymerization yield was 95.0% by the following method. This ternary copolymer was subjected to a leveling agent in the acidic copper plating bath composition in the following examples.

(2) Composition of acidic copper plating bath composition <Acid copper plating bath composition-1>
(A) Copper ion component; copper sulfate pentahydrate 120 g / L
(B) Inorganic acid component; sulfuric acid 150 g / L
(C) Chlorine ion component; Chlorine 50mg / L
(D) Organic polymer component; polyethylene glycol ^{* 1} 2000 mg / L
(E) Brightener component; SPS ^{* 2} 1 mg / L
(F) Leveling agent component for plating; Ternary copolymer-1 500 mg / L
[Note] * 1: HO— (C ₂ H ₄ O) _n —H n = 90
* 2: NaO ₃ S—C ₃ H ₆ —S—S—C ₃ H ₆ —SO ₃ Na

(3) Next, a resin of polyimide film (trade name: Kapton 100-EN manufactured by Toray DuPont) coated with electroless nickel plating as a seed layer by the FCCL electroless nickel plating method manufactured by Ebara Eugene Co., Ltd. The film material was subjected to thick plating with a copper plating coating thickness of 10 μm using this “acidic copper plating bath composition-1” without using primary copper plating.

The wet electroplating was carried out under the conditions of 25 ° C. and an average cathode current density of 2 A / dm ² for 25 minutes under acidic aeration. Subsequently, when the obtained two-layer flexible copper-clad laminated polyimide film substrate was visually observed, the film surface was extremely smooth and exhibited a remarkable gloss appearance. In addition, the and "long-term heat resistance test (90 ° peel strength)""peeling resistance between the Ni-Cu" measured and evaluated, and the results are shown in Table 1.

  Various physical property evaluation methods and strength measurement methods measured and evaluated in connection with the present invention are described below.

<Peeling resistance between Ni-Cu>
When the resin film side of a test piece having a length of 10 cm and a width of 1 cm is fired for several seconds with fire, peeling occurs between the resin film and the coated metal. When the resin film and the coated metal are peeled off by hand, usually no metal is left on the film, but if there is peeling between the two, the seed layer Ni remains on the film, so this state change Visually judge.

<Long-term heat resistance test (90 ° peel strength)>
<JIS C 6471>
A test piece that was cut in a 10 mm width into a two-layer FCCL resin film material and exposed to a long-term heat test (150 ° C. × 168 Hr) was made to conform to “JIS C 6471”, and 90 ° peel strength N / m taking measurement. In addition, Kapton 100-EN manufactured by Toray DuPont Co., Ltd. was used as a resin film material as a test piece.

The device is a memory within the effective lightweight range, the error is ± 1% of the indicated value, the load when peeling off is 15 to 85% of the capacity of the testing machine, and the crosshead speed is about 50 mm per minute. A tensile tester that can be maintained and a recorder that can continuously record the peeling force. Moreover, it consists of an indicator having a function for maintaining the angle of the peeling direction of the copper foil with respect to the copper foil removal surface of the sample at 90 ± 5 °. After measuring the conductor width of the sample, it is fixed to a tensile tester and an indicator that can be slid in synchronization with the peeling speed in the direction perpendicular to the pulling direction is used. In addition, the "normal state (normal state) " shown in Table 1 shows the measured value in the air of 20-30 degreeC normal temperature and a normal pressure.

<Weight average molecular weight of copolymer (Mw)>
The weight average molecular weight (Mw) of the copolymer was measured by gel permeation chromatography (GPC method) using Hitachi L-6000 type high performance liquid chromatograph.
The eluent flow path pump is Hitachi L-6000, the detector is a Shodex RI-101 differential refractive index detector, and the column is a water gel filtration type GS-220HQ (exclusion limit molecular weight 3,000) and GS of Shodex Asahi Pack. -620HQ (exclusion limit molecular weight 2 million) connected in series was used. Samples were prepared with an eluent to a concentration of 0.5 g / 100 ml, and 20 μl was used. As an eluent, a 0.4 mol / liter sodium chloride aqueous solution was used.

  The column temperature was 30 ° C. and the flow rate was 1.0 ml / min. A calibration curve is obtained using polyethylene glycol having a molecular weight of 106, 194, 440, 600, 1470, 4100, 7100, 10300, 12600, 23000 or the like as a standard substance, and the weight average molecular weight of the copolymer ( Mw) was determined.

<Polymerization yield of copolymer>
It calculated | required from the peak area ratio obtained by GPC method.

Comparative Example 1
Instead of “acidic copper plating bath composition-1” in Example 1, plating was performed in the same manner as in Example 1 except that “copper sulfate plating bath composition H-1” shown below was used. Each appearance and “Ni-Cu peel resistance” were evaluated for the plated substrate, and the results are shown in Table 1.

<Acid copper plating bath composition H-1>
(A) Copper sulfate pentahydrate 120 g / L
(B) Sulfuric acid 150g / L
(C) Chloride ion 50mg / L
CU-BRITE TH-R-A ^{* 3} 40ml / L
CU-BRITE TH-R-B ^{* 4} 2.5ml / L
[Note] * 3: Made by Ebara Eugene Co., Ltd., hydrocarbon organic compounds and nitrogen organic compounds
Additives based on products.
* 4: Same as * 3, manufactured by Ebara Eugene Co., Ltd., mainly based on sulfur-based organic compounds
Additive.

Comparative Example 2
Instead of “acidic copper plating bath composition-1” in Example 1, plating was performed in the same manner as in Example 1 except that “copper sulfate plating bath composition H-2” shown below was used. Each appearance and “Ni-Cu peel resistance” were evaluated for the plated substrate, and the results are shown in Table 1.

<Acid copper plating bath composition H-2>
(A) Copper sulfate pentahydrate 120 g / L
(B) Sulfuric acid 150g / L
(C) Chloride ion 50mg / L
CU-BRITE TH ^{* 5} 5ml / L
[Note] * 5: Same hydrocarbon-based organic compound, nitrogen-based organic compound, and sulfur-based organic compound as * 3
Main additive

Comparative Example 3
Instead of “acidic copper plating bath composition-1” in Example 1, plating was performed in the same manner as in Example 1 except that “copper sulfate plating bath composition H-3” shown below was used. Each appearance and “Ni-Cu peel resistance” were evaluated for the plated substrate, and the results are shown in Table 1.

<Acid copper plating bath composition H-3>
(A) Copper sulfate pentahydrate 120 g / L
(B) Sulfuric acid 150g / L
(C) Chloride ion 50mg / L
(D) Polyethylene glycol ^{* 1} 500 mg / L
(E) SPS ^{* 2} 1 mg / L
(F) Leveling agent component; binary copolymer-2 ^{* 6} 1000 mg / L
[Note] * 1: HO— (C ₂ H ₄ O) _n —H n = 90
* 2: NaO ₃ S—C ₃ H ₆ —S—S—C ₃ H ₆ —SO ₃ Na
* 6: tetraethylammonium diallyl ethyl methyl Sulfate and the sulfur dioxide
Alternating copolymer with a molar ratio of 1/1

Example 2
Example 2 is the production of a test piece for evaluating the elongation ratio (JIS Z2241).
Using “acidic copper plating bath composition-2” having a component composition almost the same as “acidic copper plating bath composition-1” used in Example 1, a plating process similar to that of Example 1 on a SUS plate. Thus, the elongation (JIS Z2241) when the copper plating treatment was performed was measured and evaluated, and the results are shown in Table 2.

Current condition: 60 μm film formation at ^{2 A} / dm ² , temperature: 25 ° C.
<Acid copper plating bath composition-2>
(A) Copper ion component; copper sulfate pentahydrate 120 g / L
(B) Inorganic acid component; sulfuric acid 150 g / L
(C) Chlorine ion component; Chlorine 50mg / L
(D) Organic polymer component; polyethylene glycol ^{* 1} 2000 mg / L
(E) Brightener component; SPS ^{* 2} 2 mg / L
(F) Leveling agent component for plating; Ternary copolymer-1 ^{* 7} 100 mg / L
[Note] * 1: HO— (C ₂ H ₄ O) _n —H n = 90
* 2: NaO ₃ S—C ₃ H ₆ —S—S—C ₃ H ₆ —SO ₃ Na
* 7: With diallylethylmethylammonium ethyl sulfate and acrylamide
Copolymer with 8/1/8 molar ratio to sulfur dioxide

Comparative Example 4
In place of “acidic copper plating bath composition-2” in example 2, “acidic copper plating bath composition H-4” shown below was used in the same manner as in example 2 except that “acidic copper plating bath composition-2” was used. The elongation ratio (JIS Z2241) of the bath composition H-4 was measured and evaluated. The results are shown in Table 2.

<Acid copper plating bath composition H-4>
(A) Copper sulfate pentahydrate 120 g / L
(B) Sulfuric acid 150g / L
(C) Chloride ion 50mg / L
(D) Polyethylene glycol ^{* 1} 1000 mg / L
[Note] * 1: HO— (C ₂ H ₄ O) _n —H n = 90
From the above, as is clear from Table 1 and Table 2, the two-layer flexible copper-clad laminate obtained by the manufacturing method in which all the steps according to the present invention are wet processes is clearly shown in the wet process. The characteristics of the “acidic copper plating bath composition” used are utilized, and the “plated copper layer” that cannot be obtained by the conventional method is glossy in appearance and the copper layer is remarkably excellent in peeling resistance. Understood.

  In particular, in connection with the “long-term heat resistance test (90 ° peel strength)”, the two-layer flexible copper-clad base material according to the present invention is equal to or more than 400 N / m equivalent to the two-layer substrate material by the sputter plating method or metallization method It can be said that it is a two-layer flexible copper-clad laminate base material that is extremely effective.

  From the above, according to the present invention, a newly developed acidic copper plating bath composition is used for a metal-coated resin film in which conductive Ni or an alloy seed layer thereof is formed by an FCCL electroless plating method. Two-layer flexible copper-clad laminate (two-layer FCCL) formed by thick copper plating without using secondary copper plating is a copper metal-coated resin film with a smooth glossy appearance and excellent peel resistance A substrate is provided.

  Further, according to the present invention, the formation of the seed layer takes advantage of the electroless plating method and the characteristics of the acidic copper plating bath composition to be used, and the primary copper plating is performed on the conductive Ni or alloy seed layer thereof. Since the wet thick copper plating layer is formed by wet copper plating in a single step without using a metal, a two-layer flexible copper-clad laminate (two-layer FCCL) that is extremely easy to form a fine pattern is provided.

  In addition, according to the present invention, a two-layer flexible copper-clad laminate (two-layer FCCL) that exhibits such a smooth, glossy appearance, excellent peel resistance, and whose copper-coated surface is easily fine-patterned, Utilizing the characteristics of the acidic copper plating bath composition used, etc., all processes such as seed layer formation and thick plating of the copper conductive layer are wet processes, and the all copper plating process is a one-step process. Thus, a method of manufacturing a two-layer FCCL that can be manufactured with a simple apparatus, low running cost, clearly high reliability, and high productivity is provided.

Claims (4)

On a nickel seed layer made of Ni or an alloy thereof (excluding Ni-Cu) having a coating thickness in the range of 10 to 300 nm, formed in advance by an electroless plating method on a polyimide film substrate having a hydrophilic surface modified. Using the acidic copper plating bath composition, the copper plating is thickly plated with a coating thickness in the range of 0.05 to 50 μm without using the primary copper plating that is strike copper plating ,
The acidic copper plating bath composition comprises (A) a copper ion component, (B) an organic acid and / or an inorganic acid component, (C) a chlorine ion component, (D) an organic polymer component, (E) a brightener component, and (F) A two-layer flexible copper-clad laminate comprising a copolymer component of diallyldialkylammonium alkyl sulfate as a leveling agent for plating, (meth) acrylamides and sulfur dioxide . Two-layer flexible copper-clad laminate (two-layer FCCL) for wet thick plating using an acidic copper plating bath composition and a polyimide film coated with Ni or an alloy thereof (excluding Ni-Cu) as a seed layer A manufacturing method of
Forming a nickel seed layer made of Ni or an alloy thereof (excluding Ni-Cu) in a coating thickness range of 10 to 300 nm by an electroless plating method on a polyimide film surface subjected to a hydrophilic surface modification;
In the acidic copper plating bath composition, wet electroplating treatment is performed without using a primary copper plating which is a strike copper plating, and a copper conductive layer is thickened in a range of 0.05 to 50 μm on the seed layer. Plating, and
Including
The acidic copper plating bath composition comprises (A) a copper ion component, (B) an organic acid and / or an inorganic acid component, (C) a chlorine ion component, (D) an organic polymer component, (E) a brightener component, and (F) Production of a two-layer flexible copper-clad laminate comprising a copolymer component of diallyldialkylammonium alkyl sulfate as a leveling agent for plating, (meth) acrylamides and sulfur dioxide Method. The organic polymer component (D) is at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, prolunic surfactant, tetronic surfactant, polyethylene glycol / glyceryl ether, polyethylene glycol / dialkyl ether. 2. A method for producing a two-layer flexible copper-clad laminate according to 2. The method for producing a two-layer flexible copper-clad laminate according to claim 3 , wherein the (E) Brightener component is at least one selected from sulfoalkyl sulfonates, organic disulfide compounds, and dithiocarbamic acid derivatives.