JP2003301044A - Polyimide resin containing triazine ring having chelate ligand group - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyguanamineimide resin which contains a chelate ligand group and on which metal plating can be directly applied. <P>SOLUTION: A heat-resistant flexible polyguanamineimide is synthesized by reacting a triazine dichloride whose triazine ring has a chelate ligand group as a pendant, with a diamine and a tetracarboxylic acid dianhydride. A polyimide copolymer allowing electroless plating can be obtained since the chelate ligand group partly projecting from the surface coated with the resin is chelated with a metal. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to metal plating of polyimide, and more particularly to the field of electronic component manufacturing technology, and more particularly to high density polyimide flexible wiring board manufacturing technology.

The production of a wiring board by metal plating on polyimide according to the present invention is carried out by subjecting the surface of a specially synthesized polyimide resin to patterning with a plating resist, followed by ordinary plating pretreatment, that is, degreasing, pre-dip, catalyzing, After accelerating, electroless nickel plating, electroless copper plating, and electrolytic copper plating are performed, and the plating resist is removed to complete the process.

[0003]

2. Description of the Related Art It is well known that polyimide is difficult to plate, and various attempts have been made so far, but it has not yet been put to practical use. Generally, it is considered that the surface is swollen and roughened by treating the polyimide with an alkali or the like to have an anchor effect. But,
It has not been put to practical use due to problems such as high alkali concentration and high processing temperature and long processing time.

In view of the above, it has been proposed that after a palladium vapor deposition layer is formed on a polyimide, alkali treatment and electroless plating are performed, and then electrolytic plating is performed (for example, Japanese Patent Laid-Open No. 7-70762). . However, even if this method is effective in the production of a so-called composite film in which a polyimide film is plated with a metal foil, it is not preferable in terms of steps and equipment costs when a polyimide multilayer wiring board is produced by a build-up method.

[0005]

As described above, since it is difficult to plate on polyimide, no research and development has been conducted so far to overcome this problem.

[0006] Therefore, as a result of intensive studies based on the idea that plating can be achieved by providing a polyimide with a coordination group capable of forming a chelate bond with a metal, as a result, triazine dichloride and a tetracarboxylic acid having a chelate coordination group are obtained. It was clarified that polyguanamine imide obtained by copolymerization of dianhydride and diamine has metal plating property, and the present invention was achieved.

[Means for Solving the Problems]

The polyguanamine imide in the present invention includes a triazine dichloride component having a chelate coordination group [Chemical Formula 4] as a pendant on a triazine ring, and an acid dianhydride and a diamine component represented by [Chemical Formula 5] and [Chemical Formula 6]. Any polymer can be used as long as it is a polymer obtained by polymerizing and imidizing the above.

The triazine dichloride in the present invention is a monosubstituted compound synthesized from cyanuric chloride and a compound containing a chelate coordination group.

The chelate coordinating group serving as the triazine ring pendant in the present invention is represented by the general formulas (1) to (12) in [Chemical Formula 4].

[Chemical 4] Phenanthroline system (1) Bipyridyl (2) Dipyridylamine type (3) Dicarboxybiquinoline type (4) Hydroxyazobenzene type (5) Salicylaldehyde oxyanil type (6) Pyridylazoaminophenol type (7) Pyridylazonaphthol type (8) Carboxymethyl aminomethyl umbelliferone system (9) Bibenzoxazoline type (10) Diphenylpyridyltriazine type (11) Trispyridyltriazine type (12)

The triazine ring having a chelate coordinating group in the present invention may be one kind or plural kinds.

As the tetracarboxylic acid dianhydride component in the present invention, the compound represented by [Chemical Formula 5] can be used.
It is also possible to use more than one.

[0012]

[Chemical 5]

As the diamine in the present invention, the diamine compound shown in [Chemical Formula 6] can be used, but a plurality of diamine compounds can be used as described above.

[0014]

[Chemical 6]

Each component of the polyguanamine imide in the present invention may be one kind or several kinds as described above, and the tetracarboxylic acid anhydride and the diamine may be
Aromatic compounds are preferred when heat resistance is important,
When importance is attached to solubility and low dielectric properties, alicyclic compounds are suitable. Of course, both can be used together.

In the present invention, in order to adjust the molecular weight, dicarboxylic acid anhydrides such as phthalic anhydride, maleic anhydride and nadic acid anhydride, aniline and hydroxyaniline,
An amine compound such as methoxyaniline can be used as a terminal stopper.

Since the polyguanamine imide in the present invention comprises three components, if the triazine ring component is infinitely small, the physical properties are close to those of polyimide, and if the tetracarboxylic dianhydride is infinitely small, the polyguanamine imide is in physical properties. Since it is closer to guanamine, molecular design is possible depending on what kind of performance is expected of the resin.

Since the coating film formed from the polyguanamine imide of the present invention is tough, flexible and heat resistant, it can be developed as an improved material for electronic component materials, particularly conventional polyimides in terms of functionality. it can.

[0019]

The present invention will be described with reference to the following examples. The chemical structures and abbreviations of the acid dianhydride and diamine used in the following examples are shown in [Chemical Formula 2] and [Chemical Formula 3], but the compound names and abbreviations used in the Examples are shown below.

PMDA: Pyromellitic dianhydride ODPA: 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride BPDA: 3,3', 4,4'-biphenyltetracarboxylic dianhydride BCD : Bicyclooctene tetracarboxylic acid dianhydride DADE: diaminodiphenyl ether TPE-R: 1,3-bis (4-aminophenoxy) benzene BAPP: 2,2'-bis [4- (4-aminophenoxy) phenyl] propane

The method of plating the surface of the coating film of the polyguanamine imide resin and the method of measuring the peeling strength thereof in the present invention are the same as those after performing ordinary electroless nickel plating or electroless copper plating (each including a pretreatment step). , Normal electrolytic copper plating (copper pyrophosphate plating, copper sulfate plating, etc.)
The thickness of the metal layer is set to about 30 to 35 μm, a notch having a width of 1 cm is made on the surface, the metal layer at that portion is peeled off, and a load is applied in the 90 ° direction at a speed of 5 cm / min. The load when peeled off is measured.

(Example 1) 6-dipyridylamino-s-triazine-2,4-dic
Synthesis of lolide 26.9 g (146 mm) of cyanuric chloride in a 3-neck flask
ol) and 200 ml of tetrahydrofuran (THF) were added and the mixture was dissolved in an ice bath at 0 to 5 ° C. under a nitrogen atmosphere. A solution of 25.0 g (146 mmol) of 2,2'-dipyridylamine and 14.8 g (146 mmol) of triethylamine dissolved in 100 ml of THF was added dropwise with stirring within a reaction temperature range of 0 to 5 ° C, and then reacted for 2 hours. Then, the temperature was further raised to 30 to 40 ° C. and the reaction was carried out for 8 hours. After the reaction, THF was removed and the obtained yellow solid was dissolved in toluene, washed with water until neutral, separated, dehydrated with anhydrous sodium sulfate, filtered, and the toluene removed to remove toluene.
Recrystallized with a mixed solvent of hexane / hexane to give white crystals 35.0
g was obtained. The melting point is 177 ° C. Synthesis of polyguanamine imide having chelate coordination group Diamine T was added to a 100 ml three-necked flask under nitrogen atmosphere.
2.92 g (10 mmol) of PE-R and 20 ml of 1,3-dimethylimidazolidone (DMI) were added and the mixture was cooled to 0 in an ice bath.
Cooled to ° C. To this, 2.03 g (10 mmol) of bistrimethylsilylacetamide (BSA) was injected and 0
C. for 30 minutes, room temperature for 15 minutes, and then 6-dipyridylamino-s-triazine-2,4-dichloride.
60 g (5 mmol) and PMDA 1.09 g (5 mmo
1) was added at the same time and reacted at 20 ° C. for 1 hour and at 80 ° C. for 24 hours. A yellow transparent and flexible polyguanamine imide film was obtained by heating this polymerization solution at 250 ° C. for imidization (FIG. 1). The glass transition point and 5% weight loss temperature of the obtained film were measured (Table 1). Plating of polyguanamine imide film The resulting polyguanamine imide film layer is OPC-
OPC-SAL- after immersing in 380 Condeclean M (Okuno Pharmaceutical Co., Ltd., the same below) at 65 ° C. for 5 minutes and washing with water.
Immerse in M for 1 minute at room temperature and immediately soak in OPC-80 Catalyst M for 5 minutes at room temperature and wash with water. Then OPC-555
Immerse in accelerator M for 5 minutes at room temperature, wash with water, and place in TMP chemical nickel bath for 10 minutes at room temperature to perform electroless nickel plating. Then, if necessary, it is immersed in a copper displacement agent ANC act bath at room temperature for 1 to 2 minutes to form a copper displacement layer. Then 25
Anode current density of 2 in a copper sulfate plating bath adjusted to -30 ℃
Electroplating was performed at A / dm ² for 60 minutes to form a 30 μm copper plating layer. 1 with a cutter knife on this copper plating layer
Make a notch of cm width and peel it off from the film layer.
When a load was applied in the 0 degree direction and the load when peeled at a speed of 5 cm / min was measured, the results shown in Table 1 were obtained. (Examples 2 to 3) A chelate coordination group-containing triazine dichloride in Example 1 was reacted in the same manner as in Example 1 except that the molar ratio of PMDA was changed to prepare a polyguanamine imide film. Was measured. In addition, the film was plated and the peel strength was measured. The results are shown in Table 1. (Example 4) DADE as the diamine in Example 1
Was reacted in the same manner except that ODPA was used as the acid dianhydride to form a polyguanamine imide film, and
g, 5% weight loss temperature was measured. In addition, the film was plated and the peel strength was measured. The results are shown in Table 1. (Example 5) BAPB as the diamine in Example 1
Was similarly reacted with BPDA as an acid dianhydride and BCD in an equimolar manner to form a polyguanamine imide film, and Tg, 5% weight loss temperature was measured. In addition, the film was plated and the peel strength was measured. The results are shown in Table 1. (Example 6) DADE as the diamine in Example 1
And TPE-R were reacted in the same manner except that ODPA was used as the acid dianhydride to form a polyguanamine imide film, and the Tg, 5% weight loss temperature was measured. In addition, the film was plated and the peel strength was measured. The results are shown in Table 1. (Example 7) Instead of the chelate coordinating group 2,2'-dipyridylamine in Example 1, 5-amino-
The reaction was conducted in the same manner except that 1,10-phenanthroline was reacted to prepare a polyguanamine imide film,
g, 5% weight loss temperature was measured. In addition, the film was plated and the peel strength was measured. The results are shown in Table 1. (Comparative Examples 1 and 2) Films of polyimide or polyguanamine reacted by removing either 6-dipyridylamino-s-triazine-2,4-dichloride and PMDA in Example 1 were prepared, and Tg was 5%. The weight loss temperature was measured. In addition, the film was plated and the peel strength was measured. The results are shown in Table 1.

The synthetic reaction formula of polyguanamine imide is shown in [Fig.
1].

[Figure 1]

The test results measured in Examples 1 to 7 and Comparative Examples 1 and 2 are summarized in Table 1.

[Table 1]

EFFECT OF THE INVENTION Plating of a coating film obtained by applying a polyimide varnish and drying it is almost impossible unless a special surface treatment is performed. However, in polyguanamine imide copolymerized with triazine dichloride, which is a heat-resistant compound with a chelate coordination group, palladium ions, which are plating catalyst metals, are easily adsorbed to the chelate coordination groups protruding on the coating surface, resulting in As a result, the adhesion of the metal plating has been greatly improved.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4J043 PA06 PA08 PB03 PB08 PB11                       PB15 PB22 PB23 PB24 PC016                       PC066 PC146 PC166 QB15                       QB21 QB26 QB31 QB50 QB52                       RA08 RA34 RA35 RA37 SA06                       SA43 SA54 SB05 TA22 TA43                       TB05 UA032 UA121 UA122                       UA131 UA132 UA141 UA142                       UA151 UA161 UA171 UA181                       UA262 UB021 UB061 UB062                       UB121 UB131 UB152 UB301                       UB302 UB351 VA021 VA031                       VA041 VA062 WA09 XB05                       XB07 XB09 ZA60 ZB50

Claims (2)

[Claims] 1. A triazine ring having general formulas (1) to (12):
And a triazine dichloride (A) having a structure of [Chemical formula 1] or a chelate coordination group similar thereto, and tetracarboxylic dianhydride (B) and [Chemical formula 3] shown in [Chemical formula 2].
A polyguanamine imide resin, which is synthesized by reacting the diamine (C) shown in 1. [Chemical 1] Phenanthroline system (1) Bipyridyl (2) Dipyridylamine type (3) Dicarboxybiquinoline type (4) Hydroxyazobenzene type (5) Salicylaldehyde oxyanil type (6) Pyridylazoaminophenol type (7) Pyridylazonaphthol type (8) Carboxymethyl aminomethyl umbelliferone system (9) Bibenzoxazoline type (10) Diphenylpyridyltriazine type (11) Trispyridyltriazine type (12) 2. A chelate coordination group-containing triazine dichloride (A), which is a raw material of a polyguanamine imide resin, and a tetracarboxylic dianhydride (B) are in a molar ratio of (A) /
(A) + (B) is 10 to 90/100, preferably 30 to
A polyguanamine imide resin containing a chelate coordination group, which is 70/100. [Chemical 2] [Chemical 3]