JPH0881627A - Molded form - Google Patents

Abstract

PURPOSE: To obtain a molded form excellent in chemical resistance, low water absorption, high-temperature rigidity and metal adhesion as well as soldering heat resistance, highly low in property change such as dimensional change, therefore suitably usable as a circuit component such as a printed wiring board or mold board, electromagnetic wave shielding member, lamp reflector, metal -alternative decorative resin molded form, etc. CONSTITUTION: This molded form is obtained by providing a metallic layer on the surface of a molded form made from a polyamide composition comprising (a) 100 pts.wt. of a polyamide made up of dicarboxylic acid component with terephthalic acid accounting for 60--100mol% of the total dicarboxylic acid components and diamine component with 1,9-nonanediamine accounting for 60-100mol% of the total diamine components, having the intrinsic viscosity [η]determined at 30 deg.C in conc. H2 SO4 of 0.4-3.0dL/g, with >=10% of the terminal group blocked, and (b) 0.01-100 pts.wt. of a filler.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel molded article having a metal layer on the surface of a polyamide molded article. For more information,
The present invention relates to a molded article having a metal layer on the surface thereof, which has excellent solder heat resistance as well as various properties such as chemical resistance, low water absorption, and rigidity at high temperature. The molded product of the present invention is a printed wiring board,
It can be suitably used for a circuit component such as a molded substrate, an electromagnetic wave shield member, a lamp reflector, and a resin molded body for metal substitute decoration.

[0002]

2. Description of the Related Art Molded products in which a metal layer is formed on a plastic surface by a plating method are often used as printed circuit boards, molded circuit boards and other circuit components, electromagnetic wave shielding members, metal alternative decorative resin molded products, and the like. ABS resin, nylon, polyacetal, polycarbonate, polybutylene terephthalate, and the like are used for the molded body. In recent years, the surface mounting method (SMT) is rapidly spreading in the method of mounting electronic components on circuit components such as printed wiring boards and molded substrates. Corresponding to this trend, circuit components such as a printed wiring board and a mold substrate are required to have high heat resistance (hereinafter referred to as solder heat resistance) to withstand a solder melting temperature. In order to meet such demands, investigations have been made in the case of using a high heat resistant resin such as liquid crystal polymer, polyimide, 6T-based polyamide mainly composed of hexamethylenediamine and terephthalic acid, 46 nylon composed of tetramethylenediamine and adipic acid. Is being done. For example, JP-A-3
In JP-A-197558, a polyamide composition in which a polyamide composed of a terephthalic acid component and an isophthalic acid component and a 1,6-hexamethylenediamine component contains an inorganic filler is used as a material for a molded article having a metal layer on its surface. It is described that this can be done.

[0003]

However, even the molded product using the above-mentioned high heat resistant resin still has insufficient solder heat resistance, and further, chemical resistance, low water absorption, metal layer adhesion, etc. A molded product excellent in various properties is required.

The object of the present invention is to have excellent soldering heat resistance as compared with a conventional molded article having a metal layer on the surface thereof, and also chemical resistance, low water absorption, high temperature rigidity, toughness, metal layer adhesion, etc. Another object of the present invention is to provide a molded product having a metal layer on the surface which is excellent in various properties.

[0005]

As a result of intensive studies to solve the above problems, the present inventors have found that a polyamide composition comprising a polyamide containing terephthalic acid and 1,9-nonanediamine as main components and a filler. The present invention was completed by discovering that a molded product excellent in the above performance can be obtained by using

According to the present invention, the above-mentioned object is (a) a dicarboxylic acid component in which 60 to 100 mol% of the dicarboxylic acid component is terephthalic acid, and 60 to 100 of the diamine component.
It comprises a diamine component having a mol% of 1,9-nonanediamine, an intrinsic viscosity [η] measured at 30 ° C. in concentrated sulfuric acid of 0.4 to 3.0 dl / g, and 10% or more of its terminal groups. Achieved by providing a molded product having a metal layer on the surface of a molded product obtained from a polyamide composition consisting of 100 parts by weight of a sealed polyamide and (b) 0.01 to 100 parts by weight of a filler. It

The present invention will be specifically described below. The polyamide used in the present invention, as a dicarboxylic acid component,
The terephthalic acid component is 60 mol% or more, preferably 75 mol% or more, more preferably 90 mol% or more. When the content of the terephthalic acid component is less than 60 mol%, various physical properties such as solder heat resistance and chemical resistance of the obtained molded product are deteriorated, which is not preferable.

Other dicarboxylic acid components other than the terephthalic acid component include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid,
Aliphatic dicarboxylic acids such as trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid; 1,3-cyclopentanedicarboxylic acid, 1,4 An alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid;
Isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,
7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3
-Phenylenedioxydiacetic acid, diphenic acid, dibenzoic acid, 4,4'-oxydibenzoic acid, diphenylmethane-
4,4'-dicarboxylic acid, diphenyl sulfone-4,
Aromatic dicarboxylic acids such as 4'-dicarboxylic acid and 4,4'-biphenyldicarboxylic acid, or any mixture thereof can be mentioned. Of these, aromatic dicarboxylic acids are preferably used. Further, polyvalent carboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can be used within the range where melt molding is possible.

The polyamide used in the present invention has a 1,9-nonanediamine component as a diamine component in an amount of 60 mol% or more, preferably 75 mol% or more, more preferably 90 mol% or more. Further, as a diamine component, in addition to the 1,9-nonanediamine component, 2-methyl-
By copolymerizing a specific amount of the 1,8-octanediamine component, a molded product having more excellent mechanical properties such as impact resistance can be obtained, which is preferable. The copolymerization ratio (molar ratio) of the 1,9-nonanediamine component and the 2-methyl-1,8-octanediamine component is preferably 60:40 to 99: 1, and 7
It is more preferably 0:30 to 95: 5.

As diamine components other than the 1,9-nonanediamine component and the 2-methyl-1,8-octanediamine component, ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1 , 8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 3-methyl-1,
5-pentanediamine, 2,2,4-trimethyl-1,
6-hexanediamine, 2,4,4-trimethyl-1,
Aliphatic diamines such as 6-hexanediamine and 5-methyl-1,9-nonanediamine; alicyclic diamines such as cyclohexanediamine, methylcyclohexanediamine and isophoronediamine; p-phenylenediamine, m
-Phenylenediamine, xylenediamine, 4,4'-
Aromatic diamines such as diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ether and the like, or any mixture thereof can be mentioned.

The polyamide used in the present invention comprises 10% or more, preferably 40% or more of the terminal groups of its molecular chain.
% Or more, and more preferably 70% or more of the terminal groups are blocked with the terminal blocking agent. By sealing the ends of the polyamide, the moldability is further improved, and it becomes possible to obtain a molded product having excellent surface beauty and the like.

The terminal blocking agent is not particularly limited as long as it is a monofunctional compound reactive with an amino group or a carboxyl group at the polyamide terminal, but from the viewpoint of reactivity and stability of the terminal blocking agent. , Monocarboxylic acid or monoamine is preferable, and monocarboxylic acid is more preferable from the viewpoint of easy handling. In addition, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters and monoalcohols can be used.

The monocarboxylic acid used as the terminal blocking agent is not particularly limited as long as it has reactivity with an amino group, and examples thereof include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, Aliphatic monocarboxylic acids such as caprylic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α -Aromatic monocarboxylic acids such as naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid and phenylacetic acid,
Alternatively, mention may be made of any mixture thereof.
Among these, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, from the viewpoints of reactivity, stability of the capped terminal, price Benzoic acid is particularly preferred.

The monoamine used as the terminal blocking agent is not particularly limited as long as it has reactivity with a carboxyl group, and examples thereof include methylamine, ethylamine, propylamine, butylamine, hexylamine and octylamine. , Aliphatic monoamines such as decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine; cycloaliphatic monoamines such as cyclohexylamine and dicyclohexylamine; aniline, toluidine, diphenylamine,
Mention may be made of aromatic monoamines such as naphthylamine or any mixtures thereof. Of these,
Butylamine, hexylamine, octylamine, in terms of reactivity, boiling point, stability of the capped end and price.
Decylamine, stearylamine, cyclohexylamine, aniline are particularly preferred.

The amount of the end-capping agent used varies depending on the reactivity, boiling point, reaction apparatus, reaction conditions of the end-capping agent used, etc. It is preferably used in the range of 0.1 to 15 mol%.

The polyamide used in the present invention can be produced by any method known as a method for producing a crystalline polyamide. For example, solution polymerization method or interfacial polymerization method using acid chloride and diamine as raw materials; melt polymerization method using dicarboxylic acid and diamine as raw materials,
It can be produced by a solid phase polymerization method, a melt extruder polymerization method, or the like. Below, an example of the manufacturing method of polyamide is shown.

An end-capping agent and, if necessary, a catalyst are first added all at once to a diamine and a dicarboxylic acid to prepare a nylon salt, which is once heated at a temperature of 200 to 250 ° C. in concentrated sulfuric acid at 30 ° C. Viscosity [η] is 0.1
A polyamide can be easily obtained by using a prepolymer of 5 to 0.25 dl / g and further subjecting it to solid phase polymerization or polymerization using a melt extruder. The intrinsic viscosity [η] of the prepolymer is 0.15 to 0.25 dl /
Within the range of g, it is possible to obtain a polyamide having a small difference in the molar balance between the carboxyl group and the amino group and a decrease in the polymerization rate in the post-polymerization stage, and having a small molecular weight distribution and excellent in various performances and moldability. When the final stage of the polymerization is carried out by solid phase polymerization, it is preferably carried out under reduced pressure or under the flow of an inert gas, and if the polymerization temperature is in the range of 200 to 250 ° C., the polymerization rate is large and the productivity is excellent. It is preferable because coloring and gelation can be effectively suppressed.
When the final stage of the polymerization is carried out by a melt extruder, it is preferable that the polymerization temperature is 370 ° C. or less because the polyamide is hardly decomposed and a polyamide having no deterioration can be obtained.

The intrinsic viscosity [η] of the polyamide used in the present invention measured in concentrated sulfuric acid at 30 ° C. is 0.4 to 3.0 d.
It is 1 / g, preferably 0.6 to 2.0 dl / g, and more preferably 0.8 to 1.8 dl / g. When the intrinsic viscosity [η] is in this range, the obtained polyamide has good mechanical performance and moldability, which is preferable.

As the above catalyst, phosphoric acid, phosphorous acid,
Hypophosphorous acid or a salt thereof, or an ester thereof, specifically, a metal salt such as potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, or antimony, Ammonium salt, ethyl ester,
Examples thereof include isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester and phenyl ester.

Examples of the filler used in the present invention include inorganic powder fillers such as zinc oxide, magnesium oxide, iron oxide, antimony oxide, titanium oxide, alumina, silica and other metal oxides; boron nitride and other metals. Nitride; sodium carbonate, potassium carbonate, calcium carbonate, zinc carbonate, magnesium carbonate, calcium silicate, lead silicate,
Inorganic salts such as magnesium silicate, calcium phosphate, lead phosphate, calcium sulfate, barium sulfate; clays such as talc, kaolin, mica, acid clay; organic such as calcium oxalate, calcium benzoate, magnesium stearate, zinc salicylate Acid salt; zinc powder, aluminum powder, graphite powder, carbon black, glass beads, etc .; high melting point polymers such as nylon 6T and nylon 22 which are organic powder fillers; pt-butyl aluminum benzoate, bis (4) phosphate -T-butylphenyl)
Examples thereof include sodium, 2,2′-methylenebis (4,6-di-t-butylphenyl) sodium phosphate, and di (pt-butylbenzoic acid) hydroxyaluminum. Above all, it is preferable to use an inorganic powder filler such as calcium carbonate, talc, or silica. By using such a filler, it is possible to improve the adhesion between the molded body and the metal layer, and to improve the performance of the molded body such as heat distortion temperature, surface beauty, chemical resistance, and low water absorption. it can. Further, in addition to the above powdery filler, a fibrous filler such as glass fiber or carbon fiber can be used, and the mechanical strength of the molded product can be improved. These fillers can be used alone or in combination of two or more. In particular, it is more preferable to use a combination of an inorganic powder filler such as calcium carbonate, talc or silica and a fibrous filler such as glass fiber.

The amount of the filler used is 0.01 to 100 parts by weight based on 100 parts by weight of polyamide, and 0.05
-80 weight part is preferable, and 0.5-70 weight part is more preferable.

In addition to the above-mentioned fillers, brominated polymers, antimony oxides, flame retardants such as metal hydroxides, hindered phenol-based, hindered amine-based, phosphorus-based and thio-based antioxidants, if necessary, A colorant, an ultraviolet absorber, a light stabilizer, an antistatic agent, a plasticizer, a lubricant, or another kind of polymer may be used as an additive.

Examples of the method of blending the above-mentioned fillers or additives used as necessary with the polyamide include a method of adding during the polycondensation reaction, a method of dry blending, a method of melt-kneading using an extruder and the like. To be

Using the polyamide composition prepared as described above, a molded article having a desired shape is produced by utilizing molding methods such as injection molding, blow molding, extrusion molding, compression molding, stretching and vacuum molding. can do.

The molded product of the present invention has a metal layer on the surface of the molded product obtained from the above polyamide composition. The portion having the metal layer may be the entire surface of the molded body or an arbitrary portion. Examples of the method of forming the metal layer on the surface of the molded body include a plating method and a method of physically attaching a metal. The plating method can be performed by a conventionally known basic process including an etching process, a chemical plating process, and an electroplating process. Examples of the etching step include a method of immersing in an acidic solution such as a hydrochloric acid-based solution, a hydrofluoric acid-based solution, a sulfuric acid-based solution, a nitric acid-based solution, a chromic acid / sulfuric acid solution, or a chromic acid / nitric acid solution. The chemical plating process and the electroplating process can be performed by a usual method. As a method of physically attaching the metal, a polyamide plate or film,
A metal plate or film is attached by heat pressing.

The molded product of the present invention is a circuit component such as a printed wiring board or a mold substrate which requires solder heat resistance, a lamp reflector which requires heat resistance, an electromagnetic wave shield member, a resin molded product for metal substitute decoration, and the like. Can be suitably used.

[0027]

EXAMPLES The molded article of the present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the examples, the terminal sealing rate, the intrinsic viscosity [η], the impact strength, the heat distortion temperature, the chemical resistance, the water absorption rate,
Solder heat resistance and metal layer adhesion were measured by the following methods.

End capping ratio : ¹ H-NMR (500 MH
z, measured in deuterated trifluoroacetic acid at 50 ° C.) to measure the number of carboxyl group end, amino group end and capped end respectively from the integrated value of the characteristic signal for each end group, The terminal sealing rate was calculated from (1). Table 1 shows chemical shift values of typical signals used for the measurement. Sealing rate (%) = [(A−B) ÷ A] × 100 (1) [In the formula, A is the total number of end groups of molecular chain (this is usually equal to twice the number of polyamide molecules). And B represents the total number of carboxyl group terminals and amino group terminals.]

[0029]

[Table 1]

Intrinsic viscosity [η] : in concentrated sulfuric acid at 30 ° C.
The intrinsic viscosity (ηinh) of the samples having the concentrations of 0.05, 0.1, 0.2, and 0.4 g / dl was measured, and the value obtained by extrapolating this to the concentration of 0 was defined as the intrinsic viscosity [η]. ηinh = [ln (t ₁ / t ₀ )] / c [wherein, ηinh represents an intrinsic viscosity (dl / g), t ₀ represents a solvent flowing time (second), and t ₁ represents a sample solution flowing down. Represents the time (seconds), and c represents the concentration of the sample in the solution (g / dl). ]

Impact strength, heat distortion temperature : injection molding at a temperature about 20 ° C. higher than the melting point of polyamide (mold temperature 150
The test piece in an absolutely dry state was measured by the following method.

[0032]

[Table 2]

Chemical resistance : about 20 ° C. above the melting point of polyamide
A test piece obtained by punching a film having a thickness of about 200 μm, which was hot pressed at a high temperature, with JIS No. 3 dumbbell was immersed in various chemicals for 7 days, and the retention rate of the tensile strength of the sample before the treatment was measured.

Water absorption : hot pressed at a temperature 20 ° C. higher than the melting point of polyamide and cooled at 150 ° C. for 5 minutes,
A film (5 cm × 5 cm) having a thickness of about 200 μm was dried under reduced pressure at 120 ° C. for 5 days, weighed, and then dipped in water at 23 ° C. for 10 days, weighed, and added to the weight before dipping for an increase amount. It was calculated as a ratio (%).

Solder heat resistance : about 20 from the melting point of polyamide
Injection molding (mold temperature 150 ° C) 40 ° C
A 100 × 1 mm test piece was left in a room at 23 ° C. and 50% RH for 15 days to control the humidity, and then about 40 mm from the end of the test piece.
The portion up to mm was immersed in a solder bath at an angle of 45 degrees for 10 seconds, and the presence or absence of deformation of the test piece was observed.

Adhesion to metal layer: To evaluate the adhesion to the metal layer, a tape peeling test (peel angle 90 °) is performed using a molded body having a plated layer or a molded body having a copper film adhered thereto by hot pressing. The presence or absence of peeling was observed by.

Reference Example 1 3272.9 g (19.70 mol) of terephthalic acid,
3165.8 g (20.0 mo) of 1,9-nonanediamine
1), benzoic acid 73.27 g (0.60 mol), and sodium hypophosphite monohydrate 6.5 g (0.
1% by weight) and 6 liters of distilled water were placed in an autoclave having an internal volume of 20 liters and purged with nitrogen. The mixture was stirred at 100 ° C for 30 minutes, and the internal temperature was raised to 210 ° C over 2 hours. At this time, the pressure in the autoclave was increased to 22 kg / cm ² . After continuing the reaction for 1 hour, 230 ℃
The temperature to 230 ° C for 2 hours,
The reaction was carried out while gradually removing the steam to maintain the pressure at 22 kg / cm ² . Next, the pressure is 10 kg / c over 30 minutes.
Lower to m ² and react for 1 hour to obtain an intrinsic viscosity [η]
0.25 dl / g of prepolymer was obtained. This one
It was dried at 00 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. This is 230 ℃, under 0.1mmHg, 1
Solid-state polymerization was performed for 0 hours to obtain a white polyamide having a melting point of 316 ° C., an intrinsic viscosity [η] of 1.35 dl / g, a terminal sealing rate of 90%.

Reference Examples 2 to 6 and 8 Using the dicarboxylic acid component and the diamine component shown in Table 3, polyamides were produced according to the method described in Reference Example 1.

[0039]

[Table 3]

Examples 1, 2 and Comparative Examples 1-5 Using a twin-screw extruder, the polyamides of Reference Examples 1, 2, 4-8 were compounded with a filler at a temperature about 20 ° C. higher than the melting point of the polyamide. To produce a polyamide composition. The above-mentioned test pieces were produced using these polyamide compositions, and the above-mentioned various performances were evaluated. The results are shown in Table 4. further,
Using these polyamide compositions, injection molding (mold temperature 150 ° C.) was performed at a temperature about 20 ° C. higher than the melting point of polyamide to prepare a molded product of 80 × 80 × 3 mm. The molded body was wiped with a cloth soaked with isopropyl alcohol, and then degreased for 3 minutes at 60 ° C. using 50 g / l OPC-250 cleaner (manufactured by Okuno Chemical Industries Co., Ltd.). Then, concentrated sulfuric acid 200ml / l, chromic acid 400g
/ L, Top Shut (Okuno Pharmaceutical Co., Ltd.) 0.3 g /
An acidic chromic acid solution consisting of 1 was prepared at 70 ° C., and the molded body was immersed in this solution for 10 minutes for surface treatment. The surface-treated molded body was pickled with a 5% aqueous solution of 38% hydrochloric acid for 3 minutes at room temperature, and then the B-20 prepared at 45 ° C.
0 Neutrizer (Okuno Pharmaceutical Co., Ltd.) 200ml /
It was immersed in an aqueous solution of 1 for 5 minutes. Next, it was immersed in a solution of a tin-palladium complex salt aqueous solution (A30 catalyst, manufactured by Okuno Seiyaku Co., Ltd.), hydrochloric acid and water (volume ratio 1: 1: 5) prepared at 25 ° C. for 4 minutes for the catalyst. I did a listing. This molded body was immersed in a 10% aqueous solution of 38% hydrochloric acid prepared at 50 ° C. for 4 minutes for acceleration, and then TMP chemical nickel solution A and solution B (Okuno Pharmaceutical ( Co., Ltd.) and water are immersed in an electroless nickel plating solution having a volume ratio of 1: 1: 4 for 10 minutes to form a nickel plating layer having an average of 1 μm on the surface of the molded body, and further electrolytic copper plating is performed. By applying, a copper plating layer was formed. Using the formed body having the metal layer on the surface thus produced, the adhesion between the metal layer and the formed body was evaluated. The results are shown in Table 4.

Example 3 Using a twin-screw extruder, a polyamide composition was prepared by blending the polyamide of Reference Example 3 with a filler at a temperature about 20 ° C. higher than the melting point of the polyamide. The above-mentioned test pieces were prepared using this polyamide composition, and the above-mentioned various performances were evaluated. The results are shown in Table 4. Further, using this polyamide composition, injection molding (mold temperature: 150 ° C.) was performed at a temperature about 20 ° C. higher than the melting point of polyamide to obtain 80 ×.
A 80 × 3 mm molded body was produced. This molded body has a thickness of 3
The adhesiveness between the metal layer and the molded body was evaluated using a molded body having a metal layer on the surface of which a 5 μm copper film was bonded by hot pressing. The results are shown in Table 4.

[0042]

[Table 4]

[0043]

EFFECTS OF THE INVENTION The molded product of the present invention is excellent in solder heat resistance, chemical resistance, low water absorption, high temperature rigidity, and metal adhesion. It can be preferably used for a circuit component such as a printed wiring board and a molded board, an electromagnetic wave shield member, a lamp reflector, and a resin molded body for metal substitute decoration.

Claims (2)

[Claims] 1. 60 to 100 of (a) dicarboxylic acid component
It is composed of a dicarboxylic acid component having terephthalic acid as a mol% and a diamine component having 60 to 100 mol% of a diamine component as 1,9-nonanediamine, and has an intrinsic viscosity [η] of 0. It was obtained from a polyamide composition consisting of 100 parts by weight of a polyamide of 4 to 3.0 dl / g and 10% or more of its terminal groups being capped, and (b) 0.01 to 100 parts by weight of a filler. A molded product having a metal layer on the surface of the molded product. 2. 60 to 100 mol% of the diamine component consists of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and 1,9-nonanediamine and 2-methyl-1,8-octanediamine. The molar ratio of 6
The molded product according to claim 1, which is 0:40 to 99: 1.