JPH11117075A - Polyolefin based resin composition, plated and molded goods and their production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyolefin based resin compsn. which allows a plating treatment with high plating strength and decreased variations without requiring an etching pretreatment (solvent treatment) stage and polarity impartation stage and to provide plated and molded goods formed by using the same. SOLUTION: This polyolefin based resin compsn. contains (A) 40 to 89.9 wt.% polyolefin based resin, (B) 10 to 50 wt.% acid soluble inorg. particles having an average particle size of 0.03 to 10 μm and (C) 0.1 to 20 wt.% at least one kind selected from a denatured polyolefin based resin and a denatured styrene based resin contg. an imide ring into which an amino group and/or formamide group is introduced via a hydrocarbon group bonded to the nitrogen atom of the imide ring. The plated and molded goods are obtd. by subjecting the molded goods consisting of this compsn. to a plating treatment without subjecting the molded goods to the etching pretreatment (solvent treatment) stage and the polarity impartation stage.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin resin composition, a plated product and a method for producing the same. More specifically, the present invention provides a polyolefin-based resin composition which has a high plating strength and can be subjected to a plating process with a small variation without requiring a pre-etching treatment (solvent treatment) step and a polarity imparting step. The present invention relates to a plated product obtained by subjecting a molded product to a plating treatment and a method for efficiently producing the plated product.

[0002]

2. Description of the Related Art Conventionally, polyolefin resins have been widely used as general-purpose plastics in many fields because of their excellent moldability, mechanical properties, durability and chemical resistance. However, since this polyolefin-based resin is non-polar, it is difficult to perform a plating process, and in reality, it is hardly used in the field of plating. Therefore, AB for plating
Expensive resins such as S resin and polycarbonate alloy are used, but these resins have poor moldability,
The rubber phase that becomes the anchor is oriented by the etching process,
It has the disadvantage that the plating strength of the product varies.
Therefore, a polyolefin-based resin composition that can be plated has been strongly desired.

[0003] The inventors of the present invention previously blended an elastomer or an acid-soluble inorganic particle with a polyolefin resin and performed a polarity-imparting step in a plating process, so that the pre-etching process (solvent process) was omitted. It has been found that plating can be performed. However, in this case, since a polarity-imparting step is required, the equipment in the conventional plating process cannot be used as it is, and a trouble such as replacement of a product rack is required, which inevitably increases the plating cost. Occurred. Therefore, the present inventors have further studied and found that the plating treatment can be performed by adding a cationic surfactant without requiring a polarity-imparting step. However, in this case, by adding a surfactant, physical properties such as heat resistance may be slightly reduced, and bleeding of the surfactant may contaminate a mold or a product. Was not satisfactory.

[0004]

Under such circumstances, the present invention makes it possible to perform a plating treatment with a high plating strength and a small variation without the need for a polarity imparting step without using a surfactant. It is an object of the present invention to provide a polyolefin-based resin composition and a plated molded product using the same.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object, and as a result, the polyolefin resin has acid-soluble inorganic particles, specific modified olefin resin and modified styrene resin. It has been found that a composition in which an antioxidant, a metal deactivator, and a thermoplastic elastomer are blended at a predetermined ratio, as required, can be suitable for the purpose. The present invention has been completed based on such findings. That is, the present invention relates to (A)
40 to 89.9% by weight of polyolefin resin, (B) 10 to 50 acid-soluble inorganic particles having an average particle size of 0.03 to 10 μm
% By weight and (C) a modified olefin resin or a modified styrene resin containing an imide ring having an amino group and / or a formamide group introduced via a hydrocarbon group bonded to a nitrogen atom of the imide ring. At least one kind 0.1
It is intended to provide a polyolefin-based resin composition containing from 20 to 20% by weight, and a plated molded article obtained by plating a molded article made of the polyolefin-based resin composition. Further, the plated molded article is obtained by sequentially performing an etching treatment, a catalyst carrying treatment, an electroless copper plating and / or an electroless nickel plating treatment, and optionally an electroplating treatment on a molded product made of the above polyolefin resin composition. Alternatively, it can be manufactured by sequentially performing an etching process, a catalyst supporting process, and an electroplating process.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The polyolefin resin of the component (A) in the polyolefin resin composition of the present invention is not particularly limited. For example, ethylene; propylene; butene-1; 3-methylbutene-1; Penten-1; homopolymers of α-olefins such as 4-methylpentene-1 and copolymers thereof, and copolymers thereof with other copolymerizable unsaturated monomers. Representative examples include high density, medium density, low density polyethylene, linear low density polyethylene, polyethylenes such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, propylene homopolymer, propylene Examples thereof include polypropylenes such as ethylene block copolymers and random copolymers, propylene-ethylene-diene compound copolymers, and polybutene-1 and poly-4-methylpentene-1. These polyolefin resins may be used alone or in combination of two or more.

As the acid-soluble inorganic particles of the component (B) in the composition of the present invention, those having an average particle diameter in the range of 0.03 to 10 μm are used. This average particle diameter is 0.03 μm
If it is less than 10 μm, the plating strength may not be sufficiently exhibited. If it exceeds 10 μm, both the impact resistance and the plating strength may be reduced. Considering plating strength and impact strength, the preferred range of the average particle size is 0.1 to 3 μm.
m. The acid-soluble inorganic particles are not particularly limited, and acid-soluble inorganic particles can be appropriately selected from those conventionally used as inorganic fillers for plastics. Examples of such a powder include powders of calcium carbonate, magnesium carbonate, magnesium hydroxide, basic magnesium oxysulfate and the like. These acid-soluble inorganic particles may be used alone or in combination of two or more.

The modified olefin resin and the modified styrene resin as the component (C) in the composition of the present invention have an amino group and / or a formamide group introduced through a hydrocarbon group bonded to a nitrogen atom of an imide ring. Is used. Such modified olefin-based resin and modified styrene-based resin are not particularly limited as long as they have the above-mentioned properties, and are variously limited, for example, JP-A-4-2963.
No. 40, No. 5-32901, No. 5-3290
No. 2, JP-A-5-239273, JP-A-5-2392
Nos. 74, 6-16877 and the like. Specific examples of such modified olefin-based resin and modified styrene-based resin include the general formula (I) in the molecule of the olefin-based resin and the styrene-based resin, respectively.

[0009]

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Preferred are those having a functional group represented by the following formula: In the general formula (I),
R ¹ and R ² each independently represent a hydrogen atom, a carbon number of 1 to 6;
Represents an alkyl group or an aryl group having 6 to 8 carbon atoms;
³ is an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group having 5 to 17 carbon atoms, an arylene group having 6 to 12 carbon atoms,
An arylalkylene group having 7 to 12 carbon atoms or 4 to 4 carbon atoms
And 30 polyoxyalkylene groups. X is

[0011]

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(R ⁴ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, Y is a hydrogen atom or a CHO group). As the olefin resin in the modified olefin resin, any resin containing an olefin component may be used.
There is no particular limitation, and various types such as polyethylene (linear low density polyethylene (LLDPE), low density polyethylene (LDPE), very low density polyethylene (VLDP)
E), high-density polyethylene (HDPE)), polypropylene, polybutene, polyisobutene, ethylene-propylene copolymer, ethylene-propylene copolymer rubber (EPR), ethylene-butene copolymer (EBM), E
PDM, ethylene-α-olefin copolymers such as ethylene-propylene-butene copolymer, ethylene-butylene copolymer, copolymers of propylene with other α-olefins such as propylene-butene copolymer, Are various ethylene copolymers (ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer (E
VOH), an ethylene-maleic anhydride copolymer, an ethylene-alkyl (meth) acrylate copolymer, etc.), poly (4-methyl-1-pentene), and amorphous polyolefins and olefins having impaired crystallinity Series thermoplastic elastomer (TPO). These may be used alone or in combination of two or more. The term "copolymer" as used herein means a random, block, or random block copolymer, or a graft copolymer.

On the other hand, the styrene resin in the modified styrene resin is not particularly limited as long as it is an elastic resin containing a styrene component, and various resins such as styrene-butadiene rubber [random styrene-butadiene copolymer] (SBR), SBS, SIS], S
Examples include hydrogenated products of BS and SIS, such as SEBS and SEPS. These may be used alone or in combination of two or more. In addition, the molecular weight of the olefin resin and the styrene resin may be appropriately selected according to various situations, but in the case of the olefin resin, the number average molecular weight is usually 1,000 to 50,000,
It is preferably in the range of 1,000 to 30,000, and in the case of a styrene resin, the number average molecular weight is usually 5,000 to 50.
000, preferably from 5,000 to 200,000.

The modified olefin resin and the modified styrene resin into which the functional group represented by the general formula (I) has been introduced have a high polarity not found in ordinary polyolefin resins, and are therefore resins containing these. The composition does not require a polarity imparting step in the plating process.
The functional group may be contained alone in the molecule of the olefin-based resin or the styrene-based resin, or two or more different functional groups may be contained. The content of the functional group is:
It is preferably in the range of 0.2 to 60 mol%. If the content is less than 0.2 mol%, the effect of imparting polarity may not be sufficiently exhibited, and if it exceeds 60 mol%, the impact resistance of the composition may be reduced. The modified olefin resin and the modified styrene resin of the component (C) can be easily produced by a conventionally known method. In the composition of the present invention, the modified olefin resin and the modified styrene resin of the component (C) may be used alone or in combination of two or more. In the polyolefin-based resin composition of the present invention, the content ratio of the components (A), (B) and (C) is based on the total amount thereof.
Component (A) is 40 to 89.9% by weight, component (B) is 10 to 10% by weight.
50 weight% and component (C) are in the range of 0.1 to 20 weight%.

If the content of the component (A) is less than 40% by weight, the moldability is poor, and if it exceeds 89.9% by weight, the plating strength is reduced. If the content of the component (B) is less than 10% by weight, the plating strength is insufficient. If the content exceeds 50% by weight, the plating strength is rather lowered, and the moldability and impact resistance are also lowered. Further, when the content of the component (C) is less than 0.1% by weight, the amount of the supported catalyst is insufficient, and there is a possibility that plating may not be performed. When the content exceeds 20% by weight, the effect is improved for the amount. Not economically disadvantageous. In consideration of moldability, impact strength, amount of supported catalyst (plating ability), plating strength and economy, the preferable content ratios of component (A), component (B) and component (C) are 55 to 55, respectively.
84.8% by weight, 15-40% by weight and 0.2-10% by weight
Range.

In the polyolefin resin composition of the present invention, if necessary, the component (A), the component (B) and the component (C) may be further added together with the component (D) for the purpose of improving the performance of the composition. It may contain an antioxidant and / or (E) a metal deactivator and / or (F) a thermoplastic elastomer. The antioxidant of the component (D) is not particularly limited, and conventionally known ones, for example, phenol-based, phosphorus-based, and sulfur-based ones can be used. Here, as the phenolic antioxidant, for example, 2,6-
Di-t-butyl-4-methylphenol, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, pentaerythrityl-tetrakis [3- (3,5-di- t-butyl-4-hydroxyphenyl) propionate], 2-t-butyl-6-
(3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1-
(2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, triethylene glycol-bis- [3- (3
-T-butyl-5-methyl-4-hydroxyphenyl)
Propionate], 1,6-hexanediol-bis-
[3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis [1,1-di-
Methyl-2- [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl]
-2,4,8,10-Tetraoxaspiro [5,5] undecane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) Benzene, tris (3,5-di-t-butyl-4-
Hydroxybenzyl) isocyanurate, tris (4-
t-butyl-2,6-di-methyl-3-hydroxybenzyl) isocyanurate and the like.

Examples of the phosphorus-based antioxidant include tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite,
Bis (2,4-di-t-butylphenyl) pentaerythritol-diphosphite, bis (2,6-di-t
-Butyl-4-methylphenyl) pentaerythritol-diphosphite, bis (2,4,6-tri-t-
Butylphenyl) pentaerythritol-di-phosphite, methylenebis (2,4-di-t-butylphenyl) octylphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene-di -Phosphonite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene-di-phosphonite and the like.

Further, examples of the sulfur-based antioxidants include dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, glycerin tributyl thiopropionate, and glycerin trioctyl thiopropionate. Glycerin trilauryl thiopropionate, glycerin tristearyl thiopropionate, trimethylol ethane tributyl thiopropionate, trimethylol ethane trioctyl thiopropionate, trimethylol ethane trilauryl thiopropionate, trimethylol ethane Stearyl thiopropionate, pentaerythritol tetrabutyl thiopropionate, pentaerythritol tetraoctyl thiopropionate, pentaerythritol tetralau Lucio propionate, pentaerythritol tetra distearyl propionate.

The antioxidant of component (D) may be used alone or in combination of two or more. Also,
The content is usually in the range of 0.01 to 2.0 parts by weight per 100 parts by weight of the total of the components (A), (B) and (C). If the content is less than 0.01 part by weight, the antioxidant effect may not be sufficiently exerted. If the content exceeds 2.0 parts by weight, the effect is not improved for the amount, and it is uneconomical. In addition, other physical properties may be reduced. From the viewpoints of antioxidant effect, economy, and other physical properties, the preferred content of the component (D) is in the range of 0.1 to 1.5 parts by weight. The metal deactivator of the component (E) is not particularly limited as long as it can prevent copper damage, and conventionally known ones such as an oxalic acid derivative, a salicylic acid derivative, and a hydrazine derivative may be used. Can be Specifically, 3- (N-salicyloyl) amino-1,2,4-triazole, decamethylenecarboxylic acid disalicyloyl hydrazide, N, N-bis [3- (3,5-di-t-butyl) -4-hydroxyphenyl) propionyl] hydrazine, bis (2-isophthalate)
Phenoxypropionyl hydrazide), N-formyl-N'-
Salicilloylhydrazine, 2,2-oxamidobis- [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], oxalyl-bis-benzylidene-hydrazide and the like.

The metal deactivator of component (E) may be used alone or in combination of two or more. The content is usually in the range of 0.01 to 2.0 parts by weight per 100 parts by weight of the total of the components (A), (B) and (C). If the content is less than 0.01 part by weight, the effect of preventing copper damage may not be sufficiently exhibited. If the content is more than 2.0 parts by weight, the effect is not improved for the amount, and it is rather uneconomical. In addition, other physical properties may be reduced. From the viewpoints of copper damage prevention effect, economic efficiency, and other physical properties, the preferred content of the component (E) is in the range of 0.1 to 1.8 parts by weight.

On the other hand, the thermoplastic elastomer of the component (F) is not particularly limited, and a conventionally known thermoplastic elastomer can be used. Such materials include, for example, polysulfide rubber, thiocol rubber, acrylic rubber, urethane rubber, epichlorohydrin rubber, chlorinated rubber, styrene-butyl acrylate rubber, ethylene-methyl methacrylate-glycidyl methacrylate copolymer rubber, ethylene-methyl Ethylene-polar vinyl monomer copolymer rubber such as methacrylate-maleic anhydride copolymer rubber, natural rubber, polybutadiene, polyisoprene,
Polyisobutylene, neoprene, silicone rubber, styrene-butadiene block copolymer rubber (SBR), styrene-butadiene-styrene block copolymer (SB
S), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), styrene-isoprene block copolymer (SIR), styrene-isoprene-styrene block copolymer (SIS), hydrogenated styrene-isoprene-styrene block Copolymer (SEPS), ethylene propylene rubber (EPM), ethylene propylene diene rubber (EPDM), ethylene butylene rubber (EB)
M) and the like, and rubbers obtained by modifying them. Among them, in particular, EPM, EPDM, EBM and SEB
S is preferred.

The thermoplastic elastomer (F) may be used alone or in combination of two or more. The content is usually 1 to 80 per 100 parts by weight of the total of the components (A), (B) and (C).
It is in the range of parts by weight. If the content is less than 1 part by weight, the effect of adding the elastomer may not be sufficiently exerted. If the content exceeds 80 parts by weight, the surface hardness of the obtained molded article is reduced, and the plating film is easily damaged. Considering the effect of adding the elastomer and the surface hardness of the molded product, the preferred content of the component (F) is in the range of 5 to 50 parts by weight. The polyolefin-based resin composition of the present invention may contain, if necessary, various known additives such as light stabilizers, ultraviolet absorbers, heat stabilizers, lubricants, various fillers, as long as the object of the present invention is not impaired. Flame retardant, reinforcement,
An additive such as a pigment may be contained, and other thermoplastic resins, for example, polyvinyl chloride resin, polyamide resin, polyimide resin, polyester resin, polycarbonate resin, polyacetal resin, polyaromatic ether Ketone resin, polyphenylene ether resin,
It may contain a polyphenylene sulfide resin, a styrene resin, a polyaromatic ester resin, a polysulfone resin, an acrylate resin, or the like.

The method for preparing the resin composition is not particularly limited, and may be a conventionally known method, for example, a method in which essential components and various optional components used as required are mixed with a V-type blender,
A method of mixing with a mixer such as a ribbon blender or a Henschel mixer, a method of kneading with a kneader such as an extruder, a mixing roll, a Banbury mixer, a kneader, or a combination of a mixer and a kneader,
A kneading method can be used. The plated molded article of the present invention is obtained by molding the polyolefin resin composition thus obtained into a desired shape by a known method.
This is subjected to a plating process.

The present invention is characterized in that a plating step is not required in addition to a pre-etching treatment (solvent treatment) step in this plating treatment. If a polarity-imparting step is provided, plating will accumulate on the rack where the product is to be mounted.Therefore, the rack for the polarity-imparting step and the rack for the catalyst-carrying step must be separated from each other. This requires a lot of manpower, which inevitably raises costs significantly. As the plating treatment method, depending on the intended use of the resulting plated molded product,
For example, (1) a method of sequentially performing (a) an etching step, (b) a catalyst supporting step, (c) an electroless copper plating step and / or an electroless nickel plating step, (2) the (a) step, b) step, (c) step, and (d) a method of sequentially performing an electroplating step, (3) the above (a) step,
A method of sequentially performing the steps (b) and (d) is preferably used. The etching treatment step (a) in the methods (1), (2) and (3) is a step of forming an anchor hole on the surface of a molded product, and the etching method is not particularly limited. A method commonly used in plating of a molded article can be used. Examples of the etching agent include dichromic acid,
A mixed solution of dichromic acid / sulfuric acid, chromic acid, a mixed solution of chromic acid / sulfuric acid, trichloroethane, trichloroethylene, xylene and the like are used. After the etching treatment, the etching agent remaining on the surface of the molded article is removed by neutralization, washing, or the like.

Next, the catalyst supporting treatment step (b) in the above methods (1), (2) and (3) comprises:
In the method (2), the electroless copper plating or the electroless nickel plating in the next step is performed. In the method (3), the method for carrying out the electroplating in the next step is a method for supporting a catalyst. Is not particularly limited, and a method conventionally used in plating of a plastic molded product can be used. For example, in the methods (1) and (2), when performing electroless copper plating or electroless nickel plating in the next step, generally, a colloid of stannous chloride and palladium chloride having negative charges as catalyst particles is used. First, a colloidal substance of tin and palladium is deposited on the surface of the molded article to which polarity has been imparted by catalisting, and then tin is released by acceleration, leaving only palladium, so that electroless copper plating or non-electrolysis can be performed. A method of supporting a catalyst for electrolytic nickel plating (metal catalyst), or sensitizing (sensitizing treatment), for example, immersing a molded article with polarity in a stannous chloride solution to reduce the surface of the molded article After performing a treatment to adsorb powerful ionic tin, the molded article is activated, for example, immersed in a palladium chloride solution. To, the processing of precipitating palladium by the action of the Zuzu, electroless copper plating or electroless nickel plating catalyst (metal catalyst) can be used a method of carrying.

On the other hand, in the method (3), when direct electroplating is carried out in the next step, generally, a colloid of stannous chloride and palladium chloride having negative charges is used as catalyst particles, and the catalyst is first subjected to catalyst-listing. A method is used in which a colloidal substance of tin and palladium is deposited on the surface of a molded article having polarity, and then tin is replaced with copper. Further, in the electroless copper plating or electroless nickel plating step (c) in the methods (1) and (2), the copper ion or the electroless nickel plating is applied to the surface of the molded article that has undergone the catalyst supporting step (b). In this step, nickel ions are reduced and precipitated to form a copper or nickel film. The method of electroless copper plating or electroless nickel plating is not particularly limited, and a method conventionally used in plating a plastic molded product can be used.
For example, by immersing the molded product obtained in the above step (b) in an aqueous solution of a copper salt or a nickel salt containing a reducing agent at about 10 to 50 ° C. for about 2 to 20 minutes, copper plating or nickel plating is performed on the surface thereof. A film can be formed.
In the step (c), the electroless copper plating treatment is performed as described above, and the formed copper plating film is activated by an ordinary method. A treatment may be performed to form a nickel plating film.

Finally, (d) the electroplating step, in the above method (2), comprises electroplating the electroless copper plating film or the electroless nickel plating film provided in the step (c). On the other hand, in the method (3), the electroplating is performed directly on the surface of the molded article treated in the step (b). There is no particular limitation on the electroplating method, and a method conventionally used for plating a plastic molded product can be used. The type of plating is not particularly limited, and may be appropriately selected according to the use of the plated product. By this electroplating process, a single metal film or a multi-layer film of a plurality of metals can be provided. Generally, the uppermost film is made of chromium, such as nickel-chromium or copper-nickel-chromium. In many cases, a multilayer coating is provided. The plated product obtained by the method (1) is generally used for various electromagnetic wave shields (E
MI shield) components, for example, EMI shield components for automobiles, EMI shield components for electric vehicles, and EMI shield components for various communication devices and OA devices. On the other hand, the plated products obtained by the methods (2) and (3) have been subjected to design plating, for example, bumper corners, bumpers, fenders, radiator grills, spoilers, door handles, bumper moldings, lamp housings. And the like, as well as in the fields of home electric appliances, communication equipment, OA equipment, and housing.

[0028]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Production Example 1 (1) Preparation of reaction product of N-ethylethylenediamine and formamide In a 1-liter flask equipped with a thermometer, stirrer, dropping funnel, and reflux condenser, 44.0 g of N-ethylethylenediamine (5. 0 mol) and then 45 g (1.0 mol) of formamide were slowly added dropwise at room temperature. After completion of the dropwise addition, the mixture was heated and reacted at 80 to 120 ° C. for 9 hours. During this time, generation of ammonia gas was observed. After completion of the reaction, 61
The unreacted N-ethylethylenediamine was distilled off at a temperature of 88 ° C./88 mmHg to obtain a residue. The neutralization equivalent of the residue measured by neutralization titration was 8.59 meq. / G.

(2) Production of Modified Polypropylene Resin Xylene 3 was placed in a 1-liter flask equipped with a thermometer, stirrer, dropping funnel, and Dean-Stark separator.
00 ml and maleic anhydride-grafted polypropylene [Idemitsu Polytack H-10 manufactured by Idemitsu Petrochemical Co., Ltd.]
00P] was heated and dissolved at 140 ° C. under reflux of xylene. Next, 8.9 g of the reaction product of N-ethylethylenediamine and formamide prepared in the above (1) dissolved in 200 ml of DMF was gradually dropped into this flask over 3 hours. During this time, the reaction mixture was kept under the reflux temperature of xylene, and water azeotropic as a result of the imidization reaction was removed outside the reaction system by a Dean-Stark water separator. The reaction was continued at 140 ° C. for 10 hours. When the generation of new water was no longer observed, the reaction was terminated, and the reaction mixture was poured into 5 liters of methanol and collected as a precipitate. The precipitate was washed with methanol and dried, and as a result, the yield was 125.3 g. The resulting modified polypropylene resin is a white powder, soluble in xylene, and dissolved at 10% by weight.
As a result of measuring viscosity (25 ° C.) with a mold viscometer, 145c
ps. When a xylene cast film was prepared and its infrared absorption spectrum was measured, 1772 was obtained.
cm ^-1, the 1662cm ^-1 (shoulder) in addition to the absorption based on imide ring 1700 cm ^-1 had absorbed formamide. However, no absorption based on the amino group was observed. On the other hand, from the nuclear magnetic resonance ⁽¹³ C-NMR) spectrum due to carbon isotope was measured in CDCl _3, imide ring / non Imidomoru ratio is 100/0, the formamide group / amino group molar ratio 100/0 met Was.

Production Example 2 (1) Preparation of p-toluenesulfonate of N- (4-aminobutyl) piperazine 1-liter flask equipped with a thermometer, stirrer, dropping funnel, and Dean-Stark water separator Was charged with 500 ml of 1,3-dimethyl-2-imidazolidinone (DMI), and 95 g (0.5 mol) of p-toluenesulfonic acid monohydrate was dissolved therein at room temperature. Then, N-
72.2 g (0.46 mol) of (4-aminobutyl) piperazine was gradually added and dissolved so that the temperature of the solution did not exceed 20 ° C., and p-type of N- (4-aminobutyl) piperazine was dissolved.
A DMI solution of toluenesulfonate was prepared, from which a residue was obtained. The neutralization equivalent of this product was 2.73 meq.
/ G, and the degree of neutralization was 53.5. (2) Manufacture of modified EPR As raw material copolymer, maleic anhydride-grafted EPR
(0.5% by weight of maleic acid) and the p-toluenesulfonate of N- (4-aminobutyl) piperazine obtained in (1) above, in the same manner as in Production Example 1 (2). To produce a modified EPR. This modified EPR had an imide ring / non-imide molar ratio of 100/0 and a formamide group / amino group molar ratio of 0/100.

Production Example 3 (1) Preparation of p-toluenesulfonic acid salt of m-xylylenediamine In Production Example 2 (1), m-xylylenediamine was used in place of N- (4-aminobutyl) piperazine. Except for the above, the preparation was carried out in the same manner as in Production Example 2 (1), from which a residue was obtained. Its neutralization equivalent is 2.35 meq. / G, and the degree of neutralization was 59.1. (2) Production of Modified SEPS A maleated styrene-isoprene copolymer hydrogenated product (maleated SEPS) was used as a raw material copolymer, and the p-type of m-xylylenediamine obtained in the above (1) was used. A modified SEPS was produced in the same manner as in Production Example 1 (2) using a toluenesulfonic acid salt. This modified SEPS
Has an imide ring / non-imide molar ratio of 100/0 and a formamide / amino group molar ratio of 65/35.

Example 1 Polypropylene (trade name: ID, manufactured by Idemitsu Petrochemical Co., Ltd.)
EMITSU PPJ-762HP, MI: 12 g / 1
0 minutes (230 ° C., 2.16 kgf)] 69 parts by weight, 30 parts by weight of calcium carbonate powder having an average particle diameter of 0.8 μm and 1 part by weight of the modified polypropylene resin obtained in Production Example 1 are dry-blended and then biaxially mixed. The mixture was kneaded with a kneader to obtain pellets. After drying the obtained pellets, 1
A flat plate of 40 × 140 × 3 mm was prepared. The flat plate was subjected to an etching treatment with a mixed solution of dichromic acid / sulfuric acid, washed with water and neutralized, and thereafter, without applying a polarity-imparting treatment, adsorbed and supported colloidal particles of stannous chloride / palladium chloride as a catalyst. . Next, as an accelerator, palladium was reduced to precipitate metal palladium. afterwards,
After performing electroless copper plating, electroplating was further performed in the order of nickel and chromium. Table 1 shows the evaluation results of the obtained plated products.

Example 2 Polypropylene (trade name: ID, manufactured by Idemitsu Petrochemical Co., Ltd.)
EMITSU PPE-250G, MI: 0.9 g / 10
(230 ° C., 2.16 kgf)] 73 parts by weight, 25 parts by weight of calcium carbonate powder having an average particle diameter of 0.2 μm and 2 parts by weight of the modified EPR obtained in Production Example 2 are dry-blended and then mixed in a twin-screw kneader. And kneaded to obtain pellets. After drying the obtained pellets, a sheet having a thickness of 3 mm was formed by a sheet extruder. Cut this sheet, 100x1
A sheet test piece of 00 × 3 mm was prepared. This sheet test piece is subjected to etching treatment with a mixed solution of dichromic acid / sulfuric acid, washed with water and neutralized, and then adsorbed and carried colloidal particles of stannous chloride / palladium chloride as a catalyst without performing a polarity imparting treatment. I let it. Next, as an accelerator, palladium was reduced to precipitate metal palladium. Thereafter, an electroless copper plating treatment was performed to uniformly deposit copper on the sheet surface. Next, as an activator, after activating the copper surface, electroless nickel plating was performed. Table 1 shows the evaluation results of the obtained plated products.

Example 3 Polypropylene (trade name: ID, manufactured by Idemitsu Petrochemical Co., Ltd.)
EMITSU PPJ-762HP] 69 parts by weight, 30 parts by weight of calcium carbonate powder having an average particle diameter of 0.8 μm, 1 part by weight of the modified SEPS obtained in Production Example 3, and 15 parts by weight of EPR are dry-blended and then kneaded with a twin-screw kneader. And
A pellet was obtained. After drying the obtained pellets, a flat plate of 140 × 140 × 3 mm was prepared by injection molding. The plate was subjected to an etching treatment with a mixed solution of dichromic acid / sulfuric acid, washed with water and neutralized, and then adsorbed and supported with colloidal particles of stannous chloride / palladium chloride as a catalyst without performing a polarity imparting treatment. . Next, after replacing tin with copper, electroplating was performed directly in the order of nickel and chromium. Table 1 shows the evaluation results of the obtained plated products.

Example 4 In Example 1, 0.2 parts by weight of a copper antioxidant (white powder having a melting point of 65 ° C. or more, manufactured by Asahi Denka Kogyo KK, trade name: ADK STAB ZS-27) and 0.2 parts by weight of an antioxidant (Sumitomo Chemical Co., Ltd., trade name: Sumilizer TPD "Sulfur-based")
Example 1 after adding 0.1 part by weight and dry blending.
A pellet was obtained in the same manner as described above, a flat plate was prepared, and plating was performed. Table 1 shows the evaluation results of the obtained plated products. Example 5 In Example 3, 0.2 parts by weight of a copper harm inhibitor (white powder having a melting point of 65 ° C. or higher, manufactured by Asahi Denka Kogyo KK, trade name: ADK STAB ZS-27) and 0.2 parts by weight of an antioxidant (Sumitomo Chemical) (Industrial Co., Ltd., trade name: Sumilyzer TPD "Sulfur-based") 0.1 part by weight was added, and dry blending was performed. Then, pellets were obtained in the same manner as in Example 3, and a flat plate was prepared and plated. . Table 1 shows the evaluation results of the obtained plated products.

Comparative Example 1 The procedure of Example 1 was repeated, except that the modified polypropylene resin was not used. Table 1 shows the evaluation results of the plated products. Comparative Example 2 The same procedure was performed as in Example 1 except that the calcium carbonate powder was not used. Table 1 shows the evaluation results of the plated products. Comparative Example 3 The same operation as in Example 1 was performed, except that the average particle size of the calcium carbonate powder was changed to 23 μm. Table 1 shows the evaluation results of the plated products. Comparative Example 4 In Example 1, the average particle size of the calcium carbonate powder was
The procedure was performed in the same manner as in Example 1 except that the thickness was changed to 0.02 μm. Table 1 shows the evaluation results of the plated products.

Comparative Example 5 The procedure of Example 1 was repeated, except that maleic anhydride-grafted polypropylene was used instead of the modified polypropylene resin. Table 1 shows the evaluation results of the plated products. Comparative Example 6 Same as Example 1 except that the amount of polypropylene was changed to 94.9 parts by weight, the amount of calcium carbonate powder was changed to 5 parts by weight, and the amount of modified polypropylene resin was changed to 0.1 part by weight. Was carried out. The results are shown in Table 1. Comparative Example 7 In Example 2, the amount of polypropylene was 40 parts by weight,
The procedure was performed in the same manner as in Example 2 except that the amount of the calcium carbonate powder was changed to 5 parts by weight and the amount of the modified EPR was changed to 55 parts by weight. Table 1 shows the evaluation results of the obtained plated products.

[0038]

[Table 1]

Note 1) Peeling strength of plating film A 1 cm wide slit was formed in a plated flat plate or sheet, and a 90 ° peeling test was performed to measure the peeling strength of the plating film. 2) Appearance of plated product, etc. The surface of plated flat plate or sheet was visually observed.

[0040]

The polyolefin resin composition of the present invention has a high plating strength and can be subjected to a plating treatment with a small variation without requiring a pre-etching treatment (solvent treatment) step and a polarity imparting step. It is suitably used for applications.

Claims (7)

[Claims] (A) a polyolefin-based resin 40 to 89.
9% by weight, (B) 10 to 50% by weight of acid-soluble inorganic particles having an average particle diameter of 0.03 to 10 μm, and (C) an amino group and / or a formamide group via a hydrocarbon group bonded to a nitrogen atom of an imide ring. A polyolefin-based resin composition comprising at least 0.1 to 20% by weight of at least one selected from a modified olefin-based resin containing an imide ring and a modified styrene-based resin into which is introduced. 2. An antioxidant (D) of 0.01 to 100 parts by weight per total amount of the components (A), (B) and (C).
2.0 parts by weight and / or (E) a metal deactivator 0.01 to 2.
The polyolefin-based resin composition according to claim 1, which contains 0 parts by weight. 3. The polyolefin resin according to claim 1, further comprising (F) 1 to 80 parts by weight of a thermoplastic elastomer per 100 parts by weight of the total amount of the components (A), (B) and (C). Composition. 4. The polyolefin resin composition according to claim 1, which is used for plating. 5. A plated molded article obtained by plating a molded article comprising the polyolefin resin composition according to claim 4. 6. A molded article comprising the polyolefin-based resin composition according to claim 4, which is sequentially subjected to an etching treatment, a catalyst-carrying treatment, an electroless copper plating and / or an electroless nickel plating treatment, and optionally an electroplating treatment. A method for producing a plated product, characterized by the following. 7. A method for producing a plated molded article, comprising sequentially performing an etching treatment, a catalyst carrying treatment, and an electroplating treatment on a molded article made of the polyolefin resin composition according to claim 4.