JP7143063B2 - Plating improver, molded article for plating, molded article and plating method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a plating improver, a molding for plating, a plating molding and a plating method. More specifically, the present invention relates to a plateability improver that gives a molded body for plating capable of forming a metal film or alloy film with excellent adhesion on the surface thereof by plating, a molded body for plating containing the same, The present invention relates to a plated compact having a metal film or an alloy film, and a plating method.

Conventionally, a plated compact provided with a metal film or an alloy film obtained by plating the surface of the compact has, for example, a metallic appearance, improved design, durability and weather resistance. It is used in vehicle parts, electric/electronic parts, OA equipment parts, household appliances, housing parts, clothing accessories, etc. for the purpose of enhancing, antistatic, conducting, and electromagnetic wave shielding properties.
As a plating method for the molded body, etching (surface roughening), neutralization, catalyst application, activation, electroless plating, acid activation, electroplating, etc. are successively carried out, so-called catalyst accelerator. The Later method and, among these, the direct plating method, which omits the electroless plating process, are known.

As a thermoplastic resin composition which is excellent in moldability, impact resistance, etc., and provides a molded body suitable for forming a metal layer or an alloy layer on the surface thereof by plating, a composition mainly composed of ABS resin is known. ing. (Patent Documents 1, 2, etc.)

JP-A-2002-338636 JP 2007-177223 A

With the expansion of the use of plated molded articles, there is a need for a plating composition that provides a molded article with excellent adhesion to a metal layer produced by plating. In addition, when an impact is applied to the molded body, if the molded body undergoes brittle fracture, fragments will scatter. In order to suppress this, there is a need for a plating composition for producing compacts that undergo ductile fracture upon impact.

The present invention is a molded article that has a tendency to undergo ductile fracture against impact from the outside, has excellent impact resistance, and is capable of forming a metal layer or alloy layer with excellent adhesion on the surface thereof by plating. An object of the present invention is to provide a plating improver that gives a (plating compact), a plating compact containing the same, a plated compact having a metal layer or an alloy layer, and a plating method.

The present invention has been made to solve at least part of the problems described above, and can be implemented as the following aspects or application examples.

Application example 1
One embodiment of the plating improver of the present invention contains heterophasic polymer particles having a coefficient of variation of particle size of 40 to 90%.

Application example 2
In the hetero-phase polymer particles, the content of polymer particles having a particle diameter of 0.05 μm or more is 80% by volume or more of the total hetero-phase polymer particles, and the content is 0.05 μm or more and less than 0.15 μm. The content of polymer particles having a particle size is preferably 10 to 60% by volume based on the total heterophase polymer particles.

Application example 3
Another embodiment of the plating improver of the present invention further contains water.

Application example 4
One aspect of the molded article for plating of the present invention contains the plating improver according to any one of Application Examples 1 to 3 and a thermoplastic resin.

Application example 5
The content ratios of the heterophase polymer particles and the thermoplastic resin contained in the plating improver are 10 to 80% by mass and 20 to 90% by mass, respectively, when the total of both is 100% by mass. is preferred.

Application example 6
One aspect of the plated article of the present invention comprises the plated article described in Application Example 4 or 5, and a plated layer provided on the surface of the plated article.

Application example 7
One aspect of the plating method of the present invention is a method for forming a plating layer on the molding for plating according to Application Example 4 or 5, wherein the molding for plating is etched at 30 to 80°C. , a method of forming a plating layer.

The plating improver and the molding for plating of the present invention are suitable for forming a metal layer or an alloy layer having excellent adhesion. And it is excellent in impact resistance against impact from the outside.
According to the molded article for plating of the present invention, a plated molded article excellent in the formability of a metal layer such as a copper layer or an alloy layer by plating and the adhesion of these layers to a substrate is provided.
Since the plated compact of the present invention has excellent adhesion of the metal layer or alloy layer to the base molding portion, it also has excellent appearance.
According to the plating method of the present invention, it is possible to efficiently form a metal layer or an alloy layer having excellent adhesion to the undercoat portion.

FIG. 2 is a cross-sectional view of a hetero-phase polymer particle having a core-shell hetero-phase structure; FIG. 2 is a cross-sectional view of a heterophasic polymer particle having an island-in-sea heterophasic structure. FIG. 2 is a cross-sectional view of a heterophase polymer particle having an octopus-like heterophase structure. FIG. 4 is a cross-sectional view of another heterophase polymer particle having a octopus-like heterophase structure; FIG. 2 is a cross-sectional view of a heterophasic polymer particle having a side-by-side heterophasic structure. FIG. 2 is a cross-sectional view of a heterophase polymer particle having a multiparticle heterophase type heterophase structure. FIG. 2 is a cross-sectional view of a heterophase polymer particle having a raspberry-like heterophase structure; FIG. 4 is a cross-sectional view of a heterophasic polymer particle having another multiparticle heterophasic heteromorphic structure. FIG. 2 is a cross-sectional view of a heterophase polymer particle having a barrel-shaped heterophase structure.

Preferred embodiments of the present invention will be described in detail below. It should be understood that the present invention is not limited only to the embodiments described below, but includes various modifications implemented within the scope of the present invention.
In the present specification, "(meth)acrylic acid" is a concept encompassing both "acrylic acid" and "methacrylic acid". "-(Meth)acrylate" is a concept that includes both "-acrylate" and "-methacrylate". In addition, "(meth)allyl" is a concept encompassing both "allyl" and "methallyl".

1. Plating Improver The plating improver of the present invention is characterized by containing heterophasic polymer particles having a coefficient of variation in particle size of 40 to 90%. The plating improver of the present invention may contain other components (described later) as necessary.

When a molding for plating is produced using a composition containing a plating improver containing the heterophasic polymer particles according to the present invention and a thermoplastic resin, the heterophasic polymer particles are contained inside the molding. exposed to its surface. When electroplating or the like is applied to this molding for plating, the surface of the molding for plating is first subjected to a treatment such as being brought into contact with an etchant. The heterophasic polymer particles are removed to form depressions on the surface of the compact. It is presumed that the concave portions formed in this manner function as anchor holes that improve the adhesion of the plating film, and that a plating film exhibiting good adhesion strength can be produced.
Each component contained in the plating improver of the present invention will be described in detail below.

1-1. Heterophasic Polymer Particles The heterophasic polymer particles according to the present invention are particles composed of two or more different phases rather than a homogeneous phase.
The cross-sectional structure of the heterophase polymer particles includes a core-shell heterophase structure (Fig. 1), an island-in-sea heterophase structure (Fig. 2), an octopus-like heterophase structure (Figs. 3 and 4), and a juxtaposed type (Fig. side-by-side) hetero-phase structure (Fig. 5), raspberry-like hetero-phase structure (Fig. 7), multi-particle hetero-phase structure (Figs. 6 and 8), barrel-like hetero-phase structure (Fig. 9), and the like. Of these heterogeneous structures, the core-shell heteromorphic structure (FIG. 1) is preferred. The plating property improver of the present invention may contain one hetero-phase particle formed by combining two or more of the various hetero-phase structures as described above.

The heterophase polymer particles are preferably single particles formed by two or more polymers with different chemical structures or two or more block-structured polymers with different chemical structures.
When the above heterophasic polymer particles are composed of two or more polymers having different chemical structures, a polymer having a chemical structure with excellent mechanical properties such as impact resistance is used in combination with the plating improver of the present invention. It is preferably combined with a polymer having a chemical structure that has a high affinity with the thermoplastic resin (styrene resin, acrylic resin, polycarbonate resin, polyamide resin, polyester resin, etc.) to be used. Further, when the heterophase polymer particles are composed of a polymer having two or more block structures with different chemical structures, a block having a chemical structure excellent in mechanical properties such as impact resistance and a thermoplastic resin are combined. It is preferable to have a block having a chemical structure with a high affinity for and phase-separate to form a hetero-phase structure.

Homogeneous polymer particles composed of a single polymer having a chemical structure with excellent mechanical properties such as impact resistance, and a single polymer having a chemical structure with a high affinity for thermoplastic resins. In a composition obtained by kneading homogenous polymer particles composed of It is difficult to disperse uniformly in resin. However, the heterophasic polymer particles contained in the plating improver of the present invention are single particles formed by two or more polymers having different chemical structures as described above or polymers having two or more block structures with different chemical structures. In the case of particles, non-homogeneous dispersion in the thermoplastic resin due to differences in polymers can be suppressed, and uniform mixing in the thermoplastic resin can be facilitated.

The heterophasic polymer particles are uniformly exposed on the surface of the molding for plating according to the present invention, which is produced using a composition in which the above heterophasic polymer particles are uniformly dispersed in a thermoplastic resin. When plating is performed to form a metal film or an alloy film on a molding for plating, the exposed heterophase polymer particles are etched (surface roughening) by, for example, bringing the surface of the molding for plating into contact with an etchant. Removed by processing. As a result, uniform anchor holes are formed on the surface of the compact. It is presumed that by forming a plating layer on the surface of the formed body having anchor holes thus produced, a plating film exhibiting good adhesion strength can be produced.

When the heterophasic polymer particles are composed of two or more polymers having different chemical structures, one of the polymers is the polymer A having a chemical structure excellent in mechanical properties such as main impact resistance. and the mass ratio (A/B) of the polymer B having a chemical structure having a high affinity with another main thermoplastic resin is preferably 1/0.1 to 1/1.5, more It is preferably 1/0.3 to 1/1. Further, the ratio of the total amount of the polymer A and the polymer B is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 85% by mass or more with respect to the whole heterophasic polymer particles. .

When the heterophasic polymer particles are composed of a polymer having two or more block structures with different chemical structures, the proportion of the block structure in the polymer is one of the main impact resistance properties of the polymer. The mass ratio (A'/B' ) is preferably 1/0.1 to 1/1.5, more preferably 1/0.3 to 1/1. Further, the ratio of the total amount of the block structure A' and the block structure B' is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 85% by mass or more with respect to the whole heterophasic polymer particles. is.

In the molding for plating produced by using the plating improver of the present invention containing the above-mentioned hetero-phase polymer particles and a thermoplastic resin, the hetero-phase polymer particles exposed on the surface are removed by etching to form anchors. It is speculated that it forms holes and then gives a plating film that develops good adhesion strength. However, heterophasic polymer particles that are not exposed on the surface of the molding for plating remain inside the molding for plating without being removed by etching, and affect the mechanical strength of the molding.
However, it has one major polymer A having a chemical structure with excellent mechanical properties such as impact resistance, and another major polymer B having a chemical structure having a high affinity with thermoplastic resins. Heterophase polymer particles, or block structure A' having one main chemical structure with excellent mechanical properties such as impact resistance, and another main chemical structure having high affinity with thermoplastic resins By containing the heterophasic polymer particles having the block structure B′ in the above preferred configuration, a plated compact exhibiting good mechanical properties is produced without significantly deteriorating the mechanical strength of the plated compact after etching. can do.

The particle size of the heterophasic polymer particles contained in the plating improver of the present invention is not particularly limited, but is preferably in the range of 0.03 to 1 μm.
The average particle size of the heterophase polymer particles is preferably in the range of 50 nm to 400 nm, more preferably in the range of 80 nm to 250 nm. When the average particle size of the heterophasic polymer particles is within the above range, when plating is performed on a molding for plating containing a plating improver containing the heterophasic polymer particles, etching (surface roughening) , fine anchor holes can be efficiently formed, and the adhesion of the metal film or alloy film after plating can be further improved.
The average particle size of the heterophase polymer particles was obtained by dyeing the heterophase polymer particles with osmium tetroxide and then observing the dyed polymer particles with a transmission electron microscope. For example, 200 particles can be selected arbitrarily and calculated using analysis software.

In the present invention, the coefficient of variation of the particle size of the heterophasic polymer particles is such that a molding for plating with excellent impact resistance is obtained, and when this molding for plating is plated, the adhesiveness to the base molding part is excellent. It is 40 to 90%, preferably 40 to 80%, more preferably 45 to 75%, since a metal layer or alloy layer can be efficiently formed.
The coefficient of variation can be obtained from the following formula using the volume average particle size of the heterophasic polymer particles and the standard deviation of the particle size distribution.
Variation coefficient (%) = (standard deviation / volume average particle size) x 100
The particle size of the heterophase polymer particles can be measured by observing the particles stained with osmium tetroxide with a transmission electron microscope and analyzing the TEM image, as described above. Deviations can be calculated from particle size measurements.

In the present invention, the content ratio R1 of heterophasic polymer particles having a particle diameter of 0.05 μm or more is preferably 80% by volume or more, more preferably 90% by volume or more. In addition, the content ratio R2 of the hetero-phase polymer particles having a particle diameter of 0.05 μm or more and less than 0.15 μm is preferably 10 to 60 volume, more than It is preferably 20 to 50% by volume. When the content ratios R1 and R2 of the heterophase polymer particles have the above structure, the impact resistance of the molding for plating produced using the plating improver and the thermoplastic resin and the adhesion of the metal layer formed by plating are improved. can be improved.
The content ratio R1 is calculated by the following formula, where V1 is the total volume of the heterophasic polymer particles having a particle diameter of 0.05 μm or more, and V is the total volume of the heterophasic polymer particles contained in the plating improver. can be calculated.
R1 = (V1/V) x 100
Furthermore, the content ratio R2 is defined by V2 being the total volume of the heterophasic polymer particles having a particle diameter of 0.05 μm or more and less than 0.15 μm, and V being the total volume of the heterophasic polymer particles contained in the plating improver. , can be calculated by the following formula.
R2 = (V2/V) x 100

The variation coefficient of the particle size of the heterophase polymer particles can be controlled by the conditions for producing the heterophase polymer particles. Moreover, the coefficient of variation may be controlled by preparing two or more types of heterophasic polymer particles in advance and using them in combination. For example, when controlling the coefficient of variation by using two kinds of heterophasic polymer particles (A1) and heterophasic polymer particles (A2) having different sizes from each other, the particle diameter of the heterophasic polymer particles (A1) is preferably 50. 150 nm, more preferably 60 to 120 nm, and the particle diameter of the heterophasic polymer particles (A2) is preferably 200 to 800 nm, more preferably 250 to 700 nm.

As described above, the heterophasic polymer particles of a preferred embodiment contain two or more polymers with different chemical structures or a polymer with two or more block structures with different chemical structures. In the present invention, a repeating unit derived from a conjugated diene (hereinafter referred to as "repeating unit (r1)"), which contributes to mechanical properties such as impact resistance, and a thermoplastic resin used in combination with the plating improver of the present invention Two or more polymers with different chemical structures containing a repeating unit having a functional group having a high affinity with the resin (hereinafter referred to as "repeating unit (r2)") or a polymer having two or more block structures with different chemical structures It preferably contains coalescence.
The repeating units contained in the polymer constituting such heterophasic polymer particles are described below.

By using heterophasic polymer particles having a repeating unit (r1) derived from a conjugated diene together with a thermoplastic resin, it is possible to produce a molding for plating having excellent mechanical properties such as impact resistance. In addition, the repeating unit (r1) may be of one type or two or more types.

Conjugated dienes include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene and the like. Among these, 1,3-butadiene is particularly preferred. The repeating units derived from the conjugated diene contained in the heterophasic polymer particles may be of one type or two or more types.

The content of the repeating unit (r1) is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, when the polymer containing the repeating unit (r1) derived from a conjugated diene is 100 parts by mass. be. When the molding for plating contains a plating improver containing heterophasic polymer particles having a repeating unit (r1) derived from a conjugated diene within the above range, the impact resistance can be further improved.
In addition, the heterophasic polymer particles are a total of a polymer having a repeating unit (r1) derived from a conjugated diene in an amount of 45% by mass or more and a repeating unit (r2) having a functional group having a high affinity with a thermoplastic resin. is more preferably 20% by mass or more.

The heterophasic polymer particles may contain repeating units (r2) having a functional group having a high affinity with thermoplastic resins such as styrene resins, acrylic resins, polycarbonate resins, polyamide resins and polyester resins. In this case, when the plating improver containing the hetero-phase polymer particles and the thermoplastic resin are kneaded, the hetero-phase polymer particles can be uniformly dispersed in the thermoplastic resin, and the plating is excellent in mechanical strength. can produce molded articles for

Examples of functional groups having high affinity with the thermoplastic resin include carboxyl group, carboxylic acid ester group, dicarboxylic acid anhydride group, carbonyl group, hydroxyl group, alkoxy group, epoxy group, formyl group, cyano group, amino group, Amide group, imide group, oxazoline group, isocyanate group, sulfoxide group, sulfone group, sulfonic acid group, sulfonate ester group, mercapto group, sulfide group, sulfinyl group, thiocarbonyl group, thiophosphate group, phosphonic acid group, phosphonic acid An ester group and the like can be mentioned. Among these, a carboxylic acid ester group and a cyano group are preferred. The repeating units (r2) contained in the heterophasic polymer particles may be of one type or two or more types.

Monomers that give repeating units containing carboxylic acid ester groups include unsaturated carboxylic acid esters.
As the unsaturated carboxylic acid ester, (meth)acrylic acid ester is preferable, and the (meth)acrylic acid ester includes methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, Isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, (meth)acrylic cyclohexyl acid, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate , Ethylene glycol (meth)acrylate, Ethylene glycol di(meth)acrylate, Propylene glycol di(meth)acrylate, Trimethylolpropane tri(meth)acrylate, Pentaerythritol tetra(meth)acrylate, Hexa(meth)acrylate Examples include dipentaerythritol acrylate and allyl (meth)acrylate. Among these, methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hydroxymethyl (meth)acrylate and hydroxyethyl (meth)acrylate are preferred, and (meth)acrylic acid Methyl, hydroxymethyl (meth)acrylate and hydroxyethyl (meth)acrylate are particularly preferred.

Monomers that give repeating units containing a cyano group include unsaturated nitrile compounds and the like.
The unsaturated nitrile compounds include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile, vinylidene cyanide and the like. Among these, acrylonitrile and methacrylonitrile are preferred, and acrylonitrile is particularly preferred.

The content of the repeating unit (r2) is preferably 3 to 35% by mass, more preferably 5 to 30% by mass, when the total of repeating units contained in the polymer constituting the heterophase polymer particles is 100% by mass. % by mass. When the molding for plating contains a plating improver containing heterophasic polymer particles in which the content of the repeating unit (r2) derived from an unsaturated nitrile compound is within the above range, the mechanical strength is further improved. It becomes possible.

The heterophasic polymer particles may contain repeating units other than the above (hereinafter referred to as "repeating units (r3)"). Examples of the repeating unit (r3) include a repeating unit derived from an aromatic vinyl compound, a repeating unit derived from an unsaturated carboxylic acid, a repeating unit derived from a fluorine-containing compound having an ethylenically unsaturated bond, and an ethylenically unsaturated carboxylic acid. Repeating units derived from alkylamides of acids, repeating units derived from carboxylic acid vinyl esters, repeating units derived from acid anhydrides of ethylenically unsaturated dicarboxylic acids, repeating units derived from aminoalkylamides of ethylenically unsaturated carboxylic acids A unit etc. are mentioned. The repeating units (r3) contained in the heterophasic polymer particles may be of one kind or two or more kinds. Among these, repeating units derived from aromatic vinyl compounds and repeating units derived from unsaturated carboxylic acids are preferred.

Examples of aromatic vinyl compounds include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene and the like. Of these, styrene is preferred.
Unsaturated carboxylic acids include mono- or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and the like. Among these, acrylic acid, methacrylic acid and itaconic acid are preferred.

Examples of fluorine-containing compounds having an ethylenically unsaturated bond include vinylidene fluoride, ethylene tetrafluoride, and propylene hexafluoride.
Examples of alkylamides of ethylenically unsaturated carboxylic acids include (meth)acrylamide and N-methylolacrylamide.
Vinyl carboxylates include vinyl acetate and vinyl propionate.
Aminoalkylamides of ethylenically unsaturated carboxylic acids include aminoethylacrylamide, dimethylaminomethylmethacrylamide, and methylaminopropylmethacrylamide.

In the preferred embodiment of the heterophasic polymer particles described above, the repeating units (r1), (r2) and (r3) may be distributed in any way, but at least the repeating unit (r2) is exposed on the particle surface. preferably.

Next, physical properties of the heterophasic polymer particles will be described.
In the above heterophasic polymer particles, it is preferable that the endothermic peak difference between the phases constituting the particles is 5° C. or more.
In the present invention, the heterophasic polymer particles exhibit two or more endothermic peaks in the temperature range of −100° C. to 200° C. when subjected to differential scanning calorimetry (DSC) in accordance with JIS K7121. Coalesced particles are preferred. Molded articles for plating containing a plating improver containing heterophasic polymer particles having two or more endothermic peaks in this temperature range are excellent in impact resistance and plating adhesion. The two or more endothermic peaks are more preferably in the range of -95°C to 180°C, particularly preferably in the range of -90°C to 160°C.

In addition, a molding for plating containing a plating improver containing heterophasic polymer particles exhibiting two or more endothermic peaks in the temperature range of −100° C. to 0° C. has improved elasticity and better impact resistance. becomes. In this case, the temperature of two or more endothermic peaks is preferably in the range of -95°C to -20°C, more preferably in the range of -90°C to -40°C.
Furthermore, the composition containing the plating improver containing the heterophasic polymer particles exhibiting two or more endothermic peaks in the temperature range of 50°C to 200°C is suitable for melt-kneading in the production of a molding for plating. It has fluidity and excellent moldability. In this case, the temperature of two or more endothermic peaks is preferably in the range of 70°C to 180°C, more preferably in the range of 90°C to 160°C.

The weight average molecular weight (hereinafter also referred to as “Mw”) of the heterophasic polymer particles is preferably 20,000 to 200,000, more preferably 50,000 to 150,000. This Mw is a standard polystyrene conversion value measured by gel permeation chromatography (hereinafter also referred to as "GPC").

The method for producing the heterophasic polymer particles contained in the plating improver of the present invention is not particularly limited, and the particles can be produced by conventionally known methods. For example, two-stage polymerization methods such as emulsion polymerization method, suspension polymerization method, dispersion polymerization method, seed polymerization method, a plurality of polymers are mixed in the presence or absence of a solvent, coagulated and dried, pulverized, Alternatively, a method such as spray drying to obtain a powder can be applied. As a specific example of the method for producing the heterophasic polymer particles used in the present invention, predetermined monomers are polymerized in a conventional manner until the polymerization conversion reaches 20 to 100%, followed by another polymerization. A method of adding monomers to be combined and polymerizing by a conventional method (two-stage polymerization method), or two or more latex-like polymer particles synthesized separately at room temperature to 300 ° C. for 2 to 100 hours. Examples include a method of stirring and mixing to form heterophase polymer particles.

When producing the heterophasic polymer particles of the preferred embodiment, that is, the heterophasic polymer particles containing the repeating unit (r1) derived from a conjugated diene, for example, it is produced by a known polymerization method and has a predetermined average particle size, To an aqueous dispersion (latex) of polymer particles (raw material particles) containing repeating units (r1), a monomer that provides a repeating unit having a functional group that has a high affinity with a thermoplastic resin is added, followed by emulsion polymerization. , it is preferred to apply the grafting method. As this monomer, an aromatic vinyl compound, a vinyl cyanide compound, and the like are preferable. When an aqueous dispersion (latex) in which heterophase polymer particles are dispersed in an aqueous medium is obtained by this graft polymerization, the heterophase polymer particles are precipitated by adding a coagulant, washed with water, and dried. It can be a powder containing As the coagulant, inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride and aluminum chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid, lactic acid and citric acid;

Examples of emulsifiers that can be used in the emulsion polymerization include higher alcohol sulfate salts, alkylbenzenesulfonates, alkyldiphenyl ether disulfonates, aliphatic sulfonates, aliphatic carboxylates, dehydroabietic acid salts, and naphthalene sulfones. anionic surfactants such as acid/formalin condensates and sulfate salts of nonionic surfactants; nonionic surfactants such as polyethylene glycol alkyl esters, polyethylene glycol alkylphenyl ethers, and polyethylene glycol alkyl ethers; Fluorinated surfactants such as perfluorobutylsulfonates, perfluoroalkyl group-containing phosphate esters, perfluoroalkyl group-containing carboxylates, perfluoroalkylethylene oxide adducts, and the like. The number of emulsifiers to be used may be one, or two or more.

As the polymerization initiator, organic peroxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, and paramenthane hydroperoxide are combined with reducing agents such as sugar-containing pyrophosphate formulations and sulfoxylate formulations. redox initiators; persulfates such as potassium persulfate and sodium persulfate; peroxides such as benzoyl peroxide, lauroyl peroxide, tert-butyl peroxylaurate, and tert-butyl peroxy monocarbonate; . The polymerization initiators to be used may be one kind or two or more kinds.

A chain transfer agent can be used in combination during the graft polymerization. Chain transfer agents include mercaptans such as octylmercaptan, n-dodecylmercaptan, tert-dodecylmercaptan, n-hexylmercaptan, n-hexadecylmercaptan, n-tetradecylmercaptan, and tert-tetradecylmercaptan; terpinolene, α -methylstyrene dimer, tetraethylthiuram sulfide, acrolein, methacrolein, allyl alcohol, 2-ethylhexylthioglycol and the like. Only one type of chain transfer agent may be used, or two or more types may be used.

When polymerization is performed by adding a monomer for graft polymerization to an aqueous dispersion of raw material particles containing repeating units (r1) derived from a conjugated diene, the graft ratio in the resulting heterophase polymer particles is preferably 10 to 150% by mass, more preferably 30 to 100% by mass.
In addition, this graft rate is calculated|required by the following formula.
Graft rate (mass%) = {(ST) / T} × 100
(In the formula, S is obtained by putting 1 g of the produced heterophasic polymer particles into 20 ml of acetone, shaking them with a shaker for 2 hours, and then centrifuging to separate and dry the insoluble matter and soluble matter. is the mass (g) of the insoluble matter obtained, and T is the mass (g) of the raw material particles having a repeating unit derived from a conjugated diene, contained in 1 g of the heterophasic polymer particles.)

When a monomer containing an aromatic vinyl compound and a vinyl cyanide compound is used in the above graft polymerization, the ratio of the total amount of the aromatic vinyl compound and the vinyl cyanide compound to the total amount of the monomers is On the other hand, it is preferably 70% by mass or more, more preferably 80% by mass or more.

Manufactured by adding a monomer that gives a repeating unit having a functional group having a high affinity with a thermoplastic resin to an aqueous dispersion of raw material particles containing a repeating unit (r1) derived from a conjugated diene, and graft-polymerizing the monomer. In the formed heterophasic polymer particles, the average thickness of the formed graft sites is preferably 3 to 30 nm, more preferably 4 to 25 nm.
The average thickness of the graft site can be measured by dyeing the heterophasic polymer particles with osmium tetroxide or the like by a known method and observing them with a transmission electron microscope.

The plating improver of the present invention can contain a plurality of heterophasic polymer particles. When the heterophasic polymer particles containing (A12) are produced, an aqueous dispersion containing the heterophasic polymer particles (A11) and an aqueous dispersion containing the heterophasic polymer particles (A12) are mixed, and then A coagulant may be added to the mixture. Alternatively, an aqueous dispersion containing the heterophasic polymer particles (A11) and an aqueous dispersion containing the heterophasic polymer particles (A12) may be coagulated to produce powders, and then mixed. good.

1-2. Other components The plating improver of the present invention includes water, anti-aging agents, antioxidants, ultraviolet absorbers, lubricants, plasticizers, fillers, heat stabilizers, flame retardants, antistatic agents, colorants, and other components. can contain the components of A more preferred embodiment of the present invention is a plating improver containing water. When a molding for plating is produced using a composition containing a plating improver containing water together with a thermoplastic resin, the appearance is excellent, and when plating is performed, the plating film has good adhesion. It is possible to obtain a plated compact with. In this case, the content of water in the plating improver is preferably 0.1 to 1 part by mass, more preferably 0.2 to 0.5 part by mass, with respect to 100 parts by mass of the heterophasic polymer particles. be.
The amount of water contained in the plating improver of the present invention can be quantified in accordance with JIS K7251 "Plastics - Method for Determining Moisture Content" B method (Karl Fischer method).

Generally, it has been believed that water vaporizes at a high temperature when the composition is subjected to molding and impairs the appearance of the resulting molded product. For this reason, in the thermoplastic resin composition, it has been common sense in the industry to try to avoid contamination with water as much as possible.
However, when a molded body for plating is produced using a composition containing a plating improver containing water in the above content, excellent plating properties are exhibited. Although the mechanism of this expression is not clear, the present inventors speculate that it results from the following actions.

In the molded product for plating, it is necessary to have suitable unevenness on the surface in order to improve the adhesion strength of the plating film formed on the surface. As described above, the heterophasic polymer particles, which are essential components of the plating property improver of the present invention, are not only present inside the molding for plating but are also exposed on the surface. When exposed, the exposed heterophasic polymer particles are removed and anchor pores are formed. On the other hand, the heterophasic polymer particles that are contained inside the molding for plating and are not exposed on the surface remain inside even after etching and affect the mechanical strength of the molding. Therefore, by blending a large amount of heterophasic polymer particles in a composition for producing a molded article for plating, many anchor holes can be formed on the surface of the molded article, and the adhesion strength of the plating film can be improved. , the mechanical strength itself of the molded body also changes significantly.
However, the moisture vaporized by heating during molding, moves from the interior of the molding for plating to the surface, and desorbs while moderately roughening the surface of the molding, has such an effect on the mechanical strength of the molding itself. is assumed to be small. As a result, by using a plating improver containing water as well as heterophasic polymer particles, anchor holes can be formed more effectively on the surface of the molded product while minimizing changes in the mechanical strength of the molded product itself. It is considered that the adhesion strength of the plated film was improved by forming it.

The amount of water in the plating improver of the present invention can be controlled, for example, by appropriately selecting a drying method after coagulation when heterophasic polymer particles are produced by emulsion polymerization. A specific example thereof is heat treatment at a temperature and time suitable for the synthesized heterophasic polymer particles using a dryer such as a dehumidifying dryer, a vacuum dryer, or a hot air dryer.

Components other than water are exemplified below.
Antiaging agents include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivative compounds, monophenol compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds, and thiobisphenol. compounds, hindered phenol compounds, phosphite ester compounds, imidazole compounds, nickel dithiocarbamate compounds, phosphoric acid compounds, and the like.
Antioxidants include hindered amine-based compounds, hydroquinone-based compounds, hindered phenol-based compounds, sulfur-containing compounds, phosphorus-containing compounds, and the like.
Examples of ultraviolet absorbers include benzophenone compounds, benzotriazole compounds, triazine compounds, and the like.
Lubricants include waxes, silicones, lipids, and the like.
Plasticizers include phthalates, trimellitates, pyromellitic esters, aliphatic monobasic esters, aliphatic dibasic esters, phosphoric esters, esters of polyhydric alcohols, epoxy plasticizers, polymers type plasticizers, chlorinated paraffins, and the like.

Fillers include heavy calcium carbonate, colloidal calcium carbonate, light calcium carbonate, magnesium carbonate, zinc carbonate, aluminum hydroxide, magnesium hydroxide, carbon black, clay, talc, fumed silica, calcined silica, precipitated silica, pulverized Silica, fused silica, kaolin, diatomaceous earth, zeolite, titanium oxide, quicklime, iron oxide, zinc oxide, barium oxide, aluminum oxide, magnesium oxide, aluminum sulfate, glass fiber, carbon fiber, glass balloon, shirasu balloon, saran balloon , phenol balloons, and the like.
Examples of heat stabilizers include phosphite-based heat stabilizers, lactone-based heat stabilizers, hindered phenol-based heat stabilizers, sulfur-based heat stabilizers, and amine-based heat stabilizers.

Examples of flame retardants include organic flame retardants, inorganic flame retardants, and reactive flame retardants.
Examples of organic flame retardants include brominated epoxy compounds, brominated alkyltriazine compounds, brominated bisphenol epoxy resins, brominated bisphenol phenoxy resins, brominated bisphenol polycarbonate resins, brominated polystyrene resins, and brominated crosslinked polystyrene resins. , brominated bisphenol cyanurate resin, brominated polyphenylene ether, decabromodiphenyl oxide, tetrabromobisphenol A and halogen-based flame retardants such as oligomers thereof; trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, tri hexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, etc. Phosphorus-based flame retardants such as phosphate esters, modified compounds thereof, condensed phosphate ester compounds, phosphazene derivatives containing elemental phosphorus and elemental nitrogen; guanidine salts, silicone-based compounds, phosphazene-based compounds, and the like.
Examples of inorganic flame retardants include aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zirconium compounds, molybdenum compounds, and zinc stannate.
Reactive flame retardants include tetrabromobisphenol A, dibromophenol glycidyl ether, brominated aromatic triazine, tribromophenol, tetrabromophthalate, tetrachlorophthalic anhydride, dibromoneopentyl glycol, and poly(pentabromobenzyl polyacrylate). , chlorendic acid (hetic acid), chlorendic acid anhydride (hetic acid anhydride), brominated phenol glycidyl ether, dibromocresyl glycidyl ether, and the like.

2. Molded article for plating The molded article for plating of the present invention is an article containing a plating improver and a thermoplastic resin. The molded body for plating of the present invention is produced by subjecting a composition containing a plating improver and a thermoplastic resin or a component thereof to an injection molding machine, a press molding machine, a calender molding machine, a T-die extrusion molding machine, or a profile extrusion molding machine. etc., can be conventionally manufactured by processing with a known molding apparatus.

The content ratio of the heterophasic polymer particles and the thermoplastic resin contained in the molding for plating of the present invention is suitable for forming a metal layer or alloy layer with excellent adhesion on the surface, and is resistant to external impact. Since a molding for plating with excellent impact resistance can be obtained efficiently, when the total of both is 100% by mass, it is preferably 10 to 80% by mass and 20 to 90% by mass, more preferably 15 to 90% by mass. 70% by mass and 30 to 85% by mass, more preferably 20 to 60% by mass and 40 to 80% by mass.

Examples of the thermoplastic resin include ABS resin, acrylonitrile-styrene copolymer, acrylonitrile-styrene-maleimide compound terpolymer, polystyrene, styrene-based resin such as styrene-maleic anhydride copolymer; polymethyl methacrylate, etc. polycarbonate resins; polyamide resins; polyester resins such as polybutylene terephthalate; or alloys containing at least two of these. Of these, styrene-based resins are preferred, and ABS resins are particularly preferred because the heterophasic polymer particles contained in the plating improver are uniformly dispersed and the mechanical strength is superior.

When the thermoplastic resin contains an ABS resin, the content of the heterophasic polymer particles derived from the plating improver is preferably 30 to 180 parts by mass, more preferably 50 parts by mass, based on 100 parts by mass of the thermoplastic resin. ~150 parts by mass.
When the thermoplastic resin contains an alloy of an ABS resin and a polycarbonate resin, the content of the heterophase polymer particles derived from the plating improver is preferably 15 to 90 parts per 100 parts by mass of the thermoplastic resin. parts by mass, more preferably 25 to 75 parts by mass. In terms of the impact resistance of the molding for plating and the adhesion strength of the plating film, the ratio of the polycarbonate resin to 100 parts by weight of the ABS resin is preferably 100 to 1000 parts by weight.

The molding for plating of the present invention contains other components such as an antioxidant, an antioxidant, an ultraviolet absorber, a lubricant, a plasticizer, a filler, a heat stabilizer, a flame retardant, an antistatic agent and a colorant. be able to.

By subjecting the molded body for plating of the present invention to a known plating method such as a catalyst accelerator method, a direct plating method, a chromium-free plating method, or the like, efficient formation of anchor holes and further , excellent precipitation and growth properties of the metal or alloy can be obtained, and a metal layer or alloy layer having excellent adhesion to the substrate and excellent appearance can be formed.

3. Plated molded article The plated molded article of the present invention is an article having a plated layer containing a metal or alloy on at least a part of the surface of the molded article for plating. The thickness of the plating layer is preferably 5-200 μm, more preferably 5-150 μm.

In the plated molded article of the present invention, the base molded part on which the plating layer (metal layer or alloy layer) is formed includes recesses formed by desorption of the heterophase polymer particles. , excellent adhesion to the plating layer, and excellent appearance of the plating molded product.

The plated molded product of the present invention can be produced by plating the surface of the plated molded product by applying a known method. For example, a catalyst-accelerator method in which processes such as etching (surface roughening), neutralization, catalyst application, activation, electroless plating, acid activation, and electroplating are sequentially performed on a molding for plating. Alternatively, a plated layer can be formed by a direct plating method, which omits the electroless plating step in the catalyst-accelerator method, to produce a plated compact.

The plated molded article of the present invention can be used for vehicle parts, electric appliances, electronic parts, housings, frames, handles and the like.

4. Plating Method The plating method of the present invention is a method of forming a plating layer after etching a molding for plating at 30 to 80°C.
The etchant used in the etching step is not particularly limited, but may include dichromic acid, dichromic acid/sulfuric acid mixture, chromic anhydride, chromic anhydride/sulfuric acid mixture, and the like. In this etching step, the temperature of the etchant changes the etching state and affects the size of the anchor hole. Therefore, the temperature of the etchant is 30 to 80.degree. If the temperature of the etchant is too low, formation of anchor holes will be insufficient. On the other hand, if the temperature of the etchant is too high, overetching will occur.
In the subsequent plating process, the method described above can be applied.

5. Examples Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples.

5-1. Synthesis of Heterophase Polymer Particles Synthesis Example 1
A stainless steel autoclave equipped with a stirring device, a heating and cooling device, a thermometer, and each raw material addition device was charged with 150 parts by mass of ion-exchanged water, 100 parts by mass of 1,3-butadiene, 0.5 parts by mass of tert-dodecyl mercaptan, and a high-grade 4 parts by mass of fatty acid sodium, 0.8 parts by mass of sodium carbonate, 0.075 parts by mass of potassium hydroxide and 0.15 parts by mass of potassium persulfate are charged and reacted at 80° C. for 5 hours to obtain diene polymer particles (hereinafter referred to as A water dispersion (latex) of "raw material particles L1") was obtained.

Laser Doppler/frequency analysis was performed using a Nikkiso Co., Ltd. “Microtrac UPA150 particle size analyzer” to measure the volume average particle size of the raw material particles L1. As a result, the volume average particle size of the raw material particles L1 was 83 nm. The standard deviation of the distribution was 3 nm.

Next, in a glass flask equipped with a stirrer, in a nitrogen stream, latex containing 40 parts by mass of raw material particles L1, 0.2 parts by mass of sodium pyrophosphate, and 0.004 parts by mass of ferrous sulfate heptahydrate Parts by mass and 0.3 parts by mass of glucose dissolved in 8 parts by mass of ion-exchanged water were charged, and stirred at an internal temperature of 70 ° C. to 30 parts by mass of ion-exchanged water, 0.5 parts by mass of potassium rosinate, and styrene. 45 parts by weight, 15 parts by weight of acrylonitrile, 0.45 parts by weight of tert-dodecyl mercaptan and 0.25 parts by weight of cumene hydroperoxide were continuously added over 3.5 hours. Then, this reaction solution was further stirred for 1 hour to obtain an aqueous dispersion (latex) of heterophase polymer particles P1.
After that, 0.5 part by mass of an anti-aging agent was added, and then an aqueous solution of sulfuric acid was added to solidify and dry to obtain a powder of heterophase polymer particles P1.

1 g of heterophasic polymer particles P1 was put into 20 ml of acetone and shaken for 2 hours. Next, centrifugation was performed until the mixture was completely separated into two layers, and the insoluble matter was collected, dried and solidified, and then the mass (S grams) of the insoluble matter was measured. Since the mass of the raw material particles contained in 1 g of the heterophasic polymer particles P1 is known (T grams), a graft ratio of 78% was obtained from the following formula.
Graft rate = 100 × (ST) / T

In addition, after drying and solidifying the acetone-soluble content obtained when obtaining the graft ratio, that is, the ungrafted (co)polymer, the sample dissolved in THF was subjected to GPC using a differential refractive index detector. It was measured and the weight average molecular weight (Mw) calculated from standard polystyrene was 103,000.
Furthermore, the acetone-soluble portion, that is, the content of structural units derived from a vinyl cyanide compound (acrylonitrile) constituting the ungrafted (co)polymer (vinyl cyanide compound unit amount) was measured. Nitrogen was quantified by elemental analysis of the sample, and the unit amount of the vinyl cyanide compound was calculated from the obtained nitrogen amount to be 25%.

1 g of heterophasic polymer particles P1 was put into 20 ml of acetone and shaken for 2 hours. Then, centrifugation was performed until the two layers were completely separated, and the insoluble matter was recovered and redispersed in acetone. A sample for particle measurement was prepared by diluting 40 μl of this dispersion with 100 g of water, placing this diluted solution on a TEM grid, and drying it.
The sample was then brought into contact with osmium tetroxide vapor generated by heating to dye the heterophasic polymer particles P1. Using a transmission electron microscope "JEM-1400Plus" manufactured by JEOL Ltd., arbitrarily 200 particles were observed at a magnification of 2500 times, and it was confirmed that a stained part and a non-stained part with different phases exist in one particle. did. As a result, the heterophase polymer particles P1 were found to be the core-shell type heterophase polymer particles shown in FIG.
The obtained TEM image was analyzed using image analysis software "Image-Pro Plus Ver.4.0 for Windows (registered trademark)" to measure the volume average particle diameter of the heterophase polymer particles P1, which was 90 nm. . In addition, the volume of all particles is calculated, and the volume % of particles present in the particle size range of 0.05 μm or more and less than 0.15 μm, and the particles having a particle size of 0.15 μm or more and 0.5 μm or less The volume percent of particles present in the diameter interval was calculated. Table 1 shows the results.

Further, the heterophasic polymer particles P1 were subjected to differential scanning calorimetry (DSC) according to JIS K7121 to observe the glass transition temperature Tg. Two Tgs were observed, -81°C and 103°C.

Synthesis Examples 2-7
Raw material particles L2 to L7 were obtained in the same manner as in the production of raw material particles L1 in Synthesis Example 1, except that the amount of electrolyte used and the polymerization time were appropriately adjusted. The glass transition temperature, volume average particle size, and standard deviation of the particle size distribution of the raw material particles L2 to L7 were evaluated in the same manner as in Synthesis Example 1. Table 1 shows the results.
Next, using each latex containing the raw material particles L2 to L7, the same operation as in Synthesis Example 1 was performed except that the amount of the polymerization initiator or chain transfer agent used was appropriately adjusted to obtain the heterophasic polymer particles P2 to L7. P7 was synthesized. The physical properties of the heterophasic polymer particles P2 to P7 were also evaluated in the same manner as in Synthesis Example 1. Table 1 shows the results.

Synthesis example 8
150 parts by mass of ion-exchanged water, 50 parts by mass of 1,3-butadiene, and 0.3 parts of tert-dodecyl mercaptan were placed in a stainless steel autoclave equipped with a stirring device, a heating/cooling device, a thermometer, each raw material addition device, and an auxiliary agent addition device. Parts by mass, 2 parts by mass of sodium higher fatty acid, 0.075 parts by mass of potassium hydroxide and 0.15 parts by mass of potassium persulfate were charged, and polymerization was initiated at 80°C. After 3 hours, 50 parts by mass of 1,3-butadiene and 0.3 parts by mass of tert-dodecylmercaptan were added, and the polymerization was continued for 4 hours to obtain an aqueous dispersion of raw material particles L8. The glass transition temperature, volume average particle size, and standard deviation of the particle size distribution of the obtained raw material particles L8 were evaluated in the same manner as in Synthesis Example 1. Table 1 shows the results.
Next, heterophase polymer particles P8 were synthesized in the same manner as in Synthesis Example 1 except that a latex containing raw material particles L8 was used and the amount of polymerization initiator or chain transfer agent used was appropriately adjusted. The physical properties of the heterophasic polymer particles P8 were also evaluated in the same manner as in Synthesis Example 1. Table 1 shows the results.

5-2. Production of plating improver Example 1-1
15 parts by mass of the heterophasic polymer particles P1 and 30 parts by mass of the heterophasic polymer particles P5 were mixed to obtain a plating improver M1.

1 g of the plating improver M1 was put into 20 ml of acetone and shaken for 2 hours. Then, centrifugation was performed until the two layers were completely separated, and the insoluble matter was recovered and redispersed in acetone. A sample for particle measurement was prepared by diluting 40 μl of this dispersion with 100 g of water, placing this diluted solution on a TEM grid, and drying it.
After that, the sample was brought into contact with osmium tetroxide vapor generated by heating to dye the plating improver M1. Randomly 200 samples were observed at a magnification of 2500 using a transmission electron microscope "JEM-1400Plus" manufactured by JEOL Ltd.
The obtained TEM image is analyzed using the image analysis software "Image-Pro Plus Ver.4.0 for Windows (registered trademark)" to identify particles present in the particle size range of 0.05 μm or more and less than 0.15 μm. and the volume % of particles existing in the particle size range of 0.15 μm or more and 0.5 μm or less were calculated. Table 2 shows the results.

Further, the volume average particle size and standard deviation of the plateability improver M1 were measured in the same manner as the heterophase polymer particles P1, and the coefficient of variation was calculated by the following formula. Table 2 shows the results.
Variation coefficient (%) = (standard deviation / volume average particle size) x 100

Further, the water content of the plating improver M1 was measured according to Method B (Karl Fischer's method) of JIS K7251 "Plastics - Determination of water content". Table 2 shows the results.

Examples 1-2 to 1-12 and Comparative Examples 1-1 to 1-3
Various heterophasic polymer particles were used in the proportions shown in Table 2 to produce plating improvers M2 to M15. Then, physical properties were measured in the same manner as in Example 1-1. Table 2 shows the results.

5-3. Production and evaluation of molding for plating Example 2-1
45 parts by mass of the plating improver M1, and 55 parts by mass of an acrylonitrile/styrene copolymer as a thermoplastic resin (repeating units derived from acrylonitrile: 30% by mass, repeating units derived from styrene: 70% by mass, Weight average molecular weight Mw: 104,000) were mixed with a Henschel mixer, and then melt-kneaded (set temperature: 200° C.) using a Banbury mixer to prepare pellets of the plating composition.

1 g of the pellets was added to 20 ml of acetone (a suitable solvent that completely dissolves the thermoplastic resin) and shaken for 2 hours. Then, centrifugation was performed until the two layers were completely separated, and the insoluble matter was recovered and redispersed in acetone. 40 μl of this dispersion was diluted with 100 g of water, and the diluted solution was placed on a TEM grid and dried to prepare a sample for measuring the plating improver M1 contained in the pellets. Then, in the same manner as above, the volume % of the particles present in the particle size interval of 0.05 μm or more and less than 0.15 μm, and the particle size present in the particle size interval of 0.15 μm or more and 0.5 μm or less When the volume % of the particles was calculated, the same result as that of the plating improver M1 shown in Table 2 was obtained before the plating composition was produced.

Further, the volume average particle size and standard deviation of the plating property improver M1 recovered by the above treatment were measured, and the coefficient of variation was calculated by the following formula. The same results were obtained as with improver M1.
Variation coefficient (%) = (standard deviation / volume average particle size) x 100

Using the above pellets, injection molding is performed using an injection molding machine "J100E-C5 type" (model name) manufactured by Japan Steel Works, Ltd. under the conditions of a cylinder setting temperature of 220 ° C and a mold temperature of 40 ° C, and a size conforming to ISO 179. A test piece (notched, 2 mm thick) was obtained. Using a digital impact tester "DG-CB" (model name), Charpy impact strength (unit: kJ/m ² ) was measured according to ISO179. If the Charpy impact strength is 15 kJ/m ² , it can be judged that the impact resistance is excellent. Table 3 shows the results.

Furthermore, using the above pellets, a test piece having a length of 150 mm, a width of 70 mm, and a thickness of 3.2 mm was prepared under the above molding conditions, and copper plating was applied to the surface using the CRP process manufactured by Okuno Chemical Industry Co., Ltd. gone. Then, the peeling strength and appearance of the plated film in the obtained plated compact were evaluated by the following methods. Table 3 shows the results.

First, the specimen was degreased by immersing it in "CRP cleaner" at 40°C for 3 minutes. After that, it was washed with water at 20° C. and immersed in an etching solution (chromic acid; 400 g/l, sulfuric acid; 400 g/l) at 67° C. for 10 minutes for etching. Next, the test piece was washed with water at 20°C, pre-dipped in a 35% hydrochloric acid aqueous solution at 35°C for 1 minute, and further immersed in "CRP Catalyst" at 35°C for 6 minutes to treat the Pd-Sn colloidal catalyst. did
After that, the obtained catalyzed test piece was washed with water at 20° C. and immersed in “CRP Selector A” and “CRP Selector B” at 45° C. for 3 minutes to conduct a conductive treatment. After the conductive treatment, the test piece was washed with water at 20° C. and subjected to electrolytic copper plating at room temperature for 60 minutes to obtain a copper layer having a thickness of 40 μm. Then, the test piece with the copper layer was washed with water at 20°C and dried at 80°C for 2 hours.
Peeling strength was measured according to JIS H 8630 in order to evaluate the adhesion of the copper layer in the test piece with the copper layer. If this peeling strength is 1.0 kN/m or more, it can be judged that the plating adhesion is excellent.

Moreover, the test piece with a copper layer was visually observed, and the appearance was determined according to the following criteria.
"A": Appearance that can be put to practical use when the plated molded article is glossy and no excessive unevenness is observed.
"Poor": Concavities and convexities are clearly observed, impairing the aesthetic appearance and making practical use difficult.

Examples 2-2 to 2-11 and Comparative Examples 2-1 to 2-3
Plating compositions were produced in the same manner as in Example 2-1 using various plating improvers and the above acrylonitrile-styrene copolymer in the proportions shown in Table 3. Then, various evaluations were performed in the same manner as in Example 2-1. Table 3 shows the results.

Example 2-12
30 parts by mass of the plating improver M12, 20 parts by mass of the acrylonitrile-styrene copolymer, and 50 parts by mass of the polycarbonate resin "Novarex 7022R" (trade name) manufactured by Mitsubishi Engineering-Plastics Co., Ltd. are mixed in a Henschel mixer. After mixing, the mixture was melt-kneaded (set temperature: 260°C) using a Banbury mixer to prepare pellets of the plating composition.

Using the prepared pellets, an injection molding machine "J100E-C5 type" (model name) manufactured by Japan Steel Works, Ltd. was used, except that the cylinder setting temperature was 260 ° C. and the mold temperature was 60 ° C. Example 2-1 Injection molding was performed in the same manner as above to prepare a test piece. Then, various evaluations were performed. Table 3 shows the results.

As is clear from Tables 2 and 3, in Examples 2-1 to 2-12 corresponding to the present invention, it is possible to produce a plated compact having excellent plating adhesion and impact resistance and a good plating appearance. did it. On the other hand, in Comparative Examples 2-1 to 2-3, which do not correspond to the present invention, it was not possible to produce a plated compact with good impact resistance and plating adhesion.

Claims (6)

Heterogeneous polymer particles having a coefficient of variation of particle diameter of 40 to 90% (provided that 40 to 70 parts by mass of rubber-like polymer (d1) having a mass average particle diameter of 0.20 to 0.50 μm, aromatic vinyl 60 to 80% by mass of the compound (a1), 20 to 40% by mass of the vinyl cyanide compound (a2), and another monovinyl compound copolymerizable with the aromatic vinyl compound (a1) and the vinyl cyanide compound (a2). (a3) a graft copolymer (A-1) obtained by graft-polymerizing 30 to 60 parts by mass of the monomer component (a) consisting of 0 to 20 mass % (wherein the rubber-like polymer (d1) and the monomer A total of 100 parts by mass of component (a)) 10 to 30 parts by mass and 40 to 70 parts by mass of a rubber-like polymer (d2) having a mass average particle diameter of 0.06 to 0.15 μm, the monomer component (a) Graft copolymer (A-2) obtained by graft polymerization of 30 to 60 parts by mass (100 parts by mass in total of rubber-like polymer (d2) and monomer component (a)) 5 to 20% by mass and 50 to 80% by mass of the aromatic vinyl compound (b1), 20 to 50% by mass of the vinyl cyanide compound (b2), and the aromatic vinyl compound (b1) and the vinyl cyanide compound (b2) can be copolymerized. 5 to 50% by mass of a copolymer (B) obtained by copolymerizing 0 to 20% by mass of another monovinyl compound (b3) and 20 to 70% by mass of a polycarbonate resin (C), and the graft copolymer The rubber-like polymer (d1) and the rubber-like polymer ( The total proportion of d2) is 10 to 20% by mass, and the graft copolymer (A-1), the graft copolymer (A-2), the copolymer (B), and the polycarbonate resin (C) The graft copolymer (A-1 ) and the above graft copolymer (A-2)) and water ,
The coefficient of variation is derived from the following formula,
Variation coefficient (%) = (standard deviation / volume average particle size) x 100
(The volume average particle size and standard deviation are calculated from the measured values obtained by observation with a transmission electron microscope.)
The heterophasic polymer particles are a plating improver containing heterophasic polymer particles (A1) having a volume average particle diameter of 50 nm to 160 nm and heterophasic polymer particles (A2) having a volume average particle diameter of 210 nm to 400 nm . In the heterophasic polymer particles,
The content of polymer particles having a particle size of 0.05 μm or more is 80% by volume or more with respect to the total heterophase polymer particles,
2. The plating improver according to claim 1, wherein the content of polymer particles having a particle size of 0.05 μm or more and less than 0.15 μm is 10 to 60% by volume based on the total heterophase polymer particles. A molded article for plating, comprising the plating improver according to claim 1 or 2 and a thermoplastic resin. The content ratios of the hetero-phase polymer particles and the thermoplastic resin contained in the plating improver are 10 to 80% by mass and 20 to 90% by mass, respectively, when the total of both is 100% by mass. 4. The molding for plating according to claim 3. A plated molded article comprising the molded article for plating according to claim 3 or 4 and a plating layer disposed on the surface of the molded article for plating. A method for forming a plating layer on the molding for plating according to claim 3 or 4, wherein the molding for plating is etched at 30 to 80 ° C., and then the plating layer is formed.

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