JP2019014948A - Plating composition, plating molding, plated molding and plating method - Google Patents

Abstract

To provide: a plating composition mixed with a molding material for forming a plating resin molding together with a thermoplastic resin, excellent in shock resistance and capable of providing a plating molding capable of efficiently forming a metal film or an alloy film on the surface by plating; and the plating molding, and the like.SOLUTION: The plating composition includes a heterogeneous phase polymer particles and water. A water content rate is 0.1-1 mass% to the whole plating composition; the coefficient of variation in the particle sizes of the heterogeneous phase polymer particles is, preferably, 40-90%. The content rate of polymer particles having a particle size of 0.05 μm or more to the whole heterogeneous phase polymer particles is 80 vol.%, and the content rate of polymer particles having a particle size of 0.05 μm or more and less than 0.15 μm to the whole heterogeneous phase polymer particles is, preferably, 10-60 vol.%.SELECTED DRAWING: None

Description

  The present invention relates to a plating composition, a plating molded body, a plating molded body, and a plating method. More specifically, the present invention relates to a plating composition, a plating provided with a metal film or an alloy film, which gives a molded article for plating capable of forming a metal film or an alloy film having excellent adhesion on the surface by plating. The present invention relates to a molded body and a plating method.

Conventionally, a plated molded body provided with a metal film or an alloy film obtained by plating on the surface of the molded body has, for example, a metallic appearance, improved design, durability and weather resistance. It is used in vehicle parts, electrical / electronic parts, OA equipment parts, home appliances, residential parts, clothing items, etc. for the purpose of enhancing, providing anti-static properties, conducting properties, and electromagnetic wave shielding.
As a method for plating a molded body, a so-called catalyst accelerator is used in which steps such as etching (surface roughening), neutralization, catalyst application, activation, electroless plating, acid activation, and electroplating are sequentially performed. The direct plating method in which the electroless plating process and the electroless plating process are omitted is known.

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

JP 2002-338636 A JP 2007-177223 A

  Along with the expansion of the use of the plated body, there is a need for a molding material for plating that gives a molded body with better adhesion to a metal layer produced by plating. Further, when an impact is applied to the molded body, fragments are scattered when the molded body is brittlely broken. In order to suppress this, there is a need for a molding material for plating for producing a molded body that is ductile fractured against impact.

  The present invention has a tendency to be ductile fractured against an external impact, is excellent in impact resistance, and can form a metal layer or alloy layer excellent in adhesion by plating on its surface. It is an object of the present invention to provide a plating composition provided with a (molded body for plating), a plated body including a metal layer or an alloy layer, and a plating method.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

Application example 1
One aspect | mode of the composition for plating of this invention contains heterophasic polymer particle | grains and water, and the content rate of water is 0.1-1 mass% with respect to the whole composition for plating.

Application example 2
The variation coefficient of the particle diameter of the heterophasic polymer particles is preferably 40 to 90%.

Application example 3
In the heterogeneous polymer particles, the content ratio of the polymer particles having a particle diameter of 0.05 μm or more is 80% by volume or more with respect to the whole heterophasic polymer particles, and is 0.05 μm or more and less than 0.15 μm. The content ratio of the polymer particles having a particle size is preferably 10 to 60% by volume with respect to the whole of the heterogeneous polymer particles.

Application example 4
One aspect | mode of the molded object for plating of this invention contains the composition for plating as described in any one of the application examples 1 thru | or 3, and a thermoplastic resin.

Application example 5
In the molded article for plating according to the present invention, the content ratio of the heterophasic polymer particles and the thermoplastic resin contained in the plating composition is 10 to 80 masses, respectively, when the total of both is 100 mass%. % And 20 to 90% by mass are preferable.

Application Example 6
One aspect of the plated molded body of the present invention includes the plated molded body according to Application Example 4 or 5, and a plated layer disposed on the surface of the plated molded body.

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

The plating composition and plating molded body 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 with respect to the impact from the outside.
According to the plated molded body of the present invention, a plated molded body having excellent formability of a metal layer such as a copper layer or an alloy layer by plating and adhesion of these layers to the base is provided.
Since the plated molded body of the present invention is excellent in the adhesion of the metal layer or alloy layer to the underlying molded portion, the appearance is also excellent.
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 base molding part.

Sectional drawing of the heterophasic polymer particle which has a core-shell heterophasic structure. Sectional drawing of the heterophasic polymer particle which has a sea island-like (island in sea) heterophasic structure. Sectional drawing of the heterophasic polymer particle | grains which have an octopus-like heterophasic structure. Sectional drawing of the heterophasic polymer particle which has another octopus-like heterophasic structure. Sectional drawing of the heterophasic polymer particle which has a juxtaposition type | mold (side-by-side) heterophase structure. Sectional drawing of the heterophasic polymer particle which has a multi-particle heterophasic heterophase structure. Sectional drawing of the heterophasic polymer particle which has a raspberry-like heterophasic structure. Sectional drawing of the heterophasic polymer particle which has another multiparticulate heterophasic type heterostructure. Sectional drawing of the heterophasic polymer particle which has a daruma-like heterophasic structure.

Hereinafter, preferred embodiments according to the present invention will be described in detail. It should be understood that the present invention is not limited only to the embodiments described below, and includes various modifications that are implemented within the scope not changing the gist 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 encompassing both “˜acrylate” and “˜methacrylate”. “(Meth) allyl” is a concept that encompasses both “allyl” and “methallyl”.

1. The plating composition of the present invention contains heterophasic polymer particles and water, and the water content is 0.1 to 1% by mass relative to the total plating composition. And The plating composition of this invention can contain another component (after-mentioned) as needed.

When a plating molding is produced using a plating molding material containing the plating composition of the present invention and a thermoplastic resin, the heterophasic polymer particles are not only contained within the molding, Exposed on the surface. When electroplating or the like is applied to the plating molding, first, a treatment such as bringing the surface of the plating molding into contact with an etching solution is performed. At this time, the surface of the plating molding is exposed. The heterophasic polymer particles are removed, and concave portions are formed on the surface of the molded body. It is assumed that the recess formed in this manner functions as an anchor hole that improves the adhesion of the plating film, and a plating film that exhibits good adhesion strength can be produced.
Hereinafter, each component contained in the plating composition of the present invention will be described in detail.

1-1. Heterogeneous polymer particles The heterophasic polymer particles according to the present invention are particles composed of two or more phases that are different from each other, not a homogeneous phase.
The cross-sectional structure of the heterophasic polymer particles includes a core-shell heterogeneous structure (FIG. 1), a sea-island (island-in-sea) heterogeneous structure (FIG. 2), an octopus-like heterogeneous structure (FIGS. 3 and 4), a juxtaposed type ( Side-by-side heterophase structures (FIG. 5), raspberry-like heterophase structures (FIG. 7), multi-particle heterophasic heterophase structures (FIGS. 6 and 8), daruma-like heterophase structures (FIG. 9), and the like. Of these heterophase structures, the core-shell heterophase structure (FIG. 1) is preferred. The plating composition of the present invention may include a composition in which two or more of the various heterophase structures as described above are combined to form one heterophasic particle.

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

  In addition, a single polymer having a chemical structure with a high affinity between a homogeneous polymer particle composed of a single polymer having a chemical structure with excellent mechanical properties such as impact resistance and a thermoplastic resin. In the composition obtained by kneading the homogeneous polymer particles composed of the thermoplastic resin together with the thermoplastic resin, the thermoplasticity due to the difference in specific gravity, particle surface tension, surface polarity, etc. between the two types of homogeneous polymer particles. It is difficult to uniformly disperse in the resin. However, the heterophasic polymer particles contained in the plating composition of the present invention are formed of a single polymer formed by two or more polymers having different chemical structures or a polymer having two or more block structures having different chemical structures. In the case of particles, heterogeneous dispersion due to the thermoplastic resin due to the difference in polymer can be suppressed, and uniform mixing in the thermoplastic resin is facilitated.

  The surface of the molding for plating of the present invention produced using a composition (molding material for plating) obtained by uniformly dispersing the heterophasic polymer particles in a thermoplastic resin is homogeneously provided on the surface of the molding. Is exposed. When plating is performed to form a metal film or alloy film on the plating molding, the exposed heterophasic polymer particles are etched (surface roughened), such as bringing the surface of the plating molding into contact with an etching solution. Removed by processing. As a result, uniform anchor holes are formed on the surface of the molded body. It is presumed that a plating film exhibiting good adhesion strength can be produced by producing a plating layer on the surface of the molded article having anchor holes thus produced.

  When the heterophasic polymer particles are composed of two or more polymers having different chemical structures, the polymer A having a chemical structure excellent in mechanical properties such as one of major impact resistance among the polymers. And the mass ratio (A / B) of the polymer B having a chemical structure having a high affinity with the other one main thermoplastic resin is preferably 1 / 0.1 to 1 / 1.5, Preferably it is 1 / 0.3 to 1/1. 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 polymers having two or more block structures having different chemical structures, the ratio of the block structure of the polymer is one of the main impact resistances of the polymer. The mass ratio (A ′ / B ′) between the block structure A ′ having a chemical structure with excellent mechanical properties and the like and the block structure B ′ having a chemical structure having a high affinity with one other main thermoplastic resin ) Is preferably 1 / 0.1 to 1 / 1.5, more preferably 1 / 0.3 to 1/1. 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. It is.

In the molding for plating produced using the molding material for plating containing the plating composition of the present invention containing the heterophasic polymer particles and the thermoplastic resin, the heterophasic polymer particles exposed on the surface are: It is assumed that an anchor hole is formed by removing by etching, and then a plated film that exhibits good adhesion strength is provided. However, the heterogeneous polymer particles that are not exposed on the surface of the plating molding remain in the plating molding without being removed by etching, and affect the mechanical strength of the molding.
However, it has a polymer A having a chemical structure with excellent mechanical properties such as one major impact resistance and a polymer B having a chemical structure with high affinity with the other one major thermoplastic resin. Heterogeneous polymer particles or a block structure A ′ having a chemical structure with excellent mechanical properties such as one major impact resistance and a chemical structure having a high affinity with the other one major thermoplastic resin By containing the heterophasic polymer particles having the block structure B ′ in the above-mentioned preferable configuration, a plated molded body showing good mechanical properties is produced without significantly deteriorating the mechanical strength of the molded body for plating after etching. can do.

The particle diameter of the heterophasic polymer particles contained in the plating composition of the present invention is not particularly limited, but is preferably in the range of 0.03 to 1 μm.
The average particle diameter of the heterophasic polymer particles is preferably in the range of 50 nm to 400 nm, and 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, the plating composition produced using the molding material for plating comprising the plating composition of the present invention containing the heterophasic polymer particles and the thermoplastic resin. When plating the molded body, fine anchor holes can be efficiently formed by etching (surface roughening), and the adhesion of the metal film or alloy film after plating can be further improved.
The average particle diameter of the heterophasic polymer particles was stained from an image obtained by dying the heterophasic polymer particles with osmium tetroxide and then observing the dyed polymer particles with a transmission electron microscope. For example, 200 particles can be arbitrarily selected and calculated using analysis software.

In the present invention, the coefficient of variation of the particle diameter of the heterophasic polymer particles gives a molded article for plating excellent in impact resistance, and when this plated article is plated, it has excellent adhesion to the underlying molded part. Therefore, it is preferably 40 to 90%, more preferably 40 to 80%, and still more preferably 45 to 75%.
The coefficient of variation can be obtained by the following formula using the volume average particle diameter of the heterophasic polymer particles and the standard deviation of the particle diameter distribution.
Coefficient of variation (%) = (standard deviation / volume average particle diameter) × 100
The particle diameter of the heterophasic polymer particles can be measured by observation with a transmission electron microscope of the particles stained with osmium tetroxide and analysis of the TEM image as described above. The deviation can be calculated from the measured particle diameter.

In the present invention, the content ratio R1 of the heterophasic polymer particles having a particle diameter of 0.05 μm or more is preferably 80% by volume or more, more preferably, based on the whole heterophasic polymer particles contained in the plating composition. 90% by volume or more. Further, the content ratio R2 of the heterophasic polymer particles having a particle diameter of 0.05 μm or more and less than 0.15 μm is preferably 10 to 60% by volume with respect to the entire heterophasic polymer particles contained in the plating composition, More preferably, it is 20-50 volume%. Since the content ratios R1 and R2 of the heterophasic polymer particles have the above-described configuration, the impact resistance of the plating molded body produced using the plating molding material including the plating composition and the thermoplastic resin, and the metal by plating It is possible to improve the adhesion of the layer and the like.
The content ratio R1 is represented 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 composition. Can be calculated.
R1 = (V1 / V) × 100
Further, the content ratio R2 is V2 as 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 as the total volume of the heterophasic polymer particles contained in the plating composition. Can be calculated by the following equation.
R2 = (V2 / V) × 100

  The variation coefficient of the particle diameter of the heterophasic polymer particles can be controlled by the production conditions of the heterophasic polymer particles. Alternatively, the coefficient of variation may be controlled by preparing two or more kinds of heterophasic polymer particles in advance and using them together. For example, when the coefficient of variation is controlled by using two kinds of different-phase polymer particles (A1) and different-phase polymer particles (A2) having different sizes, the particle diameter of the different-phase polymer particles (A1) is preferably 50. It is -150 nm, More preferably, it is 60-120 nm, and the particle diameter of a heterophasic polymer particle (A2) becomes like this. Preferably it is 200-800 nm, More preferably, it is 250-700 nm.

As described above, the heterophasic polymer particles of a preferred embodiment contain two or more polymers having different chemical structures or a polymer having two or more block structures having different chemical structures. In the present invention, a repeating unit derived from a conjugated diene that contributes to mechanical properties such as impact resistance (hereinafter referred to as “repeating unit (r1)”) and a thermoplastic used in combination with the plating composition of the present invention. Two or more polymers having different chemical structures or repeating units having two or more block structures having different chemical structures including a repeating unit having a functional group having high affinity with the resin (hereinafter referred to as “repeating unit (r2)”). It is preferable to contain a coalescence.
Hereinafter, the repeating unit contained in the polymer constituting such heterophasic polymer particles will be described.

  A metal molding excellent in mechanical properties such as impact resistance by using together with a thermoplastic resin a heterogeneous polymer particle having a repeating unit (r1) derived from a conjugated diene and water. Can be manufactured. The repeating unit (r1) may be only one type or two or more types.

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

The content ratio 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 the conjugated diene is 100 parts by mass. is there. The molding for plating uses a molding material containing a composition for plating containing heterophasic polymer particles and water in which the content ratio of the repeating unit (r1) derived from the conjugated diene is within the above range, and a thermoplastic resin. If it is obtained, the impact resistance can be further improved.
Further, the heterophasic polymer particle is a total of the repeating unit (r2) having a functional group having a high affinity for the thermoplastic resin and the polymer in which the repeating unit (r1) derived from the conjugated diene is 45% by mass or more. It is more preferable to contain the polymer which is 20 mass% or more.

  The heterophasic polymer particles can contain a repeating unit (r2) having a functional group having a high affinity with a thermoplastic resin such as a styrene resin, an acrylic resin, a polycarbonate resin, a polyamide resin, or a polyester resin. In the case, when the plating composition containing the heterophasic polymer particles and water and the thermoplastic resin are kneaded, the heterophasic polymer particles can be uniformly dispersed in the thermoplastic resin, and the mechanical strength is excellent. A molded product for plating can be produced.

  As the functional group having high affinity with the thermoplastic resin, 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, sulfonic acid ester group, mercapto group, sulfide group, sulfinyl group, thiocarbonyl group, thiophosphoric acid group, phosphonic acid group, phosphonic acid An ester group etc. are mentioned. Of these, carboxylic acid ester groups and cyano groups are preferred. The repeating unit (r2) contained in the heterophasic polymer particles may be only one type or two or more types.

Examples of the monomer that gives a repeating unit containing a carboxylic acid ester group include unsaturated carboxylic acid esters.
As the unsaturated carboxylic acid ester, a (meth) acrylic acid ester is preferable. As the (meth) acrylic acid ester, 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, Ethyl di (meth) acrylate Glycol, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, allyl (meth) acrylate, etc. It is done. Of 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.

Examples of the monomer giving a repeating unit containing a cyano group include unsaturated nitrile compounds.
Examples of the unsaturated nitrile compound include acrylonitrile, methacrylonitrile, ethacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile, vinylidene cyanide and the like. Of 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 when the total number of repeating units contained in the polymer constituting the heterophasic polymer particles is 100% by mass. % By mass. The molded article for plating contains, in particular, a composition for plating containing heterophasic polymer particles having a content ratio of the repeating unit (r2) derived from the unsaturated nitrile compound within the above range and water, and a thermoplastic resin. If it is obtained using a molding material, the mechanical strength can be further improved.

  The heterophasic polymer particles may include a repeating unit other than the above (hereinafter referred to as “repeating unit (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 unit derived from alkylamide of acid, repeating unit derived from carboxylic acid vinyl ester, repeating unit derived from acid anhydride of ethylenically unsaturated dicarboxylic acid, repeating derived from aminoalkylamide of ethylenically unsaturated carboxylic acid Examples include units. The repeating unit (r3) contained in the heterophasic polymer particles may be only one type or two or more types. Among these, a repeating unit derived from an aromatic vinyl compound and a repeating unit derived from an unsaturated carboxylic acid are preferable.

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

Examples of the fluorine-containing compound having an ethylenically unsaturated bond include vinylidene fluoride, tetrafluoroethylene, and hexafluoropropylene.
Examples of the alkyl amide of the ethylenically unsaturated carboxylic acid include (meth) acrylamide, N-methylol acrylamide and the like.
Examples of the carboxylic acid vinyl ester include vinyl acetate and vinyl propionate.
Examples of the aminoalkylamide of ethylenically unsaturated carboxylic acid include aminoethylacrylamide, dimethylaminomethylmethacrylamide, methylaminopropylmethacrylamide and the like.

  In the heterophasic polymer particles of the preferred embodiment, the repeating units (r1), (r2) and (r3) may be distributed in any way, but at least the repeating units (r2) are exposed on the surface of the particles. It is preferable.

Next, the physical properties of the heterophasic polymer particles will be described.
In the heterophasic polymer particles, it is preferable that the endothermic peak difference between a plurality of phases constituting the particles is 5 ° C. or more.
Further, in the present invention, when the heterophasic polymer particles are subjected to differential scanning calorimetry (DSC) in accordance with JIS K7121, there are two or more endothermic peaks in a temperature range of −100 ° C. to 200 ° C. It is preferably a coalesced particle. A molded article for plating obtained by using a molding composition containing a heterogeneous polymer particle having two or more endothermic peaks in this temperature range and a plating composition containing water and a thermoplastic resin has excellent resistance to resistance. Has impact and plating adhesion. The two or more endothermic peaks are more preferably in the range of -95 ° C to 180 ° C, and particularly preferably in the range of -90 ° C to 160 ° C.

Moreover, the plating obtained using the molding material containing the composition for plating containing the heterophasic polymer particle which shows two or more endothermic peaks in the temperature range of -100 degreeC-0 degreeC, and water, and a thermoplastic resin. The molded article has improved elasticity and better impact resistance. In this case, the temperature of the two or more endothermic peaks is preferably in the range of -95 ° C to -20 ° C, and more preferably in the range of -90 ° C to -40 ° C.
Furthermore, a molding material comprising a plating composition containing two-phase endothermic polymer particles showing two or more endothermic peaks in a temperature range of 50 ° C. to 200 ° C. and water, and a thermoplastic resin, produces a molding for plating. It has an appropriate fluidity during melt kneading and has excellent moldability. In this case, the temperature of two or more endothermic peaks is preferably in the range of 70 ° C to 180 ° C, and 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. The Mw is a standard polystyrene equivalent value measured by gel permeation chromatography (hereinafter also referred to as “GPC”).

  The method for producing the heterophasic polymer particles contained in the plating composition of the present invention is not particularly limited and can be produced by a conventionally known method. For example, emulsion polymerization method, suspension polymerization method, dispersion polymerization method, seed polymerization method and other two-stage polymerization methods, mixing a plurality of polymers in the presence or absence of a solvent, coagulating and drying, pulverizing, Alternatively, a method of spray-drying into a powder by a method such as a spray drying method can be applied. As a specific example of the method for producing heterophasic polymer particles used in the present invention, polymerization is carried out by a conventional method using a predetermined monomer until the polymerization conversion rate becomes 20 to 100%, and then another heavy polymer particle is produced. Add a monomer that becomes a coalescence and polymerize by a conventional method (two-stage polymerization method) or two or more kinds of latex-like polymer particles synthesized separately at room temperature to 300 ° C. for 2 to 100 hours Examples thereof include a method of stirring and mixing to form heterophasic polymer particles.

  When producing the heterophasic polymer particles of the above preferred embodiment, that is, the heterophasic polymer particles containing the repeating unit (r1) derived from the conjugated diene, for example, it has a predetermined average particle diameter produced by a known polymerization method, A monomer that gives a repeating unit having a functional group having high affinity with a thermoplastic resin is added to an aqueous dispersion (latex) of polymer particles (raw material particles) containing the repeating unit (r1) and subjected to emulsion polymerization. It is preferable to apply a grafting method. As this monomer, aromatic vinyl compounds, vinyl cyanide compounds and the like are preferable. When an aqueous dispersion (latex) in which the heterophasic polymer particles are dispersed in an aqueous medium is obtained by this graft polymerization, the coagulant is added to cause precipitation, and then the aqueous polymer particles are washed and dried. It can be set as the 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, and the like can be used.

  Examples of emulsifiers that can be used in emulsion polymerization include higher alcohol sulfates, alkylbenzene sulfonates, alkyl diphenyl ether disulfonates, aliphatic sulfonates, aliphatic carboxylates, dehydroabietic acid salts, naphthalene sulfones. Anionic surfactants such as acid / formalin condensates and sulfate salts of nonionic surfactants; Nonionic surfactants such as alkyl esters of polyethylene glycol, alkyl phenyl ethers of polyethylene glycol, alkyl ethers of polyethylene glycol; Fluorosurfactants such as perfluorobutyl sulfonate, perfluoroalkyl group-containing phosphates, perfluoroalkyl group-containing carboxylates, and perfluoroalkylethylene oxide adducts. It is. Only one type of emulsifier may be used, or two or more types may be used.

  In addition, as a polymerization initiator, a combination of an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide and a reducing agent such as a sugar-containing pyrophosphate prescription and a sulfoxylate prescription is combined. Redox initiators: persulfates such as potassium persulfate and sodium persulfate; peroxides such as benzoyl peroxide, lauroyl peroxide, tert-butyl peroxylaurate, tert-butyl peroxymonocarbonate, etc. . Only one type of polymerization initiator may be used, or two or more types may be used.

  A chain transfer agent can be used in combination during the graft polymerization. Examples of chain transfer agents include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan; terpinolenes, 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 a repeating unit (r1) derived from a conjugated diene, the graft ratio in the resulting heterophasic polymer particles is preferably It is 10-150 mass%, More preferably, it is 30-100 mass%.
In addition, this graft ratio is calculated | required by a following formula.
Graft ratio (mass%) = {(S−T) / T} × 100
(In the formula, S is obtained by adding 1 g of the produced heterophasic polymer particles to 20 ml of acetone, shaking with a shaker for 2 hours, and then centrifuging to separate and dry insoluble and soluble components. The mass (g) of the insoluble matter obtained, and T is the mass (g) of the raw material particles having repeating units derived from the 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 graft polymerization, the ratio of the total amount of the aromatic vinyl compound and the vinyl cyanide compound used is based on the total amount of the monomers. , Preferably it is 70 mass% or more, More preferably, it is 80 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 then performing graft polymerization. In the produced heterophasic polymer particles, the average thickness of the formed graft site is preferably 3 to 30 nm, more preferably 4 to 25 nm.
The average thickness of the graft site can be measured by staining the heterophasic polymer particles with osmium tetroxide or the like and observing with a transmission electron microscope by a known method.

  The plating composition of the present invention can contain a plurality of heterophasic polymer particles, and is a case where the heterophasic polymer particles of such an embodiment are produced. For example, the heterophasic polymer particles (A11) and the heterophasic particles are produced. When producing heterophasic polymer particles containing polymer particles (A12), an aqueous dispersion containing heterophasic polymer particles (A11) and an aqueous dispersion containing heterophasic polymer particles (A12) are mixed. Thereafter, a coagulant may be added to the mixed solution. Further, the aqueous dispersion containing the heterophasic polymer particles (A11) and the aqueous dispersion containing the heterophasic polymer particles (A12) are each solidified to produce each powder, and then mixed. Good.

1-2. Water The plating composition of the present invention contains water, and the content ratio is 0.1 to 1% by mass, preferably 0.2 to 0.5% by mass, based on the entire plating composition. It is. When a molding for plating is produced using a molding material for plating containing the composition for water containing the above water content together with a thermoplastic resin, the appearance is excellent, and when plating is performed, it is good. A plated molded body having a plated film having adhesiveness can be obtained.
The water contained in the plating composition of the present invention can be quantified in accordance with method B (Karl Fischer method) of JIS K7251 “Plastics—How to determine moisture content”.

In general, it has been considered that water vaporizes at a high temperature when the molding material for plating is used for molding, and impairs the appearance of the resulting molded body. For this reason, it has been common knowledge in the industry to avoid mixing water as much as possible in thermoplastic plating molding materials.
However, if a molded article for plating is produced using a plating composition containing water in the above content ratio and a thermoplastic resin, excellent plating characteristics are exhibited. Although this expression mechanism is not clear, the present inventors presume that it is caused by the following actions.

In the molded article for plating, in order to improve the adhesion strength of the plating film formed on the surface, appropriate irregularities are required on the surface. As described above, the heterophasic polymer particles, which are essential components of the plating composition of the present invention, are not only present inside the plating molding but also exposed to the surface, so that the plating molding is in contact with the etching solution. In this case, the exposed heterophasic polymer particles are removed, and anchor holes are formed. On the other hand, the heterophasic polymer particles that are contained in the plating molding and are not exposed on the surface remain in the interior even after etching, and affect the mechanical strength of the molding. For this reason, although a large amount of heterophasic polymer particles are blended in the molding material for producing a molding for plating, a large number of anchor holes can be produced on the surface of the molding, and the adhesion strength of the plating film can be improved. In addition, the mechanical strength of the molded body itself changes greatly.
However, moisture that evaporates by heating during molding, moves from the inside of the molding for plating to the surface, and desorbs while appropriately roughing the surface of the molding, affects the mechanical strength of the molding itself. I guess is small. As a result, by using a plating composition containing water as well as heterophasic polymer particles, anchor holes are more effectively formed on the surface of the molded body while suppressing changes in the mechanical strength of the molded body itself to a minimum. It is considered that the adhesion strength of the plating film was improved.

  The amount of water in the plating composition 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.

1-3. Other components The plating composition of the present invention comprises an anti-aging agent, an antioxidant, an ultraviolet absorber, a lubricant, a plasticizer, a filler, a heat stabilizer, a flame retardant, an antistatic agent, a colorant and the like. Can be contained.

Antiaging agents include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivative compounds, monophenol compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds, thiobisphenols. Compounds, hindered phenol compounds, phosphite compounds, imidazole compounds, nickel dithiocarbamate salts, phosphate compounds and the like.
Examples of the antioxidant include hindered amine compounds, hydroquinone compounds, hindered phenol compounds, sulfur-containing compounds, and phosphorus-containing compounds.
Examples of ultraviolet absorbers include benzophenone compounds, benzotriazole compounds, and triazine compounds.
Examples of the lubricant include wax, silicone, lipid and the like.
Plasticizers include phthalates, trimellitic esters, pyromellitic esters, aliphatic monobasic esters, aliphatic dibasic esters, phosphate esters, polyhydric alcohol esters, epoxy plasticizers, polymers Examples thereof include mold plasticizers and chlorinated paraffins.

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, pulverization 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 And phenol balloon.
Examples of the heat stabilizer include a phosphite heat stabilizer, a lactone heat stabilizer, a hindered phenol heat stabilizer, a sulfur heat stabilizer, and an amine heat stabilizer.

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

2. Molding for plating The molding for plating of the present invention is an article containing a plating composition and a thermoplastic resin. The molding for plating of the present invention comprises a molding material for plating containing a plating composition and a thermoplastic resin, or individual raw material components constituting this molding material, an injection molding device, a press molding device, a calendar molding device, a T-die. It can manufacture by processing with a conventionally well-known shaping | molding apparatus, such as an extrusion molding apparatus and a profile extrusion molding apparatus.

  The content ratio of the heterophasic polymer particles and the thermoplastic resin contained in the molded article for plating of the present invention is suitable for the formation of a metal layer or an alloy layer having excellent adhesion on the surface, and against an external impact. Since a molded article for plating excellent in impact resistance can be obtained efficiently, preferably 10 to 80 mass% and 20 to 90 mass%, more preferably 15 to 50 mass%, respectively, when the total of both is 100 mass%. They are 70 mass% and 30-85 mass%, More preferably, they are 20-60 mass and 40-80 mass%.

  Examples of the thermoplastic resin include ABS resin, acrylonitrile / styrene copolymer, acrylonitrile / styrene / maleimide compound terpolymer, polystyrene, styrene resin such as styrene / maleic anhydride copolymer; polymethyl methacrylate, etc. An acrylic resin, a polycarbonate resin, a polyamide resin, a polyester resin such as polybutylene terephthalate, or an alloy containing at least two of them. Of these, styrene resins are preferred, and ABS resins are particularly preferred because the heterophasic polymer particles contained in the plating composition are homogeneously dispersed and are superior in mechanical strength.

When the thermoplastic resin contains an ABS resin, the content ratio of the heterophasic polymer particles derived from the plating composition is preferably 30 to 180 parts by mass, more preferably 50, relative to 100 parts by mass of the thermoplastic resin. -150 parts by mass.
When the thermoplastic resin contains an alloy of ABS resin and polycarbonate resin, the content ratio of the heterophasic polymer particles derived from the plating composition is preferably 15 to 90 with respect to 100 parts by mass of the thermoplastic resin. It is 25 mass parts by mass, More preferably, it is 25-75 mass parts. In addition, from the viewpoint of the impact resistance of the molding for plating and the adhesion strength of the plating film, the composition of the alloy is preferably 100 to 1000 parts by mass with respect to 100 parts by mass of the ABS resin.

  The molded article for plating of the present invention contains other components such as an anti-aging agent, 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 article 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, etc., an anchor hole can be efficiently formed, Excellent metal and alloy precipitation and growth properties can be obtained, and a metal layer or alloy layer excellent in adhesion to the substrate and appearance can be formed.

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

  In the plated molded body of the present invention, since the base molded part on which the plated layer (metal layer or alloy layer) is formed includes a recess formed by detachment of the heterophasic polymer particles, the surface of the base molded part , Excellent adhesion to the plating layer and excellent appearance of the plated product.

  The plated molded body of the present invention can be produced by plating on the surface of the plated molded body by applying a known method. For example, a catalyst / accelerator method that sequentially proceeds with etching (surface roughening), neutralization, catalyst application, activation, electroless plating, acid activation, electroplating, etc. Alternatively, a plated layer can be produced by forming a plated layer by a direct plating method or the like in which the electroless plating step in the catalyst accelerator method is omitted.

  The plated molded body of the present invention can be used for vehicle parts, electrical products, electronic parts, housings, frames, handles, and the like.

4). Plating method The plating method of the present invention is a method for forming a plating layer after etching a molded article for plating at 30 to 80 ° C.
The etching solution used in the etching step is not particularly limited, and may include dichromic acid, a dichromic acid / sulfuric acid mixed solution, chromic anhydride, a chromic anhydride / sulfuric acid mixed solution, and the like. In this etching step, the etching state changes depending on the temperature of the etching solution and affects the size of the anchor hole. Therefore, the temperature of the etching solution is 30 to 80 ° C., preferably 40 to 70 ° C. If the temperature of the etching solution is too low, the formation of anchor holes becomes insufficient. On the other hand, when the temperature of the etching solution is too high, overetching occurs.
In the subsequent plating step, the method described above can be applied.

5. Examples Hereinafter, the present invention will be described by way of examples. However, the present invention is not limited to these examples.

5-1. Synthesis of heterophasic polymer particles Synthesis Example 1
In a stainless steel autoclave equipped with a stirrer, heating / cooling device, thermometer, and each raw material addition device, 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, high-grade 4 parts by weight of fatty acid sodium, 0.8 part by weight of sodium carbonate, 0.075 part by weight of potassium hydroxide and 0.15 part by weight of potassium persulfate were charged and reacted at 80 ° C. for 5 hours to obtain diene polymer particles (hereinafter, An aqueous dispersion (latex) of “raw material particles L1” was obtained.

  As a result of laser Doppler / frequency analysis using a Nikkiso Co., Ltd. “Microtrac UPA150 particle size analyzer” and measuring the volume average particle size of the raw material particles L1, the volume average particle size of the raw material particles L1 is 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 part by mass of sodium pyrophosphate, ferrous sulfate heptahydrate 0.004 A solution prepared by dissolving 10 parts by mass and 0.3 parts by mass of glucose in 8 parts by mass of ion-exchanged water was added, and 30 parts by mass of ion-exchanged water, 0.5 parts by mass of potassium rosinate at an internal temperature of 70 ° C. with stirring, styrene 45 parts by mass, 15 parts by mass of acrylonitrile, 0.45 parts by mass of tert-dodecyl mercaptan and 0.25 parts by mass of cumene hydroperoxide were continuously added over 3.5 hours. And this reaction liquid was further stirred for 1 hour, and the aqueous dispersion (latex) of heterophasic polymer particle P1 was obtained.
Thereafter, 0.5 part by mass of an anti-aging agent was added, and then an aqueous sulfuric acid solution was added to solidify and dried to obtain a powder of heterophasic polymer particles P1.

1 g of heterophasic polymer particles P1 was put into 20 ml of acetone and shaken for 2 hours. Next, the mixture was centrifuged until it was completely divided into two layers, the insoluble matter was collected, dried and solidified, and the mass (S gram) 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 gram), a graft ratio of 78% was obtained according to the following formula.
Graft rate = 100 × (ST) / T

Further, the acetone-soluble matter obtained when obtaining the graft ratio, that is, the ungrafted (co) polymer was dried and solidified, and then the sample dissolved in THF was subjected to GPC using a differential refractive index detector. It was 103,000 as a result of using for a measurement and calculating the weight average molecular weight (Mw) by standard polystyrene.
Furthermore, acetone-soluble content, that is, the content of the structural unit derived from the 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 vinyl cyanide compound unit amount was calculated from the obtained nitrogen amount and found to be 25%.

1 g of heterophasic polymer particles P1 was put into 20 ml of acetone and shaken for 2 hours. Next, the mixture was centrifuged until it was completely separated into two layers, and the insoluble matter was collected and redispersed in acetone. 40 μl of this dispersion was diluted with 100 g of water, and this diluted solution was placed on a TEM grid and dried to prepare a sample for particle measurement.
Thereafter, the sample was brought into contact with osmium tetroxide vapor generated by heating to stain the heterogeneous polymer particles P1. 200 pieces of this were observed with a transmission electron microscope “JEM-1400Plus” manufactured by JEOL Ltd. at a magnification of 2500 times, and it was confirmed that differently stained and non-stained parts existed in one particle. did. As a result, it was found that the heterophasic polymer particles P1 were core-shell type heterophasic polymer particles shown in FIG.
The obtained TEM image was measured to measure the volume average particle diameter of the heterophasic polymer particles P1 using image analysis software “Image-Pro Plus Ver. 4.0 for Windows (registered trademark)”, and found to be 90 nm. . Further, the volume of all particles is calculated, and further, the volume% of particles existing in a particle diameter section having a particle diameter of 0.05 μm or more and less than 0.15 μm, and particles having a particle diameter of 0.15 μm or more and 0.5 μm or less The volume percent of particles present in the diameter interval was calculated. The results are shown in Table 1.

  Moreover, about the different phase polymer particle P1, the differential scanning calorimetry (DSC) based on JISK7121 was performed, and the glass transition temperature Tg was observed. Two Tg's were observed, -81 ° C and 103 ° C.

Synthesis Examples 2-7
Except having adjusted the usage-amount of electrolyte and polymerization time suitably, operation similar to manufacture of the raw material particle L1 in the synthesis example 1 was performed, and raw material particle L2-L7 was obtained. The glass transition temperature, volume average particle diameter, and standard deviation of the particle diameter distribution of the raw material particles L2 to L7 were evaluated in the same manner as in Synthesis Example 1. The results are shown in Table 1.
Subsequently, the same operations as in Synthesis Example 1 were performed except that each latex containing the raw material particles L2 to L7 was used and the amount of the polymerization initiator or chain transfer agent was appropriately adjusted. 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. The results are shown in Table 1.

Synthesis Example 8
In a stainless steel autoclave equipped with a stirrer, heating / cooling device, thermometer, each raw material adding device and auxiliary agent adding device, 150 parts by mass of ion-exchanged water, 50 parts by mass of 1,3-butadiene, 0.3 of tert-dodecyl mercaptan 0.3 Part by mass, 2 parts by mass of higher fatty acid sodium, 0.075 part of potassium hydroxide and 0.15 part by mass of potassium persulfate were charged, and polymerization was started at 80 ° C. After 3 hours, 50 parts by mass of 1,3-butadiene and 0.3 parts by mass of tert-dodecyl mercaptan were added, and the polymerization was further continued for 4 hours to obtain an aqueous dispersion of raw material particles L8. The glass transition temperature, the volume average particle size, and the 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. The results are shown in Table 1.
Subsequently, using the latex containing the raw material particles L8, the heterogeneous polymer particles P8 were synthesized in the same manner as in Synthesis Example 1 except that the amount of the polymerization initiator or chain transfer agent was appropriately adjusted. The physical properties of the heterophasic polymer particles P8 were also evaluated in the same manner as in Synthesis Example 1. The results are shown in Table 1.

5-2. Production of plating composition Example 1-1
15 parts by mass of heterophasic polymer particles P1 and 30 parts by mass of heterophasic polymer particles P5 were mixed to obtain a plating composition M1. With respect to this plating composition M1, the moisture content was measured in accordance with B method (Karl Fischer method) of JIS K7251 "Plastics-Determination of moisture content". The results are shown in Table 2.

Further, 1 g of the plating composition M1 was put into 20 ml of acetone and shaken for 2 hours. Next, the mixture was centrifuged until it was completely separated into two layers, and the insoluble matter was collected and redispersed in acetone. 40 μl of this dispersion was diluted with 100 g of water, and this diluted solution was placed on a TEM grid and dried to prepare a sample for particle measurement.
Thereafter, the sample was brought into contact with osmium tetroxide vapor generated by heating to stain the plating composition M1. 200 pieces of this were observed with a transmission electron microscope “JEM-1400Plus” manufactured by JEOL Ltd. at a magnification of 2500 times.
Using the image analysis software “Image-Pro Plus Ver. 4.0 for Windows (registered trademark)”, the obtained TEM image is converted into particles having a particle size of 0.05 μm or more and less than 0.15 μm. And the volume% of particles existing in a particle diameter interval of 0.15 μm or more and 0.5 μm or less were calculated. The results are shown in Table 2.

Further, with respect to the plating composition M1, the volume average particle diameter and standard deviation were measured in the same manner as the heterophasic polymer particles P1, and the coefficient of variation was calculated by the following formula. The results are shown in Table 2.
Coefficient of variation (%) = (standard deviation / volume average particle diameter) × 100

Examples 1-2 to 1-11 and Comparative Examples 1-1 to 1-6
Using various heterophasic polymer particles in the proportions shown in Table 2, compositions for plating M2 to M17 were produced. And the physical-property measurement was performed like Example 1-1. The results are shown in Table 2.

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

  1 g of the pellets was added to 20 ml of acetone (an appropriate solvent in which the thermoplastic resin is completely dissolved) and shaken for 2 hours. Next, the mixture was centrifuged until it was completely separated into two layers, and the insoluble matter was collected and redispersed in acetone. 40 μl of this dispersion was diluted with 100 g of water, and this diluted solution was placed on a TEM grid and dried to prepare a sample for measuring the heterophasic polymer particles contained in the pellets. In the same manner as described above, the volume% of the particles existing in the particle diameter section of 0.05 μm or more and less than 0.15 μm, and the particle diameter of 0.15 μm or more and 0.5 μm or less exist in the particle diameter section. When the volume% of the particles to be calculated was calculated, the same results as the plating composition M1 shown in Table 2 before production of the plating molding material were obtained.

Moreover, about the heterophasic polymer particle | grains collect | recovered by the said process, when a volume average particle diameter and a standard deviation are measured and the variation coefficient was computed by the following formula, the molding composition for plating shown in Table 2 before manufacture is shown. The same result as the heterophasic polymer particles contained in the product M1 was obtained.
Coefficient of variation (%) = (standard deviation / volume average particle diameter) × 100

Using the above pellets, an injection molding machine “J100E-C5 type” (model name) manufactured by Nippon Steel Works Co., Ltd. was molded under the conditions of a cylinder set temperature of 220 ° C. and a mold temperature of 40 ° C. A test piece (notched, thickness 2 mm) was obtained. And Charpy impact strength (unit kJ / m < ² >) was measured based on ISO179 using digital impact tester "DG-CB" (model name). If the Charpy impact strength is 15 kJ / m ² , it can be determined that the impact resistance is excellent. The results are shown in Table 3.

  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 according to the above molding conditions, and copper plating was applied to this surface using a CRP process manufactured by Okuno Pharmaceutical Co., Ltd. went. And the peeling strength and external appearance property of the plating film in the obtained plating molded body were evaluated by the following methods. The results are shown in Table 3.

First, the test piece was immersed in a “CRP cleaner” at 40 ° C. for 3 minutes for degreasing. Thereafter, 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 with a 35% hydrochloric acid aqueous solution at 35 ° C. for 1 minute, and further immersed in a “CRP catalyst” at 35 ° C. for 6 minutes, whereby the Pd—Sn colloid catalyst treatment was performed. Went.
Thereafter, the obtained catalyst 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 conductor. Then, the test piece after the conductor treatment was washed with water at 20 ° C. and electroplated with copper at room temperature for 60 minutes to obtain a 40 μm thick copper layer. Subsequently, this test piece with a copper layer was washed with water at 20 ° C. and dried at 80 ° C. for 2 hours.
In order to evaluate the adhesiveness of the copper layer in the test piece with the copper layer, the peeling strength was measured according to JIS H 8630. If the peeling strength is 1.0 kN / m or more, it can be determined that the plating adhesion is excellent.

Moreover, the test piece with a copper layer was observed visually, and the external appearance property was determined on the following reference | standard.
“◯”: Appearance that can be put to practical use when the plated molded body is glossy and no excessive unevenness is observed.
"X": Unevenness is clearly recognized, and it is difficult to put to practical use because it impairs the beauty.

Examples 2-2 to 2-10 and comparative examples 2-1 to 2-6
Using the various plating compositions and the acrylonitrile / styrene copolymer in the ratios shown in Table 3, a molding material for plating was produced in the same manner as in Example 2-1. And various evaluation was performed like Example 2-1. The results are shown in Table 3.

Example 2-11
30 parts by mass of the plating composition M11, 20 parts by mass of the acrylonitrile / styrene copolymer and 50 parts by mass of a polycarbonate resin “NOVAREX 7022R” (trade name) manufactured by Mitsubishi Engineering Plastics Co., Ltd. Then, the mixture was melt-kneaded (set temperature: 260 ° C.) using a Banbury mixer to produce pellets made of a molding material for plating.

  Example 2-1 except that the cylinder pellet temperature was set to 260 ° C. and the mold temperature was set to 60 ° C. using the manufactured pellets by an injection molding machine “J100E-C5 type” (model name) manufactured by Nippon Steel Works. In the same manner as above, injection molding was performed to prepare a test piece. Various evaluations were performed. The results are shown in Table 3.

  As is apparent from Tables 2 and 3, in Examples 2-1 to 2-11 corresponding to the present invention, it is possible to produce a plated molded article having excellent plating adhesion and impact resistance and good plating appearance. did it. On the other hand, in Comparative Examples 2-1 to 2-6 which do not correspond to the present invention, it was not possible to produce a plated article having good impact resistance, plating adhesion and appearance.

Claims (7)

A plating composition containing heterophasic polymer particles and water,
The content rate of the said water is a composition for plating which is 0.1-1 mass% with respect to the whole said composition for plating.   The plating composition according to claim 1, wherein a coefficient of variation in particle diameter of the heterophasic polymer particles is 40 to 90%. In the heterophasic polymer particles,
The content ratio of the polymer particles having a particle diameter of 0.05 μm or more is 80% by volume or more based on the whole of the heterophasic polymer particles,
The plating composition according to claim 1 or 2, wherein a content ratio of the polymer particles having a particle diameter of 0.05 µm or more and less than 0.15 µm is 10 to 60% by volume based on the whole of the heterophasic polymer particles. object.   A molded article for plating containing the plating composition according to any one of claims 1 to 3 and a thermoplastic resin.   The contents of the heterophasic polymer particles and the thermoplastic resin contained in the plating composition are 10 to 80% by mass and 20 to 90% by mass, respectively, when the total of both is 100% by mass. The molded article for plating according to claim 4.   A plated molded body comprising the plated molded body according to claim 4 or 5 and a plated layer disposed on a surface of the plated molded body.   6. A plating method for forming a plating layer on the molding for plating according to claim 4 or 5, wherein the plating layer is formed after etching the molding for plating at 30 to 80C.

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