JP6960786B2 - Plating pellet composition, plating molded body and its manufacturing method, plating molded body and its manufacturing method, and plating method - Google Patents

Description

The present invention relates to a pellet composition for plating, a molded body for plating and a method for producing the same, a molded body for plating and a method for producing the same, and a plating method. More specifically, the present invention provides a pellet composition for plating, a molded body for plating, and a production thereof, which provides a molded body for plating capable of forming a metal film or an alloy film having excellent adhesion on the surface thereof by plating. The present invention relates to a method, a plated body provided with a metal film or an alloy film, a method for producing the same, and a plating method.

Conventionally, a plated molded body provided with a metal film or an alloy film obtained by plating the surface of the molded body has, for example, a metallic appearance, an enhanced design, durability and weather resistance. It is used in vehicle parts, electrical / electronic parts, OA equipment parts, home appliances, housing parts, clothing supplies, etc. for the purpose of enhancing, antistatic, electrical conductivity, and electromagnetic wave shielding.
As a plating method for a molded body, steps such as etching (surface roughening), neutralization, catalyst application, activation, electroless plating, acid activity, and electroplating are sequentially carried out, so-called catalyst accelerator. The lator method and the direct plating method, which omits the electroless plating process, are known.

As a thermoplastic resin composition which is excellent in molding processability, impact resistance, etc. and which gives a molded body 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.)

Japanese Unexamined Patent Publication No. 2002-338636 JP-A-2007-177223

With the expansion of applications of plated molded bodies, there is a need for a molding material for plating that provides a molded body with better adhesion to a metal layer produced by plating. Further, when an impact is applied to the molded body, the fragments are scattered when the molded body is brittlely broken. In order to suppress this, a plating molding material for producing a molded body that is ductilely fractured by impact is required.

The present invention has a tendency to be ductilely broken by an external impact, has excellent impact resistance, and can form a metal layer or an alloy layer having excellent adhesion by plating on the surface thereof. It is an object of the present invention to provide a pellet composition for plating, a molded body for plating and a method for producing the same, a molded body for plating having a metal layer or an alloy layer and a method for producing the same, and a plating method. ..

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

Application example 1
One aspect of the pellet composition for sieving of the present invention contains pellets containing a matrix phase containing a thermoplastic resin and heterophase polymer particles dispersed in the matrix phase, and is used for forming a molded body for sieving. In the pellet composition used, the content ratio of the pellets passing through the 3 mesh sieve is 98% by mass or more with respect to the total amount of the pellet composition, and the pellet composition passes through the 5 mesh sieve and 9 meshes. The content ratio of the pellets that do not pass through the sieve is 50% by mass or more with respect to the total amount of the pellet composition.

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

Application example 3
In the heterophase 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 of the heterophase 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 total of the heterophase polymer particles.

Application example 4
The content ratios of the heterophase polymer particles and the thermoplastic resin contained in the pellets are preferably 10 to 80% by mass and 20 to 90% by mass, respectively, when the total of both is 100% by mass. ..

Application example 5
One aspect of the method for producing a plated molded product of the present invention is that the plating pellet composition according to any one of Application Examples 1 to 4 is melt-kneaded and then molded into a predetermined shape.

Application example 6
One aspect of the plated molded product of the present invention is one in which the plating pellet composition according to any one of Application Examples 1 to 4 is melt-kneaded and then molded into a predetermined shape.

Application example 7
One aspect of the method for producing a plated molded product of the present invention is to melt-knead the pellet composition for plating according to any one of Application Examples 1 to 4 and then mold it into a predetermined shape to obtain the resulting plating molding. The body is etched and then plated.

Application example 8
In one aspect of the plated molded product of the present invention, the plating pellet composition according to any one of Application Examples 1 to 4 is melt-kneaded, molded into a predetermined shape, and etched into the obtained plated molded product. Then, the resin molded portion and the plating layer obtained by plating are provided.

Application example 9
One aspect of the plating method of the present invention is a method of forming a plating layer on the plating molded body according to Application Example 6, in which the plating molded body is etched at 30 to 80 ° C. and then plated. It forms a layer.

The method for producing the plating pellet composition of the present invention and the plating molded body of the present invention is suitable for forming a metal layer or an alloy layer having excellent adhesion to the surface thereof, and is resistant to external impact. A molded body for plating having excellent properties is provided.
According to the molded body for plating of the present invention, a plated 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 a base is provided.
The plated molded product of the present invention has excellent adhesion to the base molded portion of the metal layer or alloy layer, and thus has excellent appearance.
According to the plating method of the present invention, a metal layer or an alloy layer having excellent adhesion to the underlying resin molded portion can be efficiently formed.

FIG. 6 is a cross-sectional view of heterogeneous polymer particles having a core-shell heterogeneous structure. Cross-sectional view of heterophase polymer particles having a sea-island-like (island-in-sea) heterogeneous structure. Sectional drawing of the heterophase polymer particle which has an octopus-like heterophase structure. Sectional drawing of the heterophase polymer particle which has another octopus-like heterophase structure. Cross-sectional view of the heterophase polymer particles having a juxtaposed (side-by-side) heterogeneous structure. FIG. 3 is a cross-sectional view of a heterogeneous polymer particle having a multi-particle heterogeneous phase-heterogeneous structure. Sectional drawing of the heterophase polymer particle having a raspberry-like heterophase structure. FIG. 6 is a cross-sectional view of a different phase polymer particle having another multi-particle different phase different phase structure. Sectional drawing of the heterophase polymer particle which has a Daruma-like heterophase structure.

Hereinafter, preferred embodiments according to the present invention will be described in detail. It should be noted that the present invention is not limited to the embodiments described below, but should be understood to include various modifications implemented without changing the gist of the present invention.
In the present specification, "(meth) acrylic acid-" is a concept that includes both "acrylic acid-" and "methacrylic acid-". "-(Meta) acrylate" is a concept that includes both "-acrylate" and "-methacrylate". Further, "(meth) allyl" is a concept that includes both "allyl" and "methallyl".

1. 1. Plating Pellet Composition The plating pellet composition of the present invention is a pellet containing a matrix phase containing a thermoplastic resin and heterophase polymer particles dispersed in the matrix phase (hereinafter, “heterophase polymer particles”). It is a composition containing (referred to as "containing pellets"), and is a pellet composition used for forming a polymer for plating.

In the present invention, by using a plating pellet composition containing pellets containing heterophase polymer particles of a specific size, it is suitable for forming a metal layer or an alloy layer having excellent adhesion on the surface thereof, and is suitable from the outside. It is possible to obtain a molded body for plating having excellent impact resistance against impact. That is, the content ratio of the heterophase polymer particle-containing pellets passing through the 3-mesh sieve is 98% by mass or more, preferably 99% by mass or more, based on the total amount of the pellet composition. The content ratio of the heterophase polymer particle-containing pellets that pass through the 5-mesh sieve and do not pass through the 9-mesh sieve is 50% by mass or more, preferably 70% by mass, based on the total amount of the pellet composition. % Or more, more preferably 85% by mass or more. The above "mesh" is based on a standard sieving method using a Tyler sieve.

When the amount of the heterophase polymer particle-containing pellets passing through the 3-mesh sieve is 98% by mass or more, the melt-kneading of the pellet composition for plating of the present invention becomes easy, and a molded body for plating having a uniform composition can be easily obtained. be able to. Further, when the amount of the heterophase polymer particle-containing pellets that pass through the 5-mesh sieve and do not pass through the 9-mesh sieve is 50% by mass or more, when the pellet composition for plating of the present invention is melt-kneaded. , The generation of air bubbles is suppressed, and a dense molded body for plating can be produced. As a result, the mechanical strength of the plated molded product can be further improved.

In the present invention, when the pellet composition for plating is melt-kneaded and then molded into a predetermined shape to produce a molded body for plating, the heterophase polymer particles are not only contained inside the molded body but also on the surface thereof. Be exposed. When electroplating or the like is applied to the plated molded body, first, a treatment such as bringing the surface of the plated molded body into contact with an etching solution is performed, but at this time, the surface of the plated molded body is exposed. The heterophase polymer particles are removed, and recesses are formed on the surface of the molded product. It is presumed that the recess formed in this way functions as an anchor hole for improving the adhesion of the plating film, and a plating film exhibiting good adhesion strength can be produced.
Hereinafter, the constituent components of the heterophase polymer particle-containing pellet contained in the plating pellet composition of the present invention will be described in detail.

The thermoplastic resin constituting the matrix phase of the heterophase polymer particle-containing pellets is not particularly limited, but is ABS resin, acrylonitrile / styrene copolymer, acrylonitrile / styrene / maleimide compound ternary copolymer, polystyrene, styrene / Examples thereof include styrene resins such as maleic anhydride copolymers; acrylic resins such as polymethylmethacrylate; polycarbonate resins; polyamide resins; polyester resins such as polybutylene terephthalate; or alloys containing at least two of these. Of these, a styrene resin is preferable, and the heterophase polymer particles contained in the molding for plating obtained by using the pellet composition for plating are uniformly dispersed and are superior in mechanical strength. ABS resin is particularly preferred.

The heterophase polymer particles according to the present invention are not uniform phases but particles composed of two or more different phases.
The cross-sectional structure of the heterophase polymer particles includes a core-shell heterophase structure (FIG. 1), a sea-island-like (island-in-sea) heterophase structure (FIG. 2), a squid-like heterophase structure (FIGS. 3 and 4), and a juxtaposed type (FIG. 4). Examples thereof include a side-by-side) heterogeneous structure (FIG. 5), a raspberry-like heterogeneous structure (FIG. 7), a multi-particle heterogeneous phase structure (FIGS. 6 and 8), and a dull-shaped heterogeneous structure (FIG. 9). Of these heterogeneous structures, the core-shell heterogeneous structure (FIG. 1) is preferred. The heterophase polymer particle-containing pellet contained in the plating pellet composition of the present invention may include one in which two or more kinds of various different phase structures as described above are combined to form one different phase particle.

The heterophase polymer particles are preferably single particles formed by two or more polymers having different chemical structures or polymers having two or more block structures having different chemical structures.
When the heterophase polymer particles are composed of two or more polymers having different chemical structures, the polymer having a chemical structure having excellent mechanical properties such as impact resistance constitutes the thermoplastic resin. It is preferably formed in combination with a polymer having a chemical structure having a high affinity with (styrene resin, acrylic resin, polycarbonate resin, polyamide resin, polyester resin, etc.). When the heterophase polymer particles are composed of polymers having two or more block structures having different chemical structures, the block having a chemical structure having excellent mechanical properties such as impact resistance and the matrix phase are used. It is preferable to have a block having a chemical structure having a high affinity with the constituent thermoplastic resin, which is phase-separated to form a heterogeneous structure.

It should be noted that the chemical structure having a high affinity between the homogeneous polymer particles composed of a single polymer having a chemical structure having excellent mechanical properties such as impact resistance and the thermoplastic resin constituting the matrix phase. In the composition obtained by kneading the heterophase polymer particle-containing pellets containing the homogeneous polymer particles composed of a single polymer having the above, the difference in specific gravity between the two types of homogeneous polymer particles and the particle surface. Due to differences in tension and surface polarity, it is difficult to obtain a molded product that is uniformly dispersed in the matrix phase containing the thermoplastic resin. However, the different phase polymer particles constituting the different phase polymer particle-containing pellet contained in the plating pellet composition of the present invention are two or more polymers having different chemical structures or two or more blocks having different chemical structures as described above. In the case of a single particle formed by a polymer having a structure, it is possible to suppress inhomogeneous dispersion by the thermoplastic resin due to the difference in the polymer, and uniformly disperse it in the matrix phase containing the thermoplastic resin. It becomes easy.

Heterogeneous polymer particles are uniformly exposed on the surface of the plated molded product of the present invention produced by using the plating pellet composition of the present invention. When plating is performed to form a metal film or an alloy film on a molded body for plating, the exposed heterophase polymer particles are etched (surface roughened) by bringing the surface of the molded body for plating into contact with an etching solution. Removed by processing. As a result, homogeneous anchor holes are formed on the surface of the molded product. It is presumed that by forming a plating layer on the surface of the molded body having the anchor holes thus produced, a plating film exhibiting good adhesion strength can be produced.

When the heterophase polymer particles are composed of two or more polymers having different chemical structures, one of the polymers has a chemical structure having excellent mechanical properties such as major impact resistance. The mass ratio (A / B) of the polymer B to the polymer B having a chemical structure having a high affinity with the thermoplastic resin constituting the matrix phase, which is one of the other major ones, is preferably 1 / 0.1. It is ~ 1 / 1.5, more preferably 1 / 0.3 ~ 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 further preferably 85% by mass or more with respect to the entire heterophase polymer particles. ..

When the heterophase polymer particles are composed of a polymer 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. A block structure A'having a chemical structure having excellent mechanical properties such as, and a block structure B'having a chemical structure having a high affinity with the thermoplastic resin constituting the matrix phase, which is one of the other major components. The mass ratio (A'/ B') is preferably 1 / 0.1 / 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, still more preferably 85% by mass or more, based on the total amount of the heterophase polymer particles. Is.

In a molded body for plating produced by using the pellet composition for plating of the present invention, the heterophase polymer particles exposed on the surface thereof are removed by etching to form anchor holes, and then good adhesion is achieved by plating. It is presumed to give a plating film that develops strength. However, the heterophase polymer particles that are not exposed on the surface of the plated molded body remain inside the plated molded body without being removed by etching, and affect the mechanical strength of the molded body.
However, the polymer A having a chemical structure having excellent mechanical properties such as one major impact resistance and the other major chemical structure having a high affinity with the thermoplastic resin constituting the matrix phase. The heterophase polymer particles having the polymer B having the above, or the block structure A'having one main chemical structure having excellent mechanical properties such as impact resistance, and the other one main matrix phase. By containing the heterophase polymer particles having a block structure B'having a chemical structure having a high affinity with the constituent thermoplastic resin in the above preferable configuration, the mechanical strength of the molded product for plating is significantly increased after etching. A polymer molded body exhibiting good mechanical properties can be produced without deterioration.

The particle size of the heterophase polymer particles contained in the heterophase polymer particle-containing pellet according to 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, and more preferably in the range of 80 nm to 250 nm. When plating is performed on a molded body for plating produced by using the pellet composition for plating of the present invention having pellets containing different phase polymer particles containing different phase polymer particles within the above range, etching (surface roughening) is performed. ), 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 determined from an image obtained by dyeing the heterophase polymer particles with osmium tetroxide and then observing the stained polymer particles with a transmission electron microscope. Arbitrarily, for example, 200 particles can be selected and calculated using analysis software.

In the present invention, the coefficient of variation of the particle size of the heterophase polymer particles gives a plated molded body having excellent impact resistance, and when the plated molded body is plated, the adhesion to the underlying resin molded portion is obtained. It is preferably 40 to 90%, more preferably 40 to 80%, still more preferably 45 to 75%, because an excellent metal layer or alloy layer is efficiently formed.
The coefficient of variation can be obtained by the following formula using the volume average particle size of the heterophase polymer particles and the standard deviation of the particle size distribution.
Coefficient of variation (%) = (standard deviation / volume average particle size) x 100
Since 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, the volume average particle size and the standard. The deviation can be calculated from the measured value of the particle size.

In the heterophase polymer particle-containing pellet according to the present invention, the content ratio R1 of the heterophase polymer particles having a particle diameter of 0.05 μm or more is based on the total amount of the heterophase polymer particles contained in the heterophase polymer particle-containing pellet. It is preferably 80% by volume or more, more preferably 90% by volume or more. Further, the content ratio R2 of the heterophase polymer particles having a particle size of 0.05 μm or more and less than 0.15 μm is preferably 10 to 60 volumes with respect to the entire heterophase polymer particles contained in the heterophase polymer particle-containing pellets. %, More preferably 20 to 50% by volume. By having the content ratios R1 and R2 of the different phase polymer particles having the above-mentioned constitutions, the impact resistance of the plating molded body produced by using the plating pellet composition of the present invention and the adhesion of the metal layer or the like by the plating can be improved. Can be improved.
In the above content ratio R1, the total volume of the heterophase polymer particles having a particle size of 0.05 μm or more is V1, and the total volume of the heterophase polymer particles contained in the heterophase polymer particle-containing pellets is V. It can be calculated by the formula.
R1 = (V1 / V) x 100
Further, in the content ratio R2, the total volume of the heterophase polymer particles having a particle size of 0.05 μm or more and less than 0.15 μm is V2, and the total volume of the heterophase polymer particles contained in the heterophase polymer particle-containing pellets is defined as V2. As V, it can be calculated by the following formula.
R2 = (V2 / V) x 100

The coefficient of variation of the particle size of the different phase polymer particles can be controlled by the production conditions of the different phase polymer particles. Further, the coefficient of variation may be controlled by preparing two or more kinds of different phase polymer particles in advance and using them in combination. For example, when controlling the fluctuation coefficient by using two types of different-phase polymer particles (A1) and different-phase polymer particles (A2) having different sizes, the particle size of the different-phase polymer particles (A1) is preferably 50. It is ~ 150 nm, more preferably 60 to 120 nm, and the particle size of the heterophase polymer particles (A2) is preferably 200 to 800 nm, more preferably 250 to 700 nm.

As described above, the heterophase polymer particles of the preferred embodiment contain two or more polymers having different chemical structures or polymers having two or more block structures having different chemical structures. In the present invention, the affinity between the repeating unit derived from the conjugated diene (hereinafter referred to as "repeating unit (r1)"), which contributes to mechanical properties such as impact resistance, and the thermoplastic resin constituting the matrix phase. Contains two or more polymers with different chemical structures or polymers with two or more block structures with different chemical structures, including repeating units with highly functional groups (hereinafter referred to as "repeating units (r2)"). Is preferable.
Hereinafter, the repeating unit contained in the polymer constituting such heterophase polymer particles will be described.

By using a plating pellet composition containing heterophase polymer particle-containing pellets having a repeating unit (r1) derived from a conjugated diene, it is possible to produce a plated molded product having excellent mechanical properties such as impact resistance. .. The repeating unit (r1) may be of only one type or of 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-chlor-1,3-butadiene and the like. Of these, 1,3-butadiene is particularly preferable. The repeating unit derived from the conjugated diene contained in the heterophase 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. be. A molded product for plating obtained by using a pellet composition for plating containing pellets containing different phase polymer particles containing different phase polymer particles in which the content ratio of the repeating unit (r1) derived from the conjugated diene is within the above range. In, the impact resistance can be further improved.
Further, the heterophase polymer particles have a functional group having a high affinity between the polymer derived from the conjugated diene and having a repeating unit (r1) of 45% by mass or more and the thermoplastic resin constituting the matrix phase. It is more preferable to contain a polymer having a total repeating unit (r2) of 20% by mass or more.

When the heterophase polymer particles contain a repeating unit (r2) having a functional group having a high affinity with the thermoplastic resin constituting the matrix phase, for plating containing pellets containing the heterophase polymer particles. When the pellet composition is kneaded, the heterophase polymer particles can be uniformly dispersed in the thermoplastic resin, and a molded product for plating having excellent mechanical strength can be produced.

Examples of the functional group having a high affinity with the thermoplastic resin include a carboxyl group, a carboxylic acid ester group, a dicarboxylic acid anhydride group, a carbonyl group, a hydroxyl group, an alkoxy group, an epoxy group, a formyl group, a cyano group and an amino group. Amid 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, thiophosphate group, phosphonic acid group, phosphonic acid Examples include an ester group. Of these, a carboxylic acid ester group and a cyano group are preferable. The repeating unit (r2) contained in the heterophase 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, and as the (meth) acrylic acid ester, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, etc. Isobutyl (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 , (Meta) ethylene glycol acrylate, di (meth) ethylene glycol acrylate, di (meth) propylene glycol acrylate, tri (meth) trimethylol acrylate propane, tetra (meth) pentaerythritol acrylate, hexa (meth) Examples thereof include dipentaerythritol acrylate and allyl (meth) acrylate. 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 that gives a repeating unit containing a cyano group include unsaturated nitrile compounds.
Examples of the unsaturated nitrile compound include acrylonitrile, methacrylonitrile, etacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, α-isopropylacrylonitrile, vinylidene cyanide and the like. Of these, acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is particularly preferable.

The content ratio of the repeating unit (r2) is preferably 3 to 35% by mass, more preferably 5 to 30 when the total of the repeating units contained in the polymers constituting the heterophase polymer particles is 100% by mass. It is mass%. In particular, it can be obtained by using a pellet composition for plating containing pellets containing different phase polymer particles containing different phase polymer particles in which the content ratio of the repeating unit (r2) derived from the unsaturated nitrile compound is within the above range. In the molded body for plating, the mechanical strength can be further improved.

The heterophase polymer particles may contain other repeating units other than the above (hereinafter, referred to as “repeating unit (r3)”). The repeating unit (r3) includes 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. Repetitive units derived from acid alkylamides, repeating units derived from carboxylic acid vinyl esters, repeating units derived from ethylenically unsaturated dicarboxylic acid acid anhydrides, repeating units derived from ethylenically unsaturated carboxylic acid aminoalkylamides. Units and the like can be mentioned. The repeating unit (r3) contained in the heterophase polymer particles may be only one type or two or more types. Of 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 preferable.
Examples of unsaturated carboxylic acids include monocarboxylic acids and 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 preferable.

Examples of the fluorine-containing compound having an ethylenically unsaturated bond include vinylidene fluoride, ethylene tetrafluoride, and propylene hexafluoride.
Examples of the alkylamide of the ethylenically unsaturated carboxylic acid include (meth) acrylamide and N-methylol acrylamide.
Examples of the vinyl carboxylic acid ester include vinyl acetate and vinyl propionate.
Examples of the aminoalkylamide of the ethylenically unsaturated carboxylic acid include aminoethylacrylamide, dimethylaminomethylmethacrylamide, and methylaminopropylmethacrylamide.

In the heterophase polymer particles of the preferred embodiment, the repeating units (r1), (r2) and (r3) may be distributed in any manner, but at least the repeating unit (r2) is exposed on the surface of the particles. Is preferable.

Next, the physical characteristics of the heterophase polymer particles will be described.
In the heterophase polymer particles, the endothermic peak difference between the plurality of phases constituting the particles is preferably 5 ° C. or higher.
Further, in the present invention, when the heterophase polymer particles are subjected to differential scanning calorimetry (DSC) according to JIS K7121, the weight shows two or more endothermic peaks in the temperature range of -100 ° C to 200 ° C. It is preferably coalesced particles. A molded product for plating obtained by using a plating pellet composition containing pellets containing different phase polymer particles containing different phase polymer particles having two or more endothermic peaks in this temperature range has excellent impact resistance and plating. Has 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.

Further, a molded product for plating obtained by using a pellet composition for plating containing pellets containing heterophase polymer particles containing two or more endothermic polymer particles exhibiting two or more endothermic peaks in a temperature range of −100 ° C. to 0 ° C. , The elasticity is improved and the impact resistance is improved. 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.
Further, the heterophase polymer particle-containing pellets containing the heterophase polymer particles exhibiting two or more endothermic peaks in the temperature range of 50 ° C. to 200 ° C. have appropriate fluidity during melt-kneading during the production of a molded product for plating. And has excellent molding processability. In this case, the temperature of the 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 heterophase polymer particles is preferably 20,000 to 200,000, more preferably 50,000 to 150,000. This Mw is a standard polystyrene-equivalent value measured by gel permeation chromatography (hereinafter, also referred to as “GPC”).

The method for producing the heterophase polymer particles is not particularly limited, and conventionally known methods can be used for production. For example, a two-stage polymerization method such as an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, or a seed polymerization method, a plurality of polymers are mixed in the presence or absence of a solvent, coagulated and dried, and then pulverized. Alternatively, a method of spray-drying to form a powder by a method such as a spray-drying method can be applied. As a specific example of the method for producing the heterophase polymer particles used in the present invention, a predetermined monomer is polymerized by a conventional method until the polymerization conversion rate reaches 20 to 100%, followed by another weight. A method of adding a monomer to be coalesced and polymerizing 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 heterophase polymer particles.

In the case of producing the heterophase polymer particles of the above-mentioned preferred embodiment, that is, the heterophase polymer particles containing the repeating unit (r1) derived from the conjugated diene, for example, it has a predetermined average particle size prepared by a known polymerization method and has a predetermined average particle size. A monomer that gives an aqueous dispersion (latex) of polymer particles (raw material particles) containing a repeating unit (r1) a repeating unit having a functional group having a high affinity with the thermoplastic resin constituting the matrix phase. It is preferable to apply a method of adding, emulsifying, polymerizing, and grafting. As this monomer, an aromatic vinyl compound, a vinyl cyanide compound and the like are preferable. When an aqueous dispersion (latex) in which the 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, and then washed with water and dried to obtain the heterophase polymer particles. 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; and organic acids such as acetic acid, lactic acid and citric acid can be used.

Examples of emulsifiers that can be used in emulsion polymerization include sulfate ester salts of higher alcohols, alkylbenzene sulfonates, alkyldiphenyl ether disulfonates, aliphatic sulfonates, aliphatic carboxylates, dehydroavietates, and surfactants. Anionic surfactants such as acid-formalin condensates, sulfate ester salts of nonionic surfactants; nonionic surfactants such as alkyl esters of polyethylene glycol, alkyl phenyl ethers of polyethylene glycol, alkyl ethers of polyethylene glycol; Examples thereof include perfluorobutyl sulfonates, perfluoroalkyl group-containing phosphoric acid esters, perfluoroalkyl group-containing carboxylates, and fluorine-based surfactants such as perfluoroalkyl ethylene oxide adducts. The emulsifier used may be only one type or two or more types.

Further, as the polymerization initiator, an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentan hydroperoxide and a reducing agent such as a sugar-containing pyrophosphate formulation and a sulfoxylate formulation were combined. Redox-based initiators; persulfates such as potassium persulfate and sodium persulfate; peroxides such as benzoyl peroxide, lauroyl peroxide, tert-butylperoxylaurate, and tert-butylperoxymonocarbonate. .. The polymerization initiator used may be only one type or two or more types.

A chain transfer agent can be used in combination during graft polymerization. Examples of the chain transfer agent include octyl mercaptans, n-dodecyl mercaptans, tert-dodecyl mercaptans, n-hexyl mercaptans, n-hexadecyl mercaptans, n-tetradecyl mercaptans, tert-tetradecyl mercaptans and other mercaptans; -Methylstyrene dimer, tetraethylthium sulfide, achlorein, metachlorine, allyl alcohol, 2-ethylhexylthioglycol and the like can be mentioned. The chain transfer agent used may be only one type or two or more types.

When a monomer for graft polymerization is added to an aqueous dispersion of raw material particles containing a repeating unit (r1) derived from a conjugated diene and polymerization is carried out, the graft ratio in the obtained heterophase polymer particles is preferably It is 10 to 150% by mass, more preferably 30 to 100% by mass.
This graft ratio is calculated by the following formula.
Graft ratio (mass%) = {(ST) / T} x 100
(In the formula, for S, 1 g of the produced heterophase polymer particles was put into 20 ml of acetone, shaken for 2 hours by a shaker, and then centrifuged to separate and dry the insoluble and soluble components. It is the mass (g) of the obtained insoluble matter, and T is the mass (g) of the raw material particles having a repeating unit derived from the conjugated diene contained in 1 g of the heterophase 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 used to the total amount of the monomer is It is preferably 70% by mass or more, more preferably 80% by mass or more.

A monomer that gives a repeating unit having a functional group having a high affinity with the thermoplastic resin constituting the matrix phase is added to the aqueous dispersion of the raw material particles containing the repeating unit (r1) derived from the conjugated diene. In the heterophase polymer particles produced by graft polymerization, 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 heterophase polymer particles with osmium tetroxide or the like by a known method and observing with a transmission electron microscope.

The heterophase polymer particle-containing pellets can contain a plurality of types of heterophase polymer particles, and are used in the case of producing heterophase polymer particles of such an embodiment. For example, the heterophase polymer particles (A11) and When producing the heterophase polymer particles containing the heterophase polymer particles (A12), the aqueous dispersion containing the heterophase polymer particles (A11) and the aqueous dispersion containing the heterophase polymer particles (A12) are mixed. Then, a coagulant may be added to the mixed solution. Further, the aqueous dispersion containing the different phase polymer particles (A11) and the aqueous dispersion containing the different phase polymer particles (A12) may be coagulated to produce each powder and then mixed. good.

The content ratio of the heterophase polymer particles and the thermoplastic resin contained in the heterophase polymer particle-containing pellets is suitable for forming a metal layer or an alloy layer having excellent adhesion to the surface thereof, and is resistant to an external impact. Since a polymer for plating having excellent impact resistance can be efficiently obtained, 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 50%, respectively. It is 70% by mass and 30 to 85% by mass, more preferably 20 to 60% by mass and 40 to 80% by mass.

When the thermoplastic resin contains ABS resin, the content ratio of the heterophase polymer particles derived from the plating pellet composition of the present invention is preferably 30 to 180 mass by mass with respect to 100 parts by mass of the thermoplastic resin. Parts, more preferably 50 to 150 parts by mass.
When the thermoplastic resin contains an alloy of ABS resin and polycarbonate resin, the content ratio of the heterophase polymer particles derived from the plating pellet composition of the present invention is preferably 100 parts by mass of the thermoplastic resin. Is 15 to 90 parts by mass, more preferably 25 to 75 parts by mass. From the viewpoint of impact resistance of the molded product for plating and adhesion strength of the plating film, the ratio of the polycarbonate resin to 100 parts by mass of the ABS resin is preferably 100 to 1000 parts by mass.

The heterophase polymer particle-containing pellet contained in the plating pellet composition of the present invention may be composed of a thermoplastic resin and heterophase polymer particles, or may further contain other components. Examples of other components include antioxidants, antioxidants, UV absorbers, lubricants, plasticizers, fillers, heat stabilizers, flame retardants, antistatic agents, colorants and the like.

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

Fillers include heavy calcium carbonate, glazed calcium carbonate, light calcium carbonate, magnesium carbonate, zinc carbonate, aluminum hydroxide, magnesium hydroxide, carbon black, clay, talc, fumed silica, calcined silica, precipitated silica, and pulverized. Silica, molten silica, kaolin, silica soil, zeolite, titanium oxide, quicklime, iron oxide, zinc oxide, barium oxide, aluminum oxide, magnesium oxide, aluminum sulfate, glass fiber, carbon fiber, glass balloon, silas balloon, saran balloon , Phenol balloon and the like.
Examples of the heat stabilizer include a phosphite-based heat stabilizer, a lactone-based heat stabilizer, a hindered phenol-based heat stabilizer, a sulfur-based heat stabilizer, an amine-based heat stabilizer, and the like.

Examples of the flame retardant include organic flame retardants, inorganic flame retardants, reactive flame retardants and the like.
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; trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, tri Hexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresil diphenyl phosphate, dicredyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, etc. Phosphoric acid esters, modified compounds thereof, condensed phosphoric acid ester compounds, phosphorus-based flame retardants such as phosphazene derivatives containing phosphorus elements and nitrogen elements; guanidine salts, silicone-based compounds, phosphazene-based compounds and the like can be mentioned.
Examples of the inorganic flame retardant include aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zirconium compound, molybdenum compound, zinc stannate and the like.
Examples of the reaction flame retardant include tetrabromobisphenol A, dibromophenol glycidyl ether, brominated aromatic triazine, tribromophenol, tetrabromophthalate, tetrachlorophthalic anhydride, dibromoneopentyl glycol, and poly (pentabromobenzylpolyacrylate). , Chlorendic acid (hetic acid), phthalic anhydride (phthalic anhydride), brominated phenol glycidyl ether, dibromocredyl glycidyl ether and the like.

The heterophase polymer particle-containing pellets are obtained by processing a thermoplastic resin composition containing a thermoplastic resin, heterophase polymer particles, and the other components blended as needed by an extruder or the like. , Can be made. For example, the thread diameter and its cut length can be appropriately changed by adjusting the die diameter, the pick-up speed, and the like using a pelletizer. Therefore, in the plating pellet composition of the present invention, a mixture of heterophase polymer particle-containing pellets having various sizes is classified by a predetermined sieve to form a plating pellet composition of the present invention. It can be produced by mixing pellets containing heterophase polymer particles of different sizes.

The plating pellet composition of the present invention may be composed of only the above-mentioned heterophase polymer particle-containing pellets, or may be composed of the above-mentioned different-phase polymer particle-containing pellets and other pellets.
The other pellets are not particularly limited, and may be, for example, pellets made of only a thermoplastic resin, pellets containing the thermoplastic resin and the above other components, and the like. When the plating pellet composition of the present invention contains other pellets containing a thermoplastic resin, the total amount of the thermoplastic resin and the content ratio of the heterophase polymer particles are determined by the plating pellet composition of the present invention. The above preferred proportions contained in are applied.

2. Molded product for plating and its manufacturing method The molded product for plating of the present invention is an article formed into a predetermined shape after the above-mentioned pellet composition for plating of the present invention is melt-kneaded, and is the same as the above-mentioned heterophase polymer particle-containing pellet. Similarly, it has a structure in which a thermoplastic resin is used as a matrix and heterophase polymer particles are dispersed therein. And some of the heterophase polymer particles are exposed.

When the above-mentioned pellet composition for plating is melt-kneaded, a kneader, an extruder, or the like is used to melt-knead the mixture at a temperature equal to or higher than the melting point of the thermoplastic resin having the highest melting point among the thermoplastic resins contained in the pellets. do. Then, a molded body for plating is obtained by processing with a conventionally known molding apparatus such as an injection molding apparatus, a press molding apparatus, a calender molding apparatus, a T-die extrusion molding apparatus, and a deformed extrusion molding apparatus.

By applying the plated body of the present invention to a conventionally known plating method such as a catalyst accelerator method, a direct plating method, or a chrome-free plating method, anchor holes can be formed efficiently and further. , Excellent precipitation and growth of metals or alloys can be obtained, and a metal layer or alloy layer having excellent adhesion to a substrate and appearance can be formed.

3. 3. Plating molded product and method for producing the same The plated molded product of the present invention is obtained by melt-kneading the above-mentioned plating pellet composition of the present invention, molding it into a predetermined shape, and etching the obtained plated molded product. It is an article provided with a resin molded portion and a plating layer (plating film) obtained by plating. In the case of producing a plated body, for example, steps such as etching (surface roughening), neutralization, catalyst application, activation, electroless plating, acid activity, and electroplating are performed on the plated body. It is possible to apply the catalyst method that advances sequentially, the direct plating method that omits the electroless plating process in this catalyst accelerator method, and the like. Etching and plating can be performed on the entire surface or a part of the surface of the molded article for plating.
The thickness of the plating layer is not particularly limited, but is preferably 5 to 200 μm, more preferably 5 to 150 μm.

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

The plated body of the present invention can be used for vehicle parts, electric products, 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 molded body for plating at 30 to 80 ° C.
The etching solution used in the etching step is not particularly limited, but may contain chromic acid, a chromic 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 holes. 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 will be insufficient. On the other hand, if the temperature of the etching solution 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
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 in a stainless steel autoclave equipped with a stirrer, heating and cooling device, thermometer and each raw material addition device. 4 parts by mass of sodium fatty acid, 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 were charged and reacted at 80 ° C. for 5 hours to produce diene polymer particles (hereinafter referred to as “diene polymer particles”). An aqueous dispersion (latex) of (referred to as "raw material particles L1") was obtained.

Laser Doppler / frequency analysis was performed using a "Microtrack UPA150 particle size analyzer" manufactured by Nikkiso Co., Ltd., and the volume average particle size of the raw material particle L1 was measured. As a result, the volume average particle size of the raw material particle L1 was 83 nm, and the particle size was The standard deviation of the distribution was 3 nm.

Next, in a glass flask equipped with a stirrer, a latex containing 40 parts by mass of raw material particles L1, 0.2 parts by mass of sodium pyrophosphate, and 0.004 ferrous sulfate heptahydrate in a nitrogen stream. A solution prepared by dissolving 0.3 parts by mass of mass and 0.3 parts by mass of glucose in 8 parts by mass of ion-exchanged water was charged, and under stirring, 30 parts by mass of ion-exchanged water, 0.5 parts by mass of potassium loginate, and styrene at an internal temperature of 70 ° C. 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. Then, this reaction solution was further stirred for 1 hour to obtain an aqueous dispersion (latex) of the heterophase polymer particles P1.
Then, 0.5 parts by mass of an antiaging agent was added, and then an aqueous sulfuric acid solution was added to solidify and dry the mixture to obtain a powder of the heterophase polymer particles P1.

1 g of the heterophase polymer particles P1 were added to 20 ml of acetone and shaken for 2 hours. Then, centrifugation was performed until the layers were completely separated into two layers, and the insoluble matter was recovered, 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 heterophase polymer particles P1 is known (T grams), a graft ratio of 78% was obtained by the following formula.
Graft rate = 100 × (ST) / T

In addition, the acetone-soluble component obtained when determining 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 refractometer. As a result of calculating the weight average molecular weight (Mw) of standard polystyrene for measurement, it was 103,000.
Further, the acetone-soluble component, 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 unit amount of the vinyl cyanide compound was calculated from the obtained amount of nitrogen, which was 25%.

1 g of the heterophase polymer particles P1 were added to 20 ml of acetone and shaken for 2 hours. Then, centrifugation was performed until the 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 particle measurement.
Then, the sample was brought into contact with the osmium tetroxide vapor generated by heating to stain the heterophase polymer particles P1. By observing 200 of these arbitrarily with a transmission electron microscope "JEM-1400Plus" manufactured by JEOL Ltd. at a magnification of 2500 times, it was confirmed that stained and unstained parts having different phases exist in one particle. bottom. As a result, it was found that the heterophase polymer particles P1 were the core-shell type heterophase polymer particles shown in FIG.
When the volume average particle diameter of the heterophase polymer particles P1 was measured using the image analysis software "Image-Pro Plus Ver. 4.0 for Windows (registered trademark)", the obtained TEM image was 90 nm. .. Further, the volume of all particles is calculated, and further, the volume% of the particles existing in the particle size section having a particle size 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% of the particles existing in the diameter section was calculated. The results are shown in Table 1.

Further, for the heterophase polymer particles P1, differential scanning calorimetry (DSC) according to JIS K7121 was performed, and the glass transition temperature Tg was observed. Two Tg were observed, at -81 ° C and 103 ° C.

Synthesis Examples 2-8
The same operations as in the production of the raw material particles L1 in Synthesis Example 1 were carried out except that the amount of the electrolyte used and the polymerization time were appropriately adjusted to obtain the raw material particles L2 to L8. The glass transition temperature, volume average particle size, and standard deviation of the particle size distribution of the raw material particles L2 to L8 were evaluated in the same manner as in Synthesis Example 1. The results are shown in Table 1.
Next, using each latex containing the raw material particles L2 to L8, 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, and the heterophase polymer particles P2 to P2. P8 was synthesized. The physical characteristics of the different phase polymer particles P2 to P8 were also evaluated in the same manner as in Synthesis Example 1. The results are shown in Table 1.

Synthesis example 9
In a stainless steel autoclave equipped with a stirrer, a heating / cooling device, a thermometer, each raw material addition device and an auxiliary agent addition device, 150 parts by mass of ion-exchanged water, 50 parts by mass of 1,3-butadiene, 0.3 of tert-dodecyl mercaptan. 20 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 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 the raw material particles L9. The glass transition temperature, volume average particle size, and standard deviation of the particle size distribution of the obtained raw material particles L9 were evaluated in the same manner as in Synthesis Example 1. The results are shown in Table 1.
Next, the heterophase polymer particles P9 were synthesized by performing the same operation as in Synthesis Example 1 except that the amount of the polymerization initiator or chain transfer agent used was appropriately adjusted using the latex containing the raw material particles L9. The physical characteristics of the heterophase polymer particles P9 were also evaluated in the same manner as in Synthesis Example 1. The results are shown in Table 1.

5-2. Production and Evaluation of Plating Pellet Composition Example 1
First, 15 parts by mass of the different phase polymer particles P1 and 30 parts by mass of the different phase polymer particles P5 were mixed to obtain mixed particles. 1 g of this mixed particle was put into 20 ml of acetone and shaken for 2 hours. Then, centrifugation was performed until the 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 particle measurement.
The sample was then contacted with osmium tetroxide vapor generated by heating to stain the polymer particles. 200 of these were arbitrarily 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 used as particles having a particle size of 0.05 μm or more and less than 0.15 μm. And the volume% of the particles existing in the particle size section of 0.15 μm or more and 0.5 μm or less were calculated. The results are shown in Table 2.
Further, the volume average particle size and standard deviation were measured or calculated from the obtained TEM image, 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 size) x 100

Next, 45 parts by mass of mixed particles composed of 15 parts by mass of heterophase polymer particles P1 and 30 parts by mass of heterophase polymer particles P5, and as a thermoplastic resin, an acrylonitrile-styrene copolymer (repeating unit derived from acrylonitrile: repeating unit: 55 parts by mass of a powder consisting of 30% by mass, a repeating unit amount derived from styrene: 70% by mass, and a weight average molecular weight Mw: 104,000) was mixed by a Henschel mixer. Then, the mixture was melt-kneaded (set temperature 200 ° C.) using a Banbury mixer to prepare pellets having a columnar shape and a non-uniform size.

The pellets are classified into pellets that pass through a 3-mesh sieve and pellets that pass through a 5-mesh sieve and do not pass through a 9-mesh sieve, and are mixed so as to have the ratios shown in Table 2. A pellet composition M1 was obtained.

1 g of the pellet composition M1 was added to 20 ml of acetone (a suitable solvent in which the thermoplastic resin was completely dissolved) and shaken for 2 hours. Then, centrifugation was performed until the 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 mixed particles made of a heterogeneous polymer contained in the pellet composition M1. Then, in the same manner as described above, the volume% of the particles existing in the particle size section having a particle size of 0.05 μm or more and less than 0.15 μm, and the particle size section having a particle size of 0.15 μm or more and 0.5 μm or less are present. When the volume% of the particles to be produced was calculated, the same results as those of the mixed particles composed of the heterophase polymer particles P1 and the heterophase polymer particles P5 shown in Table 2 before the pellets were produced were obtained.

Further, for the mixed particles recovered by the above treatment, the volume average particle size and standard deviation were measured or calculated, and the coefficient of variation was calculated by the following formula. As a result, the same results as those of the mixed particles shown in Table 2 before producing the pellets were obtained. Got
Coefficient of variation (%) = (standard deviation / volume average particle size) x 100

Using the pellet composition M1, injection molding was performed by an injection molding machine "J100E-C5 type" (model name) manufactured by Japan Steel Works, Ltd. under the conditions of a cylinder set temperature of 220 ° C. and a mold temperature of 40 ° C. to ISO 179. A test piece of the same size (notched, 2 mm thick) was obtained. Then, using a digital impact tester "DG-CB" (model name), the Charpy impact strength (unit: kJ / m ² ) was measured in accordance with ISO179. If the Charpy impact strength is 15 kJ / m ² , it can be judged that the impact resistance is excellent. The results are shown in Table 2.

Further, using the pellet composition M1, 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 a CRP process manufactured by Okuno Pharmaceutical Industry Co., Ltd. was used on the surface of the test piece. Copper plating was performed. Then, the peeling strength and appearance of the plating film in the obtained plated body were evaluated by the following methods. The results are shown in Table 2.

First, the test piece was immersed in a "CRP cleaner" at 40 ° C. for 3 minutes to degreas it. Then, 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 to perform 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 to treat with a Pd-Sn colloidal catalyst. Was done.
Then, the obtained catalytic 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, respectively, to carry out a conductive treatment. Then, the test piece after the conductorization treatment was washed with water at 20 ° C. and plated with electrolytic copper at room temperature for 60 minutes to obtain a copper layer having a thickness of 40 μm. Next, the 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 adhesion of the copper layer in the test piece with the copper layer, the peeling strength was measured according to JIS H 8630. When this peeling strength is 1.0 kN / m or more, it can be judged that the plating adhesion is excellent.

In addition, the test piece with a copper layer was visually observed, and the appearance was judged according to the following criteria.
"○": An appearance that can be put into practical use when the plated body is glossy and no excessive unevenness is observed.
"X": Unevenness is clearly recognized, and it is difficult to put it into practical use because it spoils the aesthetic appearance.

Examples 2-13
Various heterophase polymer particles were used in the proportions shown in Table 2 to prepare mixed particles, and then the obtained mixed particles and a thermoplastic resin were used in combination to prepare pellets in the same manner as in Example 1. Pellet compositions for plating M2 to M13 were produced. Then, the physical properties were measured in the same manner as in Example 1. The results are shown in Table 2.

Example 14
10 parts by mass of the different phase polymer particles P1 and 20 parts by mass of the different phase polymer particles P5 were mixed to obtain 30 parts by mass of mixed particles. Next, 30 parts by mass of the obtained mixed particles, 20 parts by mass of the above acrylonitrile / styrene copolymer, and 50 parts by mass of a polycarbonate resin "Novalex 7022R" (trade name) manufactured by Mitsubishi Engineering Plastics Co., Ltd. were added. The mixture was mixed with an engineering plastic mixer. Then, the mixture was melt-kneaded (set temperature 260 ° C.) using a Banbury mixer to prepare pellets having a columnar shape but a non-uniform size. Then, in the same manner as in Example 1, a pellet composition for plating M14 was produced, and the particle size distribution and the like of the heterophase polymer particles contained therein were measured. The results are shown in Table 2.

Further, except that the prepared pellet composition M14 was used under the conditions of a cylinder set temperature of 260 ° C. and a mold temperature of 60 ° C. by an injection molding machine "J100E-C5 type" (model name) manufactured by Japan Steel Works, Ltd. A test piece was prepared by injection molding in the same manner as in Example 1. Then, various evaluations were performed. The results are shown in Table 2.

Comparative Examples 1-9
Various heterophase polymer particles were used in the proportions shown in Table 3 to prepare mixed particles, and then the obtained mixed particles and a thermoplastic resin were used in combination to prepare pellets in the same manner as in Example 1. Pellet compositions for plating M15 to M23 were produced. Then, the physical properties were measured in the same manner as in Example 1. The results are shown in Table 3.

As is clear from Tables 2 and 3, in Examples 1 to 14 corresponding to the present invention, it was possible to produce a plated molded product having excellent plating adhesion and impact resistance and a good plating appearance. On the other hand, in Comparative Examples 1 to 9 which do not correspond to the present invention, it was not possible to produce a plated molded product having good impact resistance, plating adhesion and appearance.

Claims (8)

A pellet composition composed of pellets containing a matrix phase containing a thermoplastic resin and heterophase polymer particles dispersed in the matrix phase, and used for forming a molded product for plating.
The content ratio of the pellets passing through the 3-mesh sieve is 98% by mass or more with respect to the total amount of the pellet composition.
5 passes through the sieve mesh, and the content ratio of the pellets does not pass through the 9 mesh sieve, based on the total amount of the pellet composition state, and are more than 50 wt%,
The particle size of the heterophase polymer particles is 0.03 to 1 μm.
The coefficient of variation of the particle size of the heterophase polymer particles is 40 to 90%, and the variation coefficient is 40 to 90%.
The content ratio of the polymer particles having a particle size of 0.05 μm or more in the heterophase polymer particles is 80% by volume or more with respect to the whole of the heterophase 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 10 to 60% by volume with respect to the total of the heterophase polymer particles.
The thermoplastic resin comprises at least one styrene resin selected from ABS resin, acrylonitrile / styrene copolymer, acrylonitrile / styrene / maleimide compound ternary polymer, polystyrene and styrene / maleic anhydride copolymer.
The heterophasic polymer particles, the graft site containing the structural unit derived from an aromatic compound and a vinyl cyanide compound, Oh Ru in different phase particles having a particle comprising a repeating unit derived from a conjugated diene, plating pellets composition thing. The plating pellet composition according to claim 1, wherein the coefficient of variation of the particle size of the heterophase polymer particles is 40 to 58%. Claimed that the content ratios of the heterophase polymer particles and the thermoplastic resin contained in the pellets are 10 to 80% by mass and 20 to 90% by mass, respectively, when the total of both is 100% by mass. The plating pellet composition according to 1 or 2. A method for producing a molded body for plating, wherein the pellet composition for plating according to any one of claims 1 to 3 is melt-kneaded and then molded into a predetermined shape. A molded body for plating, wherein the pellet composition for plating according to any one of claims 1 to 3 is melt-kneaded and then molded into a predetermined shape. The pellet composition for plating according to any one of claims 1 to 3 is melt-kneaded, molded into a predetermined shape, etched into the obtained molded body for plating, and then plated. How to make a body. The pellet composition for plating according to any one of claims 1 to 3 is melt-kneaded, molded into a predetermined shape, etched into the obtained molded body for plating, and then plated. A plated body provided with a resin molded portion and a plating layer. The method for forming a plating layer on a molded body for plating according to claim 7 , wherein the molded body for plating is etched at 30 to 80 ° C., and then the plating layer is formed.

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