KR101900143B1 - Thermoplastic resin composition for laser direct structuring process and article comprising the same - Google Patents

Thermoplastic resin composition for laser direct structuring process and article comprising the same Download PDF

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KR101900143B1
KR101900143B1 KR1020160021488A KR20160021488A KR101900143B1 KR 101900143 B1 KR101900143 B1 KR 101900143B1 KR 1020160021488 A KR1020160021488 A KR 1020160021488A KR 20160021488 A KR20160021488 A KR 20160021488A KR 101900143 B1 KR101900143 B1 KR 101900143B1
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resin composition
thermoplastic resin
weight
average molecular
polycarbonate resin
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KR20170099296A (en
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우은택
정유진
김정기
홍상현
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롯데첨단소재(주)
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013Fillers, pigments or reinforcing additives
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/10Metal compounds
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K3/22Oxides; Hydroxides of metals
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    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/20Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2026Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
    • C23C18/204Radiation, e.g. UV, laser
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31Coating with metals

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Abstract

The thermoplastic resin composition of the present invention comprises 100 parts by weight of a polycarbonate resin having a weight average molecular weight of 10,000 to 200,000 g / mol; 1 to 20 parts by weight of an additive for laser direct structuring (LDS); And 0.1 to 2 parts by weight of a lubricant containing at least one of an aliphatic carboxylic acid ester compound and a polyolefin compound. The polycarbonate resin according to the following formula 1 has a weight-average molecular weight retention of 94% or more. The thermoplastic resin composition is excellent in impact resistance, fluidity, plating ability and the like.
[Formula 1]
Weight average molecular weight retention (%) of polycarbonate resin = (Mw0 - Mw1) / Mw0 100
In the above formula (1), Mw0 is the weight average molecular weight of the polycarbonate resin before forming the thermoplastic resin composition, and Mw1 is the weight average molecular weight of the polycarbonate resin immediately after forming the thermoplastic resin composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermoplastic resin composition for a laser direct structuring process and a molded article including the thermoplastic resin composition. [0002]

The present invention relates to a thermoplastic resin composition for laser direct structuring process and a molded article comprising the same. More particularly, the present invention relates to a thermoplastic resin composition for laser direct structuring process, which is excellent in impact resistance, fluidity and plating ability, and a molded article comprising the thermoplastic resin composition.

A laser direct structuring process (LDS process) may be used to plate a metal layer on at least a part of the surface of the molded article formed from the thermoplastic resin composition. The laser direct structuring step is a step performed before the plating step, and means a step of modifying a region to be plated on the surface of a molded article by irradiating a laser beam onto the region to be plated on the surface of the molded article to have properties suitable for plating. For this purpose, the thermoplastic resin composition for producing a molded article should contain an additive for direct laser structuring capable of forming a metal nucleus by a laser. The additive decomposes upon receiving a laser to produce metal nuclei. In addition, the area irradiated with the laser has a surface roughness. Due to such metal nuclei and surface roughness, the laser modified area becomes suitable for plating.

By using the laser direct structuring process, it is possible to form an electric / electronic circuit on a three-dimensional shape of a molded article quickly and economically. For example, the laser direct structuring process can be utilized in the manufacture of antennas for portable electronic devices, radio frequency identification (RFID) antennas, and the like.

In general, the laser direct structuring additive may be composed of a metal oxide. Such an additive is an essential element of the direct laser structuring process, and in the production of the thermoplastic resin composition containing the additive, decomposition of the thermoplastic resin may be caused, which may cause generation of gas and deterioration of physical properties at the time of producing the molded article.

In addition, with the recent trend toward lighter weight and thinner products, a thermoplastic resin composition having excellent molding processability has been demanded. For this, a method of increasing the fluidity by applying a thermoplastic resin having a low molecular weight can be used, but in this case, there is a disadvantage that mechanical properties such as impact resistance of the molded article are lowered and fragile.

Therefore, it is necessary to develop a thermoplastic resin composition for laser direct structuring process, which is excellent in fluidity and plating ability, and a molded article containing the thermoplastic resin composition, without degrading the thermoplastic resin and reducing mechanical properties.

The background art of the present invention is disclosed in Korean Patent Publication No. 2011-0018319.

It is an object of the present invention to provide a thermoplastic resin composition for laser direct structuring, which is excellent in impact resistance, fluidity and plating ability.

Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the present invention relates to a thermoplastic resin composition. Wherein the thermoplastic resin composition comprises 100 parts by weight of a polycarbonate resin having a weight average molecular weight of 10,000 to 200,000 g / mol; 1 to 20 parts by weight of an additive for laser direct structuring (LDS); And 0.1 to 2 parts by weight of a lubricant containing at least one of an aliphatic carboxylic acid ester compound and a polyolefin compound. The polycarbonate resin according to the following formula 1 has a weight average molecular weight retention of 94% or more:

[Formula 1]

Weight average molecular weight retention (%) of polycarbonate resin = (Mw0 - Mw1) / Mw0 100

In the above formula (1), Mw0 is the weight average molecular weight of the polycarbonate resin before forming the thermoplastic resin composition, and Mw1 is the weight average molecular weight of the polycarbonate resin immediately after forming the thermoplastic resin composition.

In embodiments, the laser direct structuring additive may comprise a nucleating agent comprising at least one of a heavy metal complex oxide spinel and a copper salt.

In an embodiment, the aliphatic carboxylic acid ester compound may be a dehydrated condensate of an aliphatic carboxylic acid having 10 to 100 carbon atoms and a monohydric or polyhydric alcohol having 2 to 50 carbon atoms.

In an embodiment, the polyolefin compound may be a polyolefin wax having a weight average molecular weight of 100 to 1,000 g / mol.

In an embodiment, the thermoplastic resin composition may further include an inorganic filler.

In an embodiment, the content of the inorganic filler may be 5 to 90 parts by weight based on 100 parts by weight of the polycarbonate resin.

In the specific example, the thermoplastic resin composition was prepared by injection molding a 50 mm x 50 mm x 1 mm size specimen, and a 500 g weight was dropped on the specimen according to the Dupont drop measurement method, so that 50% Or more.

In the specific example, the thermoplastic resin composition was injection-molded at a injection temperature of 300 캜, a mold temperature of 60 캜, a 50% injection pressure, and a 50% injection rate using a spiral mold having a thickness of 1 mm and a width of 15 mm The flow length of the specimen may be 150 to 250 mm.

In the specific example, the thermoplastic resin composition was formed by forming a striped copper layer having a thickness of 35 탆 on a 50 mm x 50 mm x 1 mm size injection specimen through a direct laser structuring process and a plating process, And peel strength measured at a peeling speed of 50 mm / min may be 1.2 to 2 N / mm.

Another aspect of the present invention relates to a molded article formed from the thermoplastic resin composition.

In an embodiment, the shaped article may comprise a metal layer formed on at least a portion of the surface by a laser direct structuring process and a plating process.

The present invention has the effect of providing a thermoplastic resin composition for laser direct structuring process and a molded article comprising the same, which is excellent in impact resistance, fluidity, plating ability, physical properties thereof and the like.

1 schematically shows a molded article according to one embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition according to the present invention is usable in a laser direct structuring process (LDS process), and comprises: (A) a polycarbonate resin; (B) Additives for direct laser structuring; And (C) a lubricant containing at least one of an aliphatic carboxylic acid ester compound and a polyolefin-based compound, wherein when the thermoplastic resin composition is prepared or molded by the above-mentioned lubricant or the like, the amount of the polycarbonate resin The decomposition can be reduced. Specifically, in the thermoplastic resin composition of the present invention, the polycarbonate resin according to Formula 1 may have a weight average molecular weight retention of 94% or more, for example, 94.3 to 100%.

[Formula 1]

Weight average molecular weight retention (%) of polycarbonate resin = (Mw0 - Mw1) / Mw0 100

In the above formula (1), Mw0 is the weight average molecular weight of the polycarbonate resin before forming the thermoplastic resin composition, and Mw1 is the weight average molecular weight of the polycarbonate resin immediately after forming the thermoplastic resin composition.

(A) Polycarbonate resin

As the polycarbonate resin according to one embodiment of the present invention, the polycarbonate resin used in a conventional thermoplastic resin composition may preferably have a weight average molecular weight (Mw) of 10,000 to 200,000 g / mol, for example, 15,000 to 80,000 g / mol Can be used. If the weight average molecular weight of the polycarbonate resin is less than 10,000 g / mol, mechanical properties such as impact resistance and thermal stability of the thermoplastic resin composition may deteriorate. If the polycarbonate resin exceeds 200,000 g / mol, the fluidity of the thermoplastic resin composition May be deteriorated.

In the present invention, the weight average molecular weight is measured by gel permeation chromatography (GPC) after dissolving a powder sample in tetrahydrofuran (THF). At this time, a column was Shodex LF-804 (8.0.1.D. × 300 mm), and a standard sample was polystyrene.

In a specific example, the polycarbonate resin may be prepared by reacting an aromatic dihydroxy compound with a carbonate precursor such as phosgene, halogen formate or carbonic acid diester in the presence of a catalyst or the like according to a known preparation method. Aromatic polycarbonate resin or the like.

In an embodiment, the aromatic dihydroxy compound may be selected from the group consisting of bis (hydroxyaryl) alkane, bis (hydroxyaryl) cycloalkane, bis (hydroxyaryl) ether, bis (hydroxyaryl) sulfoxide, bis Aryl) sulfide, bis (hydroxyaryl) sulfone, biphenyl compounds, dihydroxybenzene compounds, combinations thereof and the like.

Specific examples of the bis (hydroxyaryl) alkane include bis (4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, bis (3,5-dibromo-4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1- 3-methylphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A), 2,2- (3,5-dimethyl-4-hydroxyphenyl) propane, 1,1-bis (2-tertiary- (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, Bis (3,5-difluoro-4-hydroxyphenyl) propane, 2,2-bis Hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) methane, 2,2-bis Bis (4-hydroxy-3-bromophenyl) propane, 2, (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy- Propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2 Bis (3-bromo-4-hydroxy-5-chlorophenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2- Butyl-4-hydroxyphenyl) butane, 1,1-bis (2-tertiary- (2-tertiary-amyl-4-hydroxy-5-methylphenyl) butane, 2,2-bis (3,5-dichloro (4-hydroxyphenyl) butane, 2,2-bis (3,5-dibromo-4-phenyl) butane, 4,4- 4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) octane and 1,1- But is not limited thereto.

Specific examples of the bis (hydroxyaryl) cycloalkane include 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, Hexane, 1,1-bis (4-hydroxyphenyl) -3,5,5-trimethylcyclohexane, and the like, but are not limited thereto.

Specific examples of the bis (hydroxyaryl) ether include bis (4-hydroxyphenyl) ether and bis (4-hydroxy-3-methylphenyl) Examples of the bis (hydroxyaryl) sulfoxide include bis (hydroxyphenyl) sulfide and bis (3-methyl-4-hydroxyphenyl) sulfide. (3-methyl-4-hydroxyphenyl) sulfoxide and bis (3-phenyl-4-hydroxyphenyl) sulfoxide. Examples of the bis (hydroxyaryl) sulfone include bis 4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone and bis Dihydroxybiphenyl, 4,4'-dihydroxy-2,2'-dimethylbiphenyl, 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 3,3-di Fluoro-4,4'-dihydroxybiphenyl , But are not limited thereto.

Specifically, the dihydroxybenzene compounds include resorcinol, 3-methylresorcinol, 3-ethyl resorcinol, 3-propyrazolesynol, 3-butyl resorcinol, Resorcinol, 3-phenylresorcinol, 2,3,4,6-tetrafluororesorcinol, 2,3,4,6-tetrabromorezolicol, catechol, hydroquinone, 3-methylhydroquinone , 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3-tertiary-butylhydroquinone, 3-phenylhydroquinone, 3-silylhydroquinone, 2,5-dichlorohydroquinone, 2,3,5,6-tetra Methylhydroquinone, 2,3,5,6-tetra-tertiary-butylhydroquinone, 2,3,5,6-tetrafluorohydroquinone, 2,3,5,6-tetrabromohydroquinone, etc. , But is not limited thereto.

In an embodiment, the carbonate precursor is at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate , Carbonyl chloride (phosgene), diphosgene, triphosgene, carbonyl bromide, bishaloformate, and the like. These may be used alone or in combination of two or more.

In an embodiment, the polycarbonate resin may be prepared by reacting the aromatic dihydroxy compound and the carbonate precursor in a molar ratio of 1: 0.9 to 1: 1.5.

In an embodiment, the polycarbonate resin may be partially or wholly substituted with an aliphatic polycarbonate resin, an aromatic and aliphatic copolycarbonate resin, a polyester carbonate resin, a polycarbonate-polysiloxane copolymer resin, etc., in addition to the aromatic polycarbonate resin It is also possible to do.

The polycarbonate resin may be a linear polycarbonate resin, a branched polycarbonate resin, or a mixture of linear and branched polycarbonate resins. For example, the branched polycarbonate resin may be used in an amount of 0.05 to 2 mol% of a trifunctional or more polyfunctional compound with respect to the (aromatic) dihydroxy compound used in the polymerization, specifically, Group in the compound of formula (I).

(B) Additives for direct laser structuring

The additive for laser direct structuring (LDS) according to one embodiment of the present invention is capable of forming a metal nucleus by a laser, and is used as an additive for direct direct structuring of a laser used in a resin composition for direct laser structuring Can be used.

In embodiments, the additive for direct laser structuring may comprise a heavy metal mixture oxide spinel and / or a copper salt.

In an embodiment, the heavy metal complex oxide spinel may be represented by the following formula (1).

[Chemical Formula 1]

AB 2 O 4

In the above formula (1), A may be a metal cation having a valence of 2, for example, magnesium, copper, cobalt, zinc, tin, iron, manganese, nickel or a combination thereof and B is a metal cation having a valence of 3, Manganese, nickel, copper, cobalt, tin, titanium, iron, aluminum, chromium, combinations thereof, and the like.

In an embodiment, the additive for direct laser structuring is selected from the group consisting of copper iron spinel, copper-containing magnesium aluminum oxide, copper chromium manganese oxide, copper manganese iron oxide (optionally oxygen deficient in each case) Salts and oxides such as copper oxide (I), copper oxide (II), copper phosphate, copper sulfate, cuprous thiocyanate and metal complex compounds, chelate compounds of copper, tin, nickel, cobalt, silver and palladium, Or a mixture of such systems and / or a mixture of copper chromium manganese mixed oxides, copper manganese iron mixed oxides, copper chromium oxides, zinc iron oxides, cobalt chromium oxides, cobalt aluminum oxides, magnesium aluminum oxides and mixtures thereof and / / RTI > and / or oxygen-deficient forms, and the like. More specifically, copper chromium oxide spinel, copper hydroxide phosphate, copper phosphate, copper sulfate, cuprous thiocyanate, combinations thereof and the like can be used.

In an embodiment, the laser direct structuring additive may be included in an amount of 1 to 20 parts by weight, for example 5 to 15 parts by weight, based on 100 parts by weight of the polycarbonate resin. If the content of the additive for direct laser structuring is less than 1 part by weight, a sufficient amount of metal nuclei can not be formed in the thermoplastic resin composition (molded product) for laser plating (metal deposition), and the plating ability There is a fear that the polycarbonate resin is decomposed during the production or molding of the thermoplastic resin composition to deteriorate the mechanical properties and the like of the thermoplastic resin composition.

(C) a lubricant

The lubricant used in the present invention can reduce the decomposition of the polycarbonate resin or the like caused by the additive for direct laser structuring or the like during the production or molding of the thermoplastic resin composition and improve the fluidity and the plating property of the thermoplastic resin composition And may include at least one of an aliphatic carboxylic acid ester compound and a polyolefin compound.

In an embodiment, the aliphatic carboxylic acid ester compound may be a dehydrated condensate of an aliphatic carboxylic acid having 10 to 100 carbon atoms and a monohydric or polyhydric alcohol having 2 to 50 carbon atoms. For example, pentaerythritol tetra stearate and the like can be used, but the present invention is not limited thereto.

In an embodiment, the polyolefin compound is a polyolefin wax having a weight average molecular weight of from 100 to 1,000 g / mol, for example from 300 to 900 g / mol, such as polyethylene wax, polypropylene wax, propylene- Wax or the like. In the weight average molecular weight range, decomposition of the polycarbonate resin by the additive for direct laser structuring or the like can be reduced during the production or molding of the thermoplastic resin composition.

In an embodiment, the lubricant may be included in an amount of 0.1 to 2 parts by weight, for example, 0.2 to 1.5 parts by weight, based on 100 parts by weight of the polycarbonate resin. If the content of the lubricant is less than 0.1 parts by weight, the decomposition reducing effect of the polycarbonate resin due to the additive for direct laser structuring or the like may not be obtained during the production or molding of the thermoplastic resin composition, and the impact resistance and workability of the thermoplastic resin composition may deteriorate If the amount is more than 2 parts by weight, the platability (plating adhesion) and thermal stability of the thermoplastic resin composition may be lowered.

The thermoplastic resin composition according to one embodiment of the present invention may further include an inorganic filler other than the additive for direct laser structuring in order to improve mechanical properties such as impact resistance and rigidity.

In an embodiment, the inorganic filler may be glass fiber, talc, wollastonite, whisker, silica, mica, basalt fiber, mixture thereof, but is not limited thereto.

In an embodiment, the average particle size of the inorganic filler may be, for example, 50 nm to 100 m. Within the above range, mechanical properties and the like can be improved without deteriorating other physical properties such as appearance characteristics.

In an embodiment, the content of the inorganic filler may be 5 to 90 parts by weight, for example, 10 to 40 parts by weight, based on 100 parts by weight of the polycarbonate resin. Within the above range, a thermoplastic resin composition having excellent impact resistance, rigidity and the like can be obtained.

The thermoplastic resin composition according to one embodiment of the present invention may further contain optional additives conventionally used in the thermoplastic resin composition insofar as the effect of the present invention is not impaired. Examples of the additives include, but are not limited to, colorants, stabilizers, antioxidants, antistatic agents, flow improvers, and the like. When the additive is used, it may be contained in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the polycarbonate resin, but is not limited thereto.

The thermoplastic resin composition according to one embodiment of the present invention may be in the form of a pellet obtained by melt-extruding the above components and mixing them at a temperature of 200 to 280 DEG C, for example, 250 to 260 DEG C using a conventional twin-screw extruder.

In the specific example, the thermoplastic resin composition was prepared as an injection sample having a size of 50 mm x 50 mm x 1 mm, and a 500 g weight was dropped on the specimen according to the Dupont drop measurement method, so that 50% Or more, for example, 75 to 130 cm. Here, the higher the height, the better the impact resistance of the thermoplastic resin composition.

In the specific example, the thermoplastic resin composition was injection-molded at a injection temperature of 300 캜, a mold temperature of 60 캜, a 50% injection pressure, and a 50% injection rate using a spiral mold having a thickness of 1 mm and a width of 15 mm The flow length of the specimen may be 150 to 250 mm, for example 150 to 180 mm. Within the above range, the thermoplastic resin composition is excellent in fluidity and molding of the thermoplastic resin composition can be facilitated.

In the specific example, the thermoplastic resin composition was formed by forming a striped copper layer having a thickness of 35 탆 on a 50 mm x 50 mm x 1 mm size injection specimen through a direct laser structuring process and a plating process, The peel strength measured at a peeling speed of 50 mm / min may be 1.2 to 2 N / mm, for example, 1.23 to 1.7 N / mm. The platability (plating adhesion) of the thermoplastic resin composition in the above range can be excellent.

The molded article according to the present invention is formed from the thermoplastic resin composition. For example, the thermoplastic resin composition can be used to produce a molded article by a molding method such as injection molding, double injection molding, blow molding, extrusion molding, or thermoforming. The molded article can be easily formed by a person having ordinary skill in the art to which the present invention belongs.

1 schematically shows a molded article according to one embodiment of the present invention. In the drawings, the size of elements constituting the invention is exaggerated for clarity of description, and is not limited thereto. 1, the molded article 10 according to one embodiment of the present invention may include a metal layer 20 formed on at least a part of the surface of the molded article 10 by a laser direct structuring process and a plating process. The molded article 10 according to one embodiment of the present invention may be a circuit carrier or the like used for manufacturing an antenna. The molded article 10 may be formed of a thermoplastic resin composition, for example, 10); Irradiating a laser beam onto a specific region (a metal layer 20 portion) on the surface of the molded product 10; And then metallizing (plating) the irradiated region to form the metal layer 20.

In the embodiment, the laser direct structuring additive contained in the molded article 10 is decomposed by the laser irradiation to generate metal nuclei. In addition, the area irradiated with the laser has a surface roughness suitable for plating. The wavelength of the laser may be 248 nm, 308 nm, 355 nm, 532 nm, 1,064 nm or 10,600 nm.

In an embodiment, the metallization process may be performed through a conventional plating process. For example, it is possible to form the metal layer 20 (electrically conductive path) on the laser-irradiated area of the surface of the molded article 10 by dipping the laser-irradiated molded article 10 into one or more electroless plating baths. Non-limiting examples of the electroless plating process include a copper plating process, a gold plating process, a nickel plating process, a silver plating process, a zinc plating process, and a tin plating process.

As described above, a molded product having a metal layer formed on at least a part of its surface by a laser direct structuring process can be easily formed by a person having ordinary skill in the art to which the present invention belongs.

Hereinafter, the present invention will be described in more detail by way of examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example

Hereinafter, specifications of each component used in Examples and Comparative Examples are as follows.

(A) Polycarbonate resin

A bisphenol-A polycarbonate resin having a weight average molecular weight of 23,000 g / mol was used.

(B) Additives for direct laser structuring

Copper chromium oxide spinel (CuCr 2 O 4 ) was used.

(C) a lubricant

(C1) pentaerythritol tetrastearate was used.

(C2) A polyethylene wax having a weight average molecular weight of 800 g / mol was used.

(C3) magnesium stearate (manufacturer: Songwon Industry, product name: SM-520) was used.

(D) inorganic filler

Glass fiber (manufacturer: KCC, product name: CS321-EC10-3) was used.

Examples 1 to 6 and Comparative Examples 1 to 6

The above components were added in the amounts shown in Table 1 and extruded at a nozzle temperature of 250 to 280 DEG C using a twin-screw extruder having an L / D of 36 and a diameter of 45 mm to prepare pellets (thermoplastic resin composition) . The pellets were dried at 100 ° C. for 3 hours or more, and then injected in a 6 Oz injection machine (molding temperature: 300 ° C., mold temperature: 60 ° C.) to prepare specimens. The properties of the prepared specimens were evaluated by the following methods, and the results are shown in Table 1 below.

How to measure property

(1) Weight average molecular weight retention ratio (unit:%): The weight average molecular weight retention ratio of the polycarbonate resin was measured according to the following formula 1.

[Formula 1]

Weight average molecular weight retention (%) of polycarbonate resin = (Mw0 - Mw1) / Mw0 100

In the above formula (1), Mw0 is the weight average molecular weight of the polycarbonate resin before forming the thermoplastic resin composition, and Mw1 is the weight average molecular weight of the polycarbonate resin immediately after forming the thermoplastic resin composition.

 (2) Impact resistance evaluation: An injection specimen having a size of 50 mm x 50 mm x 1 mm was manufactured and a 500 g weight was dropped on the specimen according to the Dupont drop measurement method to measure the height at which 50% ) Were measured and evaluated. The higher the measured height, the better the impact resistance.

(3) Evaluation of fluidity: A specimen having a thickness of 1 mm and a width of 15 mm was injection-molded using a spiral mold at an injection temperature of 300 ° C., a mold temperature of 60 ° C., a 50% injection pressure and a 50% The flow length (unit: mm) was measured. The longer the measured length, the better the fluidity.

(4) Plating property (plating adhesion) Evaluation: 50 mm × 50 mm × 1 mm size The injection specimens were aged at 25 ° C. for 6 hours and then subjected to a laser direct structuring process to form stripe- After the surface was activated and a stripe copper layer having a thickness of 35 탆 was formed through a plating process (copper electroless plating), a peel strength was measured at a peeling rate of 50 mm / min using a tensile tester (manufacturer: Zwick) peel strength (unit: N / mm) was measured.

Example Comparative Example One 2 3 4 5 6 One 2 3 4 5 6 (A) (parts by weight) 100 100 100 100 100 100 100 100 100 100 100 100 (B) (parts by weight) 11 11 11 11 11 11 11 11 11 11 11 11 (C) (parts by weight) (C1) 0.56 - 0.56 0.56 - 0.56 0.05 2.5 - 0.05 2.5 - (C2) - 0.56 0.56 - 0.56 0.56 - - - - - - (C3) - - - - - - - - 0.56 - - 0.56 (D) (parts by weight) - - - 10 10 10 - - - 10 10 10 Weight average molecular weight retention (%) 95.7 95.7 100 94.8 94.3 99.1 93.3 93.5 92.2 93.4 93.5 91.7 Impact resistance (cm) 112 112 114 80 78 87 103 108 95 73 72 60 Flowability (mm) 170 165 163 161 158 155 168 172 176 160 165 167 Plating property (N / mm) 1.43 1.46 1.47 1.36 1.32 1.38 1.41 1.39 1.35 1.37 1.33 1.30

From the results shown in Table 1, it can be seen that the thermoplastic resin composition of the present invention can reduce the decomposition of the polycarbonate resin during the production of the resin composition, and is excellent in impact resistance, fluidity, plating property and physical properties thereof.

On the other hand, in the case of the comparative example deviating from the constituent component content range of the present invention or not using the lubricant of the present invention, the impact resistance and the like were lowered compared with the examples due to the decrease in molecular weight and the like.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (11)

100 parts by weight of a polycarbonate resin having a weight average molecular weight of 10,000 to 200,000 g / mol;
1 to 20 parts by weight of an additive for laser directed structuring (LDS); And
0.1 to 2 parts by weight of a lubricant comprising an aliphatic carboxylic acid ester compound and a polyolefin compound,
The polyolefin compound is a polyolefin wax having a weight average molecular weight of 100 to 1,000 g / mol,
The thermoplastic resin composition according to claim 1, wherein the polycarbonate resin has a weight-average molecular weight retention of 99.1% or more.
[Formula 1]
Weight average molecular weight retention (%) of polycarbonate resin = (Mw0 - Mw1) / Mw0 100
In the formula (1), Mw0 is the weight average molecular weight of the polycarbonate resin before forming the thermoplastic resin composition, and Mw1 is the weight average molecular weight of the polycarbonate resin immediately after the thermoplastic resin composition is formed.
The thermoplastic resin composition according to claim 1, wherein the additive for direct laser structuring comprises a nucleating agent comprising at least one of heavy metal complex oxide spinel and copper salt.
The thermoplastic resin composition according to claim 1, wherein the aliphatic carboxylic acid ester compound is a dehydration condensate of an aliphatic carboxylic acid having 10 to 100 carbon atoms and a mono- or polyhydric alcohol having 2 to 50 carbon atoms.
delete The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition further comprises an inorganic filler.
The thermoplastic resin composition according to claim 5, wherein the content of the inorganic filler is 5 to 90 parts by weight based on 100 parts by weight of the polycarbonate resin.
The injection molding method of claim 1, wherein the thermoplastic resin composition has an injection molding size of 50 mm x 50 mm x 1 mm and a 500 g weight is dropped on the specimen according to the Dupont drop measurement method, Wherein the thermoplastic resin composition is a thermoplastic resin composition.
The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a thickness of 1 mm and a width of 15 mm using a spiral mold at an injection temperature of 300 캜, a mold temperature of 60 캜, an injection pressure of 50% Wherein the flow length of the injected specimen is 150 to 250 mm.
The thermoplastic resin composition according to claim 1, wherein a striped copper layer having a thickness of 35 탆 is formed on a 50 mm × 50 mm × 1 mm size injection specimen by a laser direct structuring process and a plating process, Wherein the peel strength measured at a peel rate of 50 mm / min is 1.2 to 2 N / mm.
A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 3 and 5 to 9.
11. A molded article according to claim 10, wherein the molded article comprises a metal layer formed on at least a part of the surface by a laser direct structuring process and a plating process.
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JP5615992B1 (en) * 2013-01-24 2014-10-29 三菱エンジニアリングプラスチックス株式会社 Resin composition for laser direct structuring, resin molded product, and method for producing resin molded product with plating layer
JP2015501868A (en) 2011-12-12 2015-01-19 ミツビシ ケミカル ヨーロッパ ゲーエムベーハー Thermoplastic composition

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JP2015501868A (en) 2011-12-12 2015-01-19 ミツビシ ケミカル ヨーロッパ ゲーエムベーハー Thermoplastic composition
JP5615992B1 (en) * 2013-01-24 2014-10-29 三菱エンジニアリングプラスチックス株式会社 Resin composition for laser direct structuring, resin molded product, and method for producing resin molded product with plating layer

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