KR101757191B1 - Laser Direct Structuring Resin - Google Patents

Abstract

Disclosed is a laser direct structured resin having improved thermal stability, more uniform surface, and improved plating and reliability. The present invention provides a direct laser structured resin comprising a polymer component, a polymer additive, and a metal compound additive, wherein the metal compound additive is surface-treated with a magnesium-based surface treatment agent.

Description

Laser Direct Structuring Resin [0001]

The present invention relates to a laser direct structured (LDS) resin, and more particularly to a laser direct structured resin comprising a polymer component, a polymer additive, a metal compound additive, and excellent plating reliability and thermal stability.

Increasing the performance of portable electronic devices as well as reducing the size and weight of components is an important market requirement. Laser direct structuring technology is increasingly used to meet these needs and enables the production of materials with ultra-fine precision, high reliability, improved miniaturization and excellent flexibility in changing and improving the functionality of the target portable electronic device.

However, existing direct laser structuring technology has a disadvantage that the plating is not adhered to the resin or is easily peeled off due to direct plating of the underlying resin. This is due to the fact that the existing LDS resin contains only additives that improve the physical properties of the resin, which increases the dispersion and smoothness of the additives on the injection surface, resulting in weak adhesion between the resin and the plated metal.

To solve this problem, a method of using copper hydroxide phosphorate as an additive has been developed. However, as the thermal stability of the copper hydroxide phosphate is lowered at such a high temperature, the color is discolored and carbonized, resulting in difficulty in injection of white, and the injection surface becomes rough during the low temperature operation, thereby causing a problem in reliability of the plating.

Korean Patent Publication No. 2016-0016957 discloses a thermally conductive polymer composition having a laser direct structuring function. In this invention, thermally conductive resin is added to the laser directly structured resin including thermally conductive filler. However, since copper hydroxide is used as an additive for improving adhesion between resin and metal to be plated, thermal discoloration at high temperature It can not be prevented.

Korean Patent No. 1297630 discloses a composition for direct laser structuring and a direct laser structuring method using the same. Although the present invention discloses a composition having a simple formulation and economic effect by adding a seeding agent, a laser absorbing agent, and the like, the composition for increasing the adhesion between the resin and the metal to be plated is not disclosed, have.

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art described above, and it is an object of the present invention to provide a laser direct structured resin improved in thermal stability, more uniform in surface, and improved in plating and reliability.

As means for solving the above-mentioned technical problem,

According to a first aspect of the present invention, there is provided a laser direct structured resin comprising a polymer component, a polymer additive, and a metal compound additive, wherein the metal compound additive is surface-treated with a magnesium- to provide.

And the metal compound additive is copper hydroxide, copper phosphate, or copper sulfate. The present invention also provides a laser directly structured resin, wherein the metal compound additive is copper hydroxide, phosphate, copper sulfate or Copper Hydroxide Phosphate.

The magnesium-based surface treatment agent may be at least one selected from the group consisting of magnesium 4-sulfophthalate, magnesium 2- (perfluorohexyl) ethyl phosphate, magnesium monophenyl phosphate, ≪ RTI ID = 0.0 > a < / RTI > laser directly structured resin.

Also, the polymer additive is an ester-based, ester-based or polycarbonate-based polymer additive.

According to a second aspect of the present invention, there is also provided a method for producing a metal compound, comprising the steps of: (a) mixing a metal-carbonic acid compound with water and then adding phosphoric acid or sulfuric acid dropwise to obtain a precipitated metal compound additive; (b) separating the precipitated metal compound additive, spraying an aqueous solution of a magnesium-based surface treatment agent on the surface, and heat-treating the surface; And (c) mixing the surface-treated metal compound additive and the polymer additive with the base polymer, and then manufacturing a laser direct structured resin.

The direct laser structured resin according to the present invention has an advantage of being able to produce a laser direct structured molding having various colors because the thermal stability, plating ability and reliability are improved by using a metal compound additive surface-treated with a magnesium type surface treatment agent .

FIG. 1 is a photograph showing the thermal discoloration test results of a resin manufactured according to an embodiment of the present invention. Sample 1 is Comparative Example 4, Sample 2 is Comparative Example 5, Sample 3 is Comparative Example 3, Sample 4 is Comparative Example 1 sample 5 is a photograph showing the results of Comparative Example 2, and Sample 6 is a result of Example 1. Fig.
2 is a graph showing the results of thermal stability tests of Comparative Examples 3 to 5 in which the PCT of the present invention is not used.
3 is a graph showing the results of performing a thermal stability test on Example 1 and Comparative Examples 1 and 2 using the PCT of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

It is to be understood that the compounds, compositions, articles, systems, devices, and / or methods of the present invention are not limited to specific synthetic methods or reagents, and that they may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting. Certain methods and materials similar or equivalent to those described herein may be used in the practice or testing of this disclosure, but are not construed as being limited thereto.

In a first aspect, the present invention provides a laser direct structured resin comprising a polymer component, a polymer additive, and a metal compound additive, wherein the metal compound additive is surface-treated with a magnesium-based surface treatment agent. do.

The polymer component may be selected from the group consisting of polypropylene, polyethylene, ethylene-based copolymers, polycarbonate, polyamide, polyester, polyoxymethylene (POM), liquid crystal polymer (LCP), polyphenylene sulfide (PEI), polyurethane, polyethersulfone (PES), polyetheretherketone (PEEK), thermosetting resin (PPE), polystyrene, acrylonitrile-butadiene-styrene terpolymer (ABS), acrylic polymer, polyetherimide thermoset polymers, or combinations thereof. When the laser is irradiated, a part of the resin is evaporated by the laser to form a large number of pores on the surface, so that the metal to be plated penetrates into the pores Anchoring creates an adhesion force between the metal and the resin. In this case, the amount of the polymer used may be 30 to 90% by weight, preferably 60 to 80% by weight, based on the whole resin. When the amount of the polymer is less than 30% by weight based on the total amount of the resin, the amount of the polymer may be relatively small, resulting in problems in durability and difficulty in exhibiting the properties of the polymer. When the amount of the polymer is more than 90% The amount of the additive is small, so that it may be difficult to adhere to the metal during the metal plating. The polymer may be a mixture of two or more kinds of polymers having different physical properties for controlling the fluidity at the time of injection, and may be used by mixing the same kind of polymers having different physical properties.

In the present invention, the laser direct structured resin includes a polymer additive. The polymer additive may be an ester-based, ester-based or polycarbonate-based polymer additive that imparts chemical resistance, stability, workability, etc. to the resin, and is preferably an ester-based additive, more preferably an ester- May be poly 1,4-cyclohexanedimethyl terephthalate (PCT).

When the polymer additive is added to the resin, the basic physical properties of the resin can be maintained by reducing the chemical influence of the plating solution, and degradation of the plating metal adhesion due to hydrolysis of the resin can be minimized. In addition, the laser pattern abnormality due to contamination of the injection surface and deterioration of the platability thereof can be minimized, and the moldability is superior to that of the polymer used as a base, thereby improving moldability in injection molding.

In the present invention, the laser direct structured resin includes a metal compound additive. The metal compound additive acts on the surface of the resin to be irradiated with the laser to increase the adhesive force with the plated metal. Therefore, the metal compound additive may be copper hydroxide, copper phosphate or copper sulfate, and preferably copper hydroxide.

In addition to the metal compound additive, the metal oxide additive may further include a metal oxide additive to enable coloring while maintaining the mechanical strength of the resin. The metal oxide additive may be a copper containing metal oxide, a titanium containing metal oxide, a tin containing metal oxide, a zinc containing metal oxide, a magnesium containing metal oxide, an aluminum containing metal oxide, a gold containing metal oxide or a silver containing metal oxide, Or an inorganic compound coated with at least one of metal oxides.

The metal compound additive may be discolored when exposed to a laser or at a high temperature to darken the color of the resin, so that it is practically impossible to inject a resin having a white color. In addition, in order to prevent such a phenomenon, when injection is performed at a low temperature, the injection surface may be roughened and the adhesion with the metal may be deteriorated during plating.

Therefore, in the present invention, surface treatment of the metal compound additive using a magnesium-based surface treatment agent improves the thermal stability of the LDS resin. The magnesium-based surface treatment agent used herein may be at least one selected from magnesium 4-sulfophthalate, magnesium 2- (perfluorohexyl) ethyl phosphate, magnesium monophenyl phosphate ), And preferably magnesium 4-sulfophthalate. The magnesium-based surface treatment agent is coated on the surface of the metal compound additive to increase the thermal stability. Accordingly, it is possible to improve the discoloration caused by the injection of the resin, thereby enabling injection into a wider range of colors. In addition, since injection is possible at a higher temperature than that of existing resins, the injection surface becomes uniform, and the reliability of the plating can be improved.

In addition, the laser direct structured resin of the present invention may further comprise a filler, a lubricant, a plasticizer, an ultraviolet absorbing additive, a dripping inhibitor, a dye, a pigment, a stabilizer, an antistatic agent, a flame retardant, an impact modifier, a colorant, an antioxidant, .

The filler is used to improve the mechanical strength and the shrinkage ratio of the resin, and is used for improving the mechanical strength and the molding shrinkage ratio of the resin. The filler is used for improving the mechanical strength and the molding shrinkage ratio of the resin. Examples thereof include silicate, silica powder, aluminum silicate (mullite), synthetic calcium silicate, zirconium silicate, fused silica, Aluminosilicate, hard kaolin, soft kaolin, calcined kaolin, silicon carbide, alumina, aluminum oxide, magnesium oxide, calcium sulfate (an anhydride, dihydrate or trihydrate thereof) Boron carbide, iron, nickel, copper, molybdenum sulfide, zinc sulfide, particulate or fibrous aluminum, bronze, zinc, copper and nickel; Flake filler, flake silicon carbide, aluminum diboride, aluminum flake, steel flake or fibrous filler. The filler is preferably contained in an amount of 10 to 30 wt% based on the LDS resin.

The impact modifier is used for improving the impact resistance. Any compound for increasing the durability of the resin according to the present invention may be used without limitation, and may be included in an amount of 1 to 10 wt% based on the LSD resin.

The antioxidant may be an organic phosphite, triphenyl phosphite, tris- (2,6-dimethylphenyl) phosphite, tris- (mixed mono - and di-nonylphenyl) phosphites, phosphonates, dimethylbenzenesphosphonates, phosphates or trimethylphosphates can be used, but are not limited thereto. The antioxidant is preferably contained in an amount of 0.01 to 2% by weight based on the LDS resin.

As the plasticizer, phthalic acid ester, dioctyl-4,5-epoxy-hexahydrophthalate, tris- (octoxycarbonylethyl) isocyanurate, tristearin or epoxidized soybean oil may be used, but not limited thereto .

As the antistatic agent, glycerol monostearate, sodium stearyl sulfonate or sodium dodecylbenzenesulfonate may be used, but the present invention is not limited thereto.

As the releasing agent, metal stearate, stearyl stearate, pentaerythritol tetrastearate, wax, montan wax or paraffin wax may be used, but it is not limited thereto.

As the lubricant, compounds capable of improving the workability of the LDS resin or reducing the load during processing can be used without limitation, and it is preferable that the LDS resin is contained in an amount of 0.1 to 1% by weight of the LDS resin.

The color improving agent is used to impart white to the resin of the present invention. Any pigment or dye having a white color can be used without limitation, but titanium dioxide (TiO ₂ ) can be preferably used. By weight.

Hereinafter, the method for producing the LDS resin according to the present invention will be described in detail.

(A) mixing a metal-carbonic acid compound with water, and then adding phosphoric acid or sulfuric acid dropwise to obtain a precipitated metal compound additive; (b) separating the precipitated metal compound additive, spraying an aqueous solution of a magnesium-based surface treatment agent on the surface, and heat-treating the surface; And (c) mixing the surface-treated metal compound additive and the polymer additive with the base polymer, and then manufacturing a laser direct structured resin.

The metal compound additive used in the LDS resin is prepared before manufacturing the LDS resin. The metal compound additive may be used as it is, but in order to improve the thermal stability and reliability, additives should be surface-treated.

First, 50 to 150 g of the metal-carbonic acid compound is added per liter of water, and then heated to 40 to 80 ° C. The metal-carbonic acid compound used herein is preferably copper carbonate. When heating is completed, 70 to 90 wt% of phosphoric acid or sulfuric acid, preferably 10 to 100 g of phosphoric acid is slowly added dropwise for 30 minutes to 2 hours, and left at the same temperature for 30 minutes to 2 hours. When the reaction is completed, the reaction mixture is cooled to room temperature, and the resulting precipitate is filtered, washed with water and dried to obtain the final product. In this case, when the copper hydroxide phosphate is produced, the metal compound additive has a pale green and an average particle diameter of 1 to 10 microns, and is 40 to 60 mol% based on the copper atom (Cu), 5 to 20 mol% Mol% and 1 to 3 mol% based on the hydrogen atom (H).

The metal compound additive thus prepared is sprayed with a magnesium-based surface treatment agent as a 5% aqueous solution and heat-treated at 100 to 200 ° C for 30 minutes to 2 hours to obtain a surface-treated metal compound additive.

Thereafter, the surface-treated metal compound additive and the polymer additive are mixed with the base polymer, and the LDS resin can be manufactured in the same manner as in the conventional method. For example, the components may be simultaneously or sequentially charged into a mixer such as a Henschel mixer, a V-type blender, a tumbler mixer, a ribbon blender, and the mixture may be melted and kneaded by a multiaxial extruder such as a single screw extruder or a twin screw extruder or a kneader or Banbury mixer To obtain an LDS resin. The extruder can be used without limitation as long as it can produce LDS resin, but preferably a twin-screw extruder (L / D = 40, feeder 20 to 40 kg / h) may be used.

Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1

1,600 g of water and 80 g of basic copper carbonate were charged into a 2-liter four-neck round bottom flask equipped with a thermometer, a reflux condenser and a stirrer, and the temperature was raised to 60 ° C.

At the same temperature, 50 g of 85% by weight phosphoric acid was gradually added dropwise over 1 hour and then aged for 1 hour. After the copper hydroxide phosphate precipitate was formed, it was cooled to room temperature, filtered, washed several times with water and dried.

A 5 wt% aqueous solution of magnesium 4-sulfophthalate was sprayed onto the copper hydroxide phosphate precipitate to a solid content of 2 wt% based on the copper hydroxide phosphate, and heat treatment was performed at 150 캜 for 1 hour, Compound additive.

, 43 parts by weight of polycarbonate (PC), 20 parts by weight of poly 1,4-cyclohexanedimethyl terephthalate (PCT), 20 parts by weight of filler (G / F), 9 parts by weight of impact modifier (modified polyolefin series) , 4 parts by weight of a surface-treated copper hydroxide phosphate additive, 0.3 part by weight of an antioxidant (triphenylphosphite), 0.3 part by weight of a lubricant (polyethylene wax), and 3.4 parts by weight of TiO ₂ were put into a mixer Next, the mixture was fed to a main feeder of a twin-screw extruder (L / D = 40, feeder 20 to 40 kg / h) and reacted by heating at 300 ° C. After the reaction was completed, .

Example 2

LDS resin was prepared in the same manner as in Example 1 except that magnesium 2- (perfluorohexyl) ethyl phosphate instead of magnesium 4-sulfophthalate was used instead of magnesium 4-sulfophthalate .

Example 3

LDS resin was prepared in the same manner as in Example 1, except that magnesium monophenyl phosphate was used in place of magnesium 4-sulfophthalate.

Comparative Example 1

LDS resin was prepared in the same manner as in Example 1 except that the surface treatment of the metal compound additive was not carried out.

Comparative Example 2

LDS resin was prepared in the same manner as in Example 1, except that the metal compound additive without surface treatment and the metal compound additive with surface treatment were mixed in the same amount.

Comparative Example 3

LDS resin was prepared in the same manner as in Example 1 except that PCT resin was not used and 65 parts by weight of PC resin was used.

Comparative Example 4

LDS resin was prepared in the same manner as in Comparative Example 3, except that the surface treatment of the metal compound additive was not carried out.

Comparative Example 5

LDS resin was prepared in the same manner as in Comparative Example 3, except that the metal compound additive without surface treatment and the metal compound additive with surface treatment were mixed in the same amount.

The compositions of the LDS resins prepared according to Examples and Comparative Examples are summarized in Table 1 (parts by weight).

division Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 PC 43 43 43 43 43 63 63 63 PCT 20 20 20 20 20 - - - G / F 20 20 20 20 20 20 20 20 Impact modifier 9 9 9 9 9 9 9 9 Metal compound additive
(Non-surface treatment) - - - 4 2 - 4 2 Metal compound additive
(Surface treatment) 4 4 4 - 2 4 - 2 Antioxidant 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Lubricant 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 TiO2 3.4 3.4 3.4 3.4 3.4 3.4 3.4 3.4

Experimental Example 1

Tensile strength, elongation, flexural strength, flexural elasticity, impact strength, HDT, MI, and specific gravity of the LDS resin prepared in Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 2 below.

[How to measure]

- Tensile strength: ASTM D638

- Elongation: ASTM D638

- Flexural Strength: ASTM D790

- Flexural elasticity: ASTM D790

- Impact strength: ASTM D256

- HDT: ASTM D648

- MI: ASTM D1238

- ASH: The specimens were pyrolyzed by heating to 700 ° C in a nitrogen-atmosphere atmosphere, and the amount of ash remaining was measured by measuring the amount of the ash.

- Specific gravity: ASTM D792

- Discoloration degree: The YI value was measured on a color difference meter (SA-2000).

- Reliability: The surface of the LDS resin was etched using laser equipment (LPKF1500), plated with copper (Cu) for the above etching site, and then left for 48 hours in an environment of 80 ° C and 80% Were measured.

Test Items Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 The tensile strength 10 mm / min 850 851 849 855 858 890 885 882 Shrinkage 3 3 3 3 3 3 3 3 Flexural strength 5mm / min 1330 1334 1331 1342 1336 1340 1331 1342 Flexural elasticity 57200 57195 57211 57120 57182 58300 57920 58120 Impact strength 1/8 " 8 8 8 8 8 8 8 8 1/4 " 7 7 7 7 7 7 7 7 HDT (18.6 kg / cm 2) 127 126 127 126 126 136 135 135 Ml) (260 DEG C / 5 kg) 15 15 16 16 16 15 16 17 ASH (%) - 27 27 27 27 27 27 27 27 importance - 1.38 1.37 1.36 1.37 1.36 1.45 1.46 1.44 Discoloration degree YI value 0.41 0.40 0.43 1.92 0.77 0.26 1.89 0.83 Thermal stability TGA
on SET (℃) 407 408 411 391 398 414 407 411 responsibility High temperature and high humidity
result PASS PASS PASS PASS PASS FAIL FAIL FAIL

As shown in Table 2, even when the surface-treated metal compound additive and the polymer additive of the present invention were used, the physical properties were not significantly affected. However, when the PCT is not used, the reliability of the metal plating is deteriorated as shown in the reliability analysis result in a high temperature and high humidity environment. Therefore, PCT affects the reliability of the metal plating.

Experimental Example 2

In order to confirm the thermal stability of each sample used in Experimental Example 1, the discoloration was also measured according to the following method. The results are shown in Table 3 and FIG. 1, and the thermal decomposition temperature of each sample was measured, 2 and Fig.

[Method of measuring discoloration degree]

L *, L * a * b * (CIE 1976) colorimetric system using a colorimeter (SA-2000) after filling the glass cell with a chip after removing moisture in the air of 50 g of the LDS resin to be measured, Measure a *, b *, ΔE and YI values. Also, the amount of change of each L *, a *, b * and YI was measured after standing for 24 hours in a high temperature and high humidity environment (temperature 80 ° C, humidity 80%).

[Measurement method of pyrolysis temperature]

The thermal decomposition starting temperature and the completion temperature of each of the Examples and Comparative Examples were measured using a thermogravimetric analyzer (TGA).

ID L * a * b * DELTA L * DELTA a * ? B * ? E * △ YI E313 [D65 / 10] Example 1 77.62 -1.38 -0.65 -0.35 0.08 0.15 0.39 0.41 Example 2 77.65 -1.37 -0.66 -0.33 0.07 0.16 0.37 0.44 Example 3 77.66 -1.36 -0.63 -0.34 0.08 0.17 0.39 0.43 Comparative Example 1 77.33 -1.47 0.04 -0.64 0 0.84 1.06 1.92 Comparative Example 2 77.66 -1.42 -0.48 -0.31 0.05 0.32 0.45 0.77 Comparative Example 3 78.09 -1.42 -0.7 0.12 0.04 0.09 0.16 0.26 Comparative Example 4 77.69 -1.41 -0.45 -0.28 0.05 0.34 0.45 0.83 Comparative Example 5 77.33 -1.47 0.04 -0.64 -0.01 0.83 1.05 1.89

As shown in Table 3 and FIG. 1, when the surface-treated metal compound additives according to the present invention (Examples 1 to 3) were used, it was found that the color discoloration degree was lowered. Therefore, when the surface-treated metal compound additive is used, it can be confirmed that the thermal stability is excellent.

Also, as shown in FIG. 2, when the surface treated metal compound additive is added without adding PCT, it can be seen that the pyrolysis temperature rises by about 7 ° C. As shown in FIG. 3, when PCT is added, When the treated metal compound additive is used, it can be seen that the pyrolysis temperature rises by about 16 ° C. Therefore, it was confirmed that when the surface-treated metal compound additive is used, the stability of enthusiasm is increased at high temperature.

The preferred embodiments of the present invention have been described in detail with reference to the drawings. It will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the appended claims.

Therefore, the scope of the present invention is defined by the appended claims rather than the foregoing detailed description, and all changes or modifications derived from the meaning, range, and equivalence of the claims are included in the scope of the present invention. .

Claims (5)

In a direct laser structured resin comprising a polymer component, poly 1,4-cyclohexanedimethyl terephthalate (PCT) and a metal compound additive,
Wherein the metal compound additive is surface-treated with a magnesium-based surface treatment agent. The method according to claim 1,
Wherein the metal compound additive is a copper hydroxide phosphor, copper phosphate or copper sulfate. The method according to claim 1,
The magnesium-based surface treatment agent may be magnesium 4-sulfophthalate, magnesium 2- (perfluorohexyl) ethyl phosphate or magnesium monophenyl phosphate. Lt; RTI ID = 0.0 > structured < / RTI > resin.
delete A method of manufacturing a laser direct structured resin according to any one of claims 1 to 3, comprising the steps of:
(a) mixing a metal-carbonic acid compound with water, and then adding phosphoric acid or sulfuric acid dropwise to obtain a precipitated metal compound additive;
(b) separating the precipitated metal compound additive, spraying an aqueous solution of a magnesium-based surface treatment agent on the surface, and heat-treating the surface; And
(c) mixing the surface-treated metal compound additive and poly (1,4-cyclohexanedimethyl terephthalate) (PCT) to the base polymer, and then manufacturing a laser direct structured resin.

Images