CN105754141B - Bismuth-containing be sensitized auxiliary agent preparation can application in the resin combination of laser direct forming - Google Patents
Bismuth-containing be sensitized auxiliary agent preparation can application in the resin combination of laser direct forming Download PDFInfo
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- CN105754141B CN105754141B CN201610154118.9A CN201610154118A CN105754141B CN 105754141 B CN105754141 B CN 105754141B CN 201610154118 A CN201610154118 A CN 201610154118A CN 105754141 B CN105754141 B CN 105754141B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses bismuth-containing sensitization auxiliary agent preparation can application in the resin combination of laser direct forming, oxide of the bismuth-containing sensitization auxiliary agent selected from bismuth, the sulfide of bismuth, the hydroxide of bismuth, the oxychloride of bismuth, bismuth salt in any one or it is two or more.Present inventor, it is found surprisingly that, bismuth-containing is sensitized auxiliary agent in the case where additive amount is down to 1wt%, and the thickness of coating of obtained resin combination has just reached 10 μm or more, coating peel strength is greater than 1.0N/mm, achieves the wholly unexpected technical effect of those skilled in the art；Moreover, the bismuth-containing sensitization auxiliary agent in the present invention is free of copper, the background color of obtained resin combination is shallower, particularly suitable for light color and/or colour LDS resin；Meanwhile the present invention can also reduce sensitization auxiliary agent dosage, reduce can laser direct forming product production cost, have very good economic benefit, the application being very suitable in industry.
Description
Technical field
The invention belongs to laser sensitization auxiliary agent field, and in particular to bismuth-containing be sensitized auxiliary agent preparation can laser direct forming
Application in resin combination.
Background technique
Laser direct structuring technique (LDS) is the scanning track that laser is controlled by computer, by laser irradiation to containing
On the product (resin combination) of laser sensitization auxiliary agent, circuit pattern is activated in a relatively short period of time, then in the area of activation
Domain plates one layer of conductive metal, to assign common plastic cement component to electric interconnection function, forms three dimensional mold interconnecting device
Part (Three-dimensional molded interconnect device, referred to as 3D-MID).
The advantage of the technology is that the component number of electronic product can be reduced and saves space, and production chains
It is good：If necessary to change conducting channel, it is only necessary to which the motion profile for adjusting laser scanning is not required to redesign mold, tool
Have the advantages that speed of production is more fast, process is more simplified, cost is more controllable, is widely used in antenna for mobile phone, aerospace, electronics
Medical treatment, automobile instrument panel, laptop etc..
Wherein, sensitization auxiliary agent (also known as laser direct forming additive) is most important work in laser direct structuring technique
One of skill condition, can directly influence plate metal in the region of activation.
Currently, the reagent type that can be used as sensitization auxiliary agent is fairly limited, mainly containing two or more special metals
Compound, such as：Copper chromium compound, copper manganese compound etc., price is costly；Moreover, such compound is as sensitization auxiliary agent
When, need to obtain in the case where additive amount is up to 12wt% 10 μm or more thickness of coating (see：CN 103450675A
[0072] section of specification), at high cost, the economy industrially applied is very poor；Meanwhile the sensitization auxiliary agent of these cuprics is past
Toward " copper evil " is brought to polymer, polymer air aging can be accelerated, shorten it so as to cause composition substrate reduced performance
Service life.
In order to overcome defect existing for existing sensitization auxiliary agent, need to develop or find that a kind of additive amount is small, effect is good, is free of
Copper and can be used to prepare can laser direct forming product sensitization auxiliary agent.
Summary of the invention
The purpose of the present invention is to provide bismuth-containing sensitization auxiliary agent preparation can be in the resin combination of laser direct forming
Using.
Bismuth-containing provided by the invention sensitization auxiliary agent preparation can application in the resin combination of laser direct forming, it is described
Bismuth-containing is sensitized appointing in the salt of oxide of the auxiliary agent selected from bismuth, the sulfide of bismuth, the hydroxide of bismuth, the oxychloride of bismuth, bismuth
Meaning is one or more kinds of.
Further, the oxide of the bismuth is selected from Bi2O3、Bi2O2.33、Bi2O2.75、Bi2O4In any one or two kinds
More than；Preferably, the oxide of the bismuth is Bi2O3。
Further, the sulfide of the bismuth is bismuth sulfide.
Further, any one or two kind of the hydroxide of the bismuth in bismuth hydroxide, inclined bismuth hydroxide；It is excellent
Choosing, the hydroxide of the bismuth is bismuth hydroxide.
Further, the oxychloride of the bismuth is bismuth oxychloride.
Further, the salt of the bismuth is selected from bismuth phosphate, bismuth sulfate, bismuth nitrate, bismuth subnitrate, basic bismuth carbonate, aluminic acid
Bismuth any one or it is two or more；Preferably, the salt of the bismuth is bismuth phosphate or basic bismuth carbonate.
Further, the average grain diameter of the bismuth-containing sensitization auxiliary agent is less than or equal to 150 μm；Preferably, the bismuth-containing is quick
The average grain diameter for changing auxiliary agent is 0.1 μm~50 μm.
The present invention also provides it is a kind of can laser direct forming resin combination, it is by the group of following weight percent
It is grouped as：Bismuth-containing is sensitized auxiliary agent 1%~60%, polymer 40%~99%；Wherein, the bismuth-containing sensitization auxiliary agent is selected from the oxygen of bismuth
Compound, the sulfide of bismuth, the hydroxide of bismuth, the oxychloride of bismuth, bismuth salt in any one or it is two or more.
Further, bismuth-containing is sensitized auxiliary agent 3%~55%, polymer 45%~97%；Preferably, it is by following weight
The group of percentage is grouped as：Bismuth-containing is sensitized auxiliary agent 5%~55%, polymer 45%~95%.
Further, it is to consist of the following components in percentage by weight：Bismuth-containing is sensitized auxiliary agent 1%~3%, polymer
97%~99%.
Further, the oxide of the bismuth is selected from Bi2O3、Bi2O2.33、Bi2O2.75、Bi2O4In any one or two kinds
More than；Preferably, the oxide of the bismuth is Bi2O3。
Further, the sulfide of the bismuth is bismuth sulfide.
Further, any one or two kind of the hydroxide of the bismuth in bismuth hydroxide, inclined bismuth hydroxide；It is excellent
Choosing, the hydroxide of the bismuth is bismuth hydroxide.
Further, the oxychloride of the bismuth is bismuth oxychloride.
Further, the salt of the bismuth is selected from bismuth phosphate, bismuth sulfate, bismuth nitrate, bismuth subnitrate, basic bismuth carbonate, aluminic acid
Bismuth any one or it is two or more；Preferably, the salt of the bismuth is bismuth phosphate or basic bismuth carbonate.
Further, the average grain diameter of the bismuth-containing sensitization auxiliary agent is less than or equal to 150 μm；Preferably, the bismuth-containing is quick
The average grain diameter for changing auxiliary agent is 0.1 μm~50 μm.
Further, the polymer is selected from polycarbonate, acrylonitrile-butadiene-styrene copolymer, styrene-the third
Alkene lonitrile copolymer, polypropylene, polyethylene terephthalate, polybutylene terephthalate (PBT), polyamide, polystyrene,
In polyphenylene oxide, polyphenylene sulfide any one or it is two or more.
The present invention also provides the preparation methods of above-mentioned resin combination, it includes the following steps：
A, bismuth-containing sensitization auxiliary agent and polymer are taken, mixes, obtains mixture；
B, by mixture melt blending obtained by step a, be granulated to get can laser direct forming resin combination.
Present inventor is found surprisingly that, bismuth-containing is sensitized auxiliary agent in the case where additive amount is down to 1wt%, made
The thickness of coating for obtaining resin combination has just reached 10 μm or more, and coating peel strength is greater than 1.0N/mm, achieves this field skill
The wholly unexpected technical effect of art personnel；Moreover, bismuth-containing of the present invention is sensitized auxiliary agent, the background color of obtained resin combination compared with
Shallowly, particularly suitable for light color and/or colour LDS resin；Meanwhile the present invention can also reduce the dosage of sensitization auxiliary agent,
Reduce can laser direct forming product production cost, have very good economic benefit, the application being very suitable in industry.
About the definition of the invention using term：Unless otherwise indicated, what group or term herein provided is initial
Definition is suitable for group or term of entire description；For the term being not specifically defined herein, it should according to open
Content and context, their meaning can be given by providing those skilled in the art.
Obviously, above content according to the present invention is not being departed from according to the ordinary technical knowledge and customary means of this field
Under the premise of the above-mentioned basic fundamental thought of the present invention, the modification, replacement or change of other diversified forms can also be made.
The specific embodiment of form by the following examples remakes further specifically above content of the invention
It is bright.But the range that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to example below.It is all to be based on above content of the present invention
The technology realized all belongs to the scope of the present invention.
Detailed description of the invention
Fig. 1 is the chemical plating effect picture of the embodiment of the present invention and comparative example.
Specific embodiment
Raw material, equipment used in the specific embodiment of the invention are known product, are obtained by purchase commercial product.
Polycarbonate：General Electric Company, PC 121R (density：1.2g/cm3；Melt flow rate (MFR)：17.5g/
10min, 300 DEG C, 1.2Kg；Heat distortion temperature：125℃).
Acrylonitrile-butadiene-styrene (ABS) (ABS):The odd beauty in Taiwan, PA747 (density：1.03g/cm3；Melt flow rate (MFR)：
1.2g/10min, 200 DEG C, 5Kg).
Polystyrene：Only son mountain petrochemical industry, GPPS-500 (density：1.04g/cm3；Melt flow rate (MFR)：5g/10min, 200
DEG C, 5Kg；Heat distortion temperature：89℃).
Polyethylene terephthalate：It is remote to spin industry, CB-602 (density：1.40g/cm3；Melting temperature：245℃).
Polybutylene terephthalate (PBT)：German BASF, PBT B4500 (density：1.3g/cm3；Melting temperature：230
℃)。
Polyamide 66：The bright Sheng of Germany, A30S (density：1.14g/cm3；Melting temperature：260℃).
Embodiment 1
Firstly, by ABS resin 99g and laser sensitization auxiliary agent bismuth oxide powder (average grain diameter is 0.5 μm) 1g in height
It is sufficiently mixed in fast blender 2 minutes；Then, mixed material is placed in melting extrusion in double screw extruder, be granulated, squeezed
Out temperature be 230 DEG C to get can laser direct forming resin combination.
Then, the laser direct forming resin combination prepared is molded into plastic sheet, injection temperature through injection molding machine
It is 240 DEG C.
Laser activation is carried out to above-mentioned plastic sheet using the following conditions：Pulsed near infrared laser, optical maser wavelength are
1064nm, mark speed are 2000mm/s, laser energy 8W, laser frequency 60KHz.
According to LDS plastic chemistry electroplating method well known in the art and technique, to the plastic sheet after laser activation
Learn copper facing.
After electroless copper, following effect and/or performance test are carried out：
(1) effect is chemically plated：Range estimation；
(2) thickness of coating of electroless copper：It is tested according to ASTM B568 (2009)；
(3) peel strength of coating：According to IPC-TM-650 2.4.28, surveyed using electroless copper peel test device
Amount.
Test result is shown in Table 1.
Embodiment 2
ABS resin 95g and laser sensitization auxiliary agent bismuth oxide powder 5g.
Test method is same as Example 1, and test result is shown in Table 1.
Embodiment 3
ABS resin 93g and laser sensitization auxiliary agent bismuth oxide powder 7g.
Test method is same as Example 1, and test result is shown in Table 1.
Embodiment 4
ABS resin 90g and laser sensitization auxiliary agent bismuth oxide powder 10g.
Test method is same as Example 1, and test result is shown in Table 1.
Embodiment 5
ABS resin 70g and laser sensitization auxiliary agent bismuth oxide powder 30g.
Test method is same as Example 1, and test result is shown in Table 1.
Embodiment 6
ABS resin 45g and laser sensitization auxiliary agent bismuth oxide powder 55g.
Test method is same as Example 1, and test result is shown in Table 1.
Embodiment 7
Polycarbonate 97g and laser sensitization auxiliary agent bismuth sulfide powder (average grain diameter is 10 μm) 3g, in high-speed mixer
It is sufficiently mixed 2 minutes；Then, mixed material is placed in melting extrusion in double screw extruder, be granulated, extrusion temperature is
260 DEG C to get can laser direct forming resin combination.
The laser direct forming resin combination prepared is molded into plastic sheet, injection temperature 265 through injection molding machine
℃。
Laser activation is carried out to above-mentioned plastic sheet using the following conditions：Pulsed near infrared laser, optical maser wavelength are
1064nm, mark speed are 2000mm/s, laser energy 8W, laser frequency 60KHz.
Effect and/or method for testing performance are same as Example 1, and test result is shown in Table 1.
Embodiment 8
Polycarbonate 95g and laser sensitization auxiliary agent bismuth sulfide powder 5g.
Test method is same as Example 7, and test result is shown in Table 1.
Embodiment 9
Polycarbonate 90g and laser sensitization auxiliary agent bismuth sulfide powder 10g.
Test method is same as Example 7, and test result is shown in Table 1.
Embodiment 10
Firstly, by polyethylene terephthalate 95g and laser sensitization auxiliary agent bismuth oxychloride powder (average grain diameter 35
μm) 5g is sufficiently mixed 2 minutes in high-speed mixer；Then, mixed material is placed in melt in double screw extruder and is squeezed
Out, be granulated, extrusion temperature be 245 DEG C to get can laser direct forming resin combination.
Then, the laser direct forming resin combination prepared is molded into plastic sheet, injection temperature through injection molding machine
It is 245 DEG C.
Laser activation is carried out to above-mentioned plastic sheet using the following conditions：Pulsed near infrared laser, optical maser wavelength are
1064nm, mark speed are 2000mm/s, laser energy 8W, laser frequency 60KHz.
Effect and/or method for testing performance are same as Example 1, and test result is shown in Table 1.
Embodiment 11
Firstly, by polybutylene terephthalate (PBT) 95g and laser sensitization auxiliary agent bismuth phosphate powder, (average grain diameter is 30 μ
M) 5g is sufficiently mixed 2 minutes in high-speed mixer；Then, mixed material is placed in melt in double screw extruder and is squeezed
Out, be granulated, extrusion temperature be 230 DEG C to get can laser direct forming resin combination.
Then, the laser direct forming resin combination prepared is molded into plastic sheet, injection temperature through injection molding machine
It is 235 DEG C.
Laser activation is carried out to above-mentioned plastic sheet using the following conditions：Pulsed near infrared laser, optical maser wavelength are
1064nm, mark speed are 2000mm/s, laser energy 8W, laser frequency 60KHz.
Effect and/or method for testing performance are same as Example 1, and test result is shown in Table 1.
Embodiment 12
Firstly, by 60g polyamide 66 and 40g laser sensitization auxiliary agent bismuth hydroxide powder (20 μm of average grain diameter) in high-speed stirring
It mixes and is sufficiently mixed in machine 2 minutes；Then, mixed material is placed in melting extrusion in double screw extruder, be granulated, squeeze out temperature
Degree for 265 DEG C to get can laser direct forming resin combination.
Then, the laser direct forming resin combination prepared is molded into plastic sheet, injection temperature through injection molding machine
It is 265 DEG C.
Laser activation is carried out to above-mentioned plastic sheet using the following conditions：Pulsed near infrared laser, optical maser wavelength are
1064nm, mark speed are 2000mm/s, laser energy 8W, laser frequency 60KHz.
Effect and/or method for testing performance are same as Example 1, and test result is shown in Table 1.
Embodiment 13
Firstly, by polystyrene 95g and laser sensitization auxiliary agent basic bismuth carbonate powder (1 μm of average grain diameter) 5g in high-speed stirring
It mixes and is sufficiently mixed in machine 2 minutes；Then, mixed material is placed in melting extrusion in double screw extruder, be granulated, squeeze out temperature
Degree for 220 DEG C to get can laser direct forming resin combination.
Then, the laser direct forming resin combination prepared is molded into plastic sheet, injection temperature through injection molding machine
It is 210 DEG C.
Laser activation is carried out to above-mentioned plastic sheet using the following conditions：Pulsed near infrared laser, optical maser wavelength are
1064nm, mark speed are 2000mm/s, laser energy 8W, laser frequency 60KHz.
Effect and/or method for testing performance are same as Example 1, and test result is shown in Table 1.
Comparative example 1
ABS resin 99.5g and laser sensitization auxiliary agent bismuth oxide powder 0.5g.
Test method is same as Example 1, and test result is shown in Table 1.
Comparative example 2~7
According to above-mentioned identical method, respectively by pure ABS resin, polycarbonate, polyethylene terephthalate, poly-
Plastic sheet is made in mutual-phenenyl two acid bromide two alcohol ester, polyamide 66, polystyrene, then carries out laser activation, effect and/or property
It can test, test result is shown in Table 1.
The test result of table 1, embodiment 1~13 and comparative example 1~7
The result shows that bismuth-containing of the present invention is sensitized auxiliary agent, in the case where additive amount is down to 1wt%, obtained resin combination
The thickness of coating of object has just reached 10 μm or more, and coating peel strength is greater than 1.0N/mm, and it is complete to achieve those skilled in the art
Unexpected technical effect；Moreover, bismuth-containing of the present invention is sensitized auxiliary agent, the background color of obtained resin combination is shallower, especially suitable
It shares in light color and/or colour LDS resin；Meanwhile the present invention can also reduce the dosage of sensitization auxiliary agent, reduction can laser
The production cost of straight forming product has very good economic benefit, the application being very suitable in industry.
Claims (11)
1. one kind can laser direct forming resin combination, it is characterised in that：It is by following components in percentage by weight group
At：Bismuth-containing is sensitized auxiliary agent 1%~60%, polymer 40%~99%；Wherein, the bismuth-containing sensitization auxiliary agent is selected from oxide, the bismuth of bismuth
Sulfide, the hydroxide of bismuth, the oxychloride of bismuth, bismuth salt in any one or it is two or more；
The oxide of the bismuth is selected from Bi2O3、Bi2O2.33、Bi2O2.75、Bi2O4；The sulfide of the bismuth is bismuth sulfide；The bismuth
Hydroxide be selected from bismuth hydroxide, inclined bismuth hydroxide；The oxychloride of the bismuth is bismuth oxychloride；The salt of the bismuth is selected from phosphorus
Sour bismuth, bismuth sulfate, bismuth nitrate, bismuth subnitrate, basic bismuth carbonate, bismuth aluminate.
2. resin combination according to claim 1, it is characterised in that：It is by following components in percentage by weight group
At：Bismuth-containing is sensitized auxiliary agent 3%~55%, polymer 45%~97%.
3. resin combination according to claim 2, it is characterised in that：It is by following components in percentage by weight group
At：Bismuth-containing is sensitized auxiliary agent 5%~55%, polymer 45%~95%.
4. resin combination according to claim 1, it is characterised in that：It is by following components in percentage by weight group
At：Bismuth-containing is sensitized auxiliary agent 1%~3%, polymer 97%~99%.
5. resin combination according to claim 1, it is characterised in that：The oxide of the bismuth is Bi2O3。
6. resin combination according to claim 1, it is characterised in that：The hydroxide of the bismuth is bismuth hydroxide.
7. resin combination according to claim 1, it is characterised in that：The salt of the bismuth is bismuth phosphate or basic carbonate
Bismuth.
8. resin combination according to claim 1, it is characterised in that：The average grain diameter of the bismuth-containing sensitization auxiliary agent is less than
Or it is equal to 150 μm.
9. resin combination according to claim 8, it is characterised in that：The average grain diameter of bismuth-containing sensitization auxiliary agent is
0.1 μm~50 μm.
10. resin combination according to claim 1, it is characterised in that：The polymer is selected from polycarbonate, propylene
Nitrile-butadiene-styrene copolymer, polypropylene, polyethylene terephthalate, gathers to benzene at styrene-acrylonitrile copolymer
Dioctyl phthalate butanediol ester, polyamide, polystyrene, polyphenylene oxide, in polyphenylene sulfide any one or it is two or more.
11. the preparation method of resin combination described in claim 1~10 any one, it is characterised in that：It includes following step
Suddenly：
A, bismuth-containing sensitization auxiliary agent and polymer are taken, mixes, obtains mixture；
B, by mixture melt blending obtained by step a, be granulated to get can laser direct forming resin combination.
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| CN201610154118.9A CN105754141B (en) | 2016-03-16 | 2016-03-16 | Bismuth-containing be sensitized auxiliary agent preparation can application in the resin combination of laser direct forming |
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| CN108786808B (en) * | 2018-06-26 | 2020-11-24 | 陕西科技大学 | Ag/BiO2-x/Bi2O3/Bi2O2.75Composite photocatalyst and preparation method and application thereof |
| CN110344030A (en) * | 2019-08-08 | 2019-10-18 | 四川大学 | A kind of highly sensitive base material and preparation method thereof for LR laser raman enhancing |
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| CN102597081A (en) * | 2009-10-29 | 2012-07-18 | 帝斯曼知识产权资产管理有限公司 | Laser-marking additive |
| CN104619783A (en) * | 2012-09-14 | 2015-05-13 | 三菱工程塑料株式会社 | Thermoplastic resin composition, resin molded article, and method for producing resin molded article having plated layer attached thereto |
| CN104725847A (en) * | 2013-12-20 | 2015-06-24 | Ems专利股份公司 | Plastics moulding composition and use thereof |
| TW201544535A (en) * | 2014-04-09 | 2015-12-01 | Shepherd Color Co | Core-shell composite inorganic metal oxides and method of preparation for prevention of thermal oxidative degradation in polymer and resin compositions |
| CN105330898A (en) * | 2015-12-08 | 2016-02-17 | 四川大学 | Laser marker additive and preparation method and application thereof |
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2016
- 2016-03-16 CN CN201610154118.9A patent/CN105754141B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102597081A (en) * | 2009-10-29 | 2012-07-18 | 帝斯曼知识产权资产管理有限公司 | Laser-marking additive |
| CN104619783A (en) * | 2012-09-14 | 2015-05-13 | 三菱工程塑料株式会社 | Thermoplastic resin composition, resin molded article, and method for producing resin molded article having plated layer attached thereto |
| CN104725847A (en) * | 2013-12-20 | 2015-06-24 | Ems专利股份公司 | Plastics moulding composition and use thereof |
| TW201544535A (en) * | 2014-04-09 | 2015-12-01 | Shepherd Color Co | Core-shell composite inorganic metal oxides and method of preparation for prevention of thermal oxidative degradation in polymer and resin compositions |
| CN105330898A (en) * | 2015-12-08 | 2016-02-17 | 四川大学 | Laser marker additive and preparation method and application thereof |
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