CN108239388A - It is a kind of can laser activation high-temperature-resistant thermoplastic composition and preparation method thereof - Google Patents
It is a kind of can laser activation high-temperature-resistant thermoplastic composition and preparation method thereof Download PDFInfo
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- CN108239388A CN108239388A CN201711290535.7A CN201711290535A CN108239388A CN 108239388 A CN108239388 A CN 108239388A CN 201711290535 A CN201711290535 A CN 201711290535A CN 108239388 A CN108239388 A CN 108239388A
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- temperature
- thermoplastic composition
- laser activation
- resistant thermoplastic
- water cooling
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0284—Details of three-dimensional rigid printed circuit boards
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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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses it is a kind of can laser activation high-temperature-resistant thermoplastic composition and preparation method thereof, the thermoplastic compounds are according to weight percent, including following components；LDP additives：8 15%, thermoplasticity fire resistant resin：73.5 89.3%, rubber solubilising polymer：1 5%, surface modifier：1 5%, graphene：0.3 0.9%, resistance to high temperature oxidation agent：0.3% 0.5%, remaining is toner or high dielectric material, the composition good product dispersibility, mechanical property and chemical plating are had excellent performance, have good plating performance and processing forming, it can be achieved that plastic material surface directly mounts component, make full use of structure space, meet high integration, miniaturization and light-weighted demand.
Description
Technical field
The present invention relates to a kind of thermoplastic compounds, be related specifically to it is a kind of can laser activation high-temperature-resistant thermoplastic combination
Object and preparation method thereof.
Background technology
At present, forming 3D circuits using the direct figure of laser (LDP) method becomes to become more and more popular.In LDP methods, swash
Light beam is mobile so as to activate the frosting in the place of conductive path to be set on product surface.Directly schemed by means of laser
Shape and the electroplating method that becomes more meticulous can obtain smaller conductive path width.In addition, the interval between conductive path can also be more
It is small.The direct figure of laser (LDP) method save final use application in space and weight, another advantage be the flexible of it
Property, if changing the design of circuit, it is thus only necessary to which the computer for controlling laser is reprogramed.
A kind of special active catalyst is used in directly graphical (LDP) method of laser.Laser is drawn on the surface of workpiece
Go out circuitous pattern, light beam, which passes through part, can cause surface microroughness, while the path of laser is also in metal active catalysis
The position of heart exposure.These active catalytic centers are exactly nuclei of crystallization when carrying out chemical plating in next step.It is workable other
Chemical plating method includes but not limited to copper facing, gold, nickel, silver, zinc, tin, chromium, cadmium etc..
Directly graphical (LDP) method circuit plate part of existing laser use epoxy resin+glass fibre or
PI, in one layer of gum copper foil of composite material surface hot pressing, then by pattern transfer, development, it is unwanted that surface is peelled off in etching
Layers of copper obtains circuit, using subtractive process, can only do planar circuit, it is impossible to stereo circuit is done, secondly, and after the completion of PCB, warp
It crosses surface installation technique and is installed to concrete structure, complex manufacturing technology.
Invention content
Present invention mainly solves directly graphical (LDP) methods of existing laser can only do planar circuit, complex manufacturing technology
The technical issues of.
In order to solve the above technical problems, the present invention provides it is a kind of can laser activation high-temperature-resistant thermoplastic composition,
It is characterized in that, the thermoplastic compounds are according to weight percent, including following components；LDP additives：8-15%；Thermoplastic
Property fire resistant resin：73.5-89.3%；Rubber solubilising polymer：1-5%；Surface modifier：1-5%；Graphene：0.3-
0.9%；Resistance to high temperature oxidation agent：0.3%-0.5%；Remaining is toner or high dielectric material
Optionally, the thermoplasticity fire resistant resin is selected from PA, PBT, LCP, PEEK, PA base fibre reinforced materials, PBT bases
One or more multicomponent alloy composite woods in fibre reinforced materials, LCP bases fibre reinforced materials, PEEK base fibre reinforced materials
Material.
Optionally, the LDP additives are selected from spinel structure type metal mixing oxide, are Co-Ti-O and Co-AL-O
[Co(AlO2)2, CAS:1345-16-0] mixed oxide, Co-Ti-O and Co-AL-O (AlO2)2, CAS:1345-16-0] salt
Compound it is one or more.
Optionally, the rubber solubilising polymer is in organosilicon or organosilicon and General Purpose Rubber elastomer blends
It is a kind of.
Optionally, the surface modifier be organic silicon modifying agent, one or both of organic titanium class modifying agent, institute
Antioxidant is stated as four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester powder or particle.
Optionally, the graphene is 16-20% single-layer graphenes, multi-layer graphene and graphite mixture.
The present invention also provides it is a kind of can laser activation high-temperature-resistant thermoplastic composition preparation method, including walking as follows
Suddenly；
S1：Drying, thermoplasticity fire resistant resin is dried at 100-160 DEG C；
S2：Take out grain, according to weight percent, by 8-15%LDP additives, 73.5-89.3% thermoplasticity fire resistant resin,
1-5% rubber solubilisings polymer, 1-5% surface modifiers, 0.3-0.9% graphenes, 0.3%-0.5% resistance to high temperature oxidation agent
It is mixed at 240-300 DEG C and takes out grain, wherein the L/D values of Granulation Equipments are controlled more than 25；
S3：Pelletizing, the pelletizing speed are 40-200RPM；
Optionally, it is described pumping grain step after to it is described can laser activation high-temperature-resistant thermoplastic composition carry out water cooling,
The water cooling behaviour is taken as 50-70 DEG C of water cooling.
Optionally, after using 50-70 DEG C of water cooling, second water cooling is carried out, the water temperature of the second water cooling is 30-45
DEG C, then third road water cooling is carried out with cold water again.
Advantageous effect：It is provided by the present invention can laser activation high-temperature-resistant thermoplastic composition can be used for molding prepare knot
Component, as a result of high-temperature-resistant thermoplastic composition, structural member surface can Direct Laser process and preparation of metallizing is three-dimensional
Conducting channel, and the thermoplasticity fire resistant resin material as matrix can be subjected to the temperature of SMT, it is possible to it realizes direct
In stereo circuit over-assemble electronic device, and this can laser activation high-temperature-resistant thermoplastic composition good dispersion, mechanical property
It is had excellent performance with chemical plating, has good plating performance and processing forming, save assembling procedure, due in structural member table
Face directly makes electronic circuit, not only saves shell space, but also facilitates the installation of other electronic components of enclosure interior, can carry significantly
The integrated level of high electronic product.
Specific embodiment
It should be understood that specific embodiment discussed below is merely to illustrate and explain the present invention, it is not to use
In the limitation present invention.
The present invention provides it is a kind of can laser activation high-temperature-resistant thermoplastic composition, which is characterized in that thermoplastic composition
Object is according to weight percent, including following components；LDP additives：8-15%；Thermoplasticity fire resistant resin：73.5-89.3%；
Rubber solubilising polymer：1-5%；Surface modifier：1-5%；Graphene：0.3-0.9%；Resistance to high temperature oxidation agent：0.3%-
0.5%；Other：0.1%.
Wherein, thermoplasticity fire resistant resin be selected from PA (benzene dicarboxylic acid butanediol ester), PBT (polyamide), (liquid crystal gathers LCP
Close object), PEEK (polyether-ether-ketone), PA bases fibre reinforced materials, PBT bases fibre reinforced materials, LCP bases fibre reinforced materials,
One or more multicomponent alloy composite materials in PEEK base fibre reinforced materials；
Wherein, the directly graphical additive of laser is selected from the direct figure compound additive of laser and is selected from spinel structure type gold
Belong to mixed oxide, LDP additives are Co-Ti-O and Co-AL-O [Co (AlO2)2, CAS:1345-16-0] mixed oxide,
Co-Ti-O and Co-AL-O [Co (AlO2)2, CAS:1345-16-0] salt compounds it is one or more；In the LDP additives
Do not contain the mixed oxide of class containing Cr common in the market, environmental protection and also will not due to Cr from high price be converted into low price when pair
Material mechanical performance is caused to decline in the destruction of the chain structures such as plastic material-C=C- ,-C-C- ,-C-O-O-C, specifically,
The weight percent of the LDP additives is 8-15%.
For above-mentioned resin modified is made to be heat-resisting material, need to add in surface modifier, in the preparation of thermoplastic compounds
In the process, the mode being pre-mixed may be used in surface modifier, can also be added in by the way of being directly blended, and surface is modified
The ratio preferred weight percent of agent addition is 1-5%, and surface modifier is organic silicon modifying agent, in organic titanium class modifying agent
One or two.
Wherein, in the present invention, suitable antioxidant was four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] seasons penta
Four alcohol ester powder or particle, antioxidant are generally used in an amount by 0.01 to 0.5 parts by weight, based on the total composition of 100 parts by weight,
Above-mentioned antioxidant has good compatibility with most polymers.
Wherein graphene is the mixture of dilute 16-20% mono-layer graphites, multi-layer graphene and graphite, wherein
Grapheme material sample is provided by CNANO companies.Some in the π of graphene-pi-conjugated key and plastic materialIn carboxyl, ketone, quinone, C
The functional group of greater activities such as=C ,-[NHCO]-or big pi bond form conjugated bonds covalent bond so that the stretching of material is strong
Degree, elasticity modulus, thermal conductivity, performance obtain more than 20% promotion.Due to the heat-resisting material of PA, PBT, LCP, PEEK base
Polar bond and double bond in functional group are far more than consumption electronic product widely used PC, PC/ABS and its fibre-reinforced compound
Material so the height of SLG contents becomes apparent from the performance influence of above four kinds of modified materials, becomes main affecting factors simultaneously
There is conjugated covalent bonds synergistic effect.
It is provided by the present invention can laser activation high-temperature-resistant thermoplastic composition can be used for molding preparation structure part, due to
Employ high-temperature-resistant thermoplastic composition, structural member surface can Direct Laser process and the three-dimensional conducting channel of preparation of metallizing,
And the thermoplasticity fire resistant resin material as matrix can be subjected to the temperature of SMT, it is possible to realize directly in stereoscopic electric
Road assembling electronic device, and this can laser activation high-temperature-resistant thermoplastic composition good dispersion, mechanical property and chemical plating
It has excellent performance, has good plating performance and processing forming, save assembling procedure, since it may be implemented in structural member table
Face directly makes electronic circuit, not only saves shell space, but also facilitates the installation of other electronic components of enclosure interior, can carry significantly
The integrated level of high electronic product.
The present invention also provides it is a kind of can laser activation high-temperature-resistant thermoplastic composition preparation method, including walking as follows
Suddenly；
S1：Drying, thermoplasticity fire resistant resin is dried at 100-160 DEG C；
S2：Take out grain, according to weight percent, by 8-15%LDP additives, 73.5-89.3% thermoplasticity fire resistant resin,
1-5% rubber solubilisings polymer, 1-5% surface modifiers, 0.3-0.9% graphenes, 0.3%-0.5% resistance to high temperature oxidation
Agent, 0.1% toner or high dielectric material mix at 240-300 DEG C and take out grain, wherein Granulation Equipments L/D values control 25 with
On；
S3：Pelletizing, the pelletizing speed are 40-200RPM；
Optionally, it is described pumping grain step after to it is described can laser activation high-temperature-resistant thermoplastic composition carry out water cooling,
The water cooling behaviour is taken as 50-70 DEG C of water cooling.
Optionally, after using 50-70 DEG C of water cooling, second water cooling is carried out, the water temperature of the second water cooling is 30-45
DEG C, then third road water cooling is carried out with cold water again.
Embodiment 1
The thermoplastic compounds are according to weight percent, including following components：
The preparation method of the thermoplastic compounds of the embodiment, includes the following steps：
Add in the thermoplastic resin PC that weight percent is 80% in an extruder, 13% molybdenum oxide copper, 3% vinyl
Triethoxysilane coupling agent and the blending of 4% acryl-modified silicone resin；It coats either dusting or is granulated finished product.
Embodiment 2
The thermoplastic compounds are according to weight percent, including following components：
Thermoplastic resin PBT79.4%
The preparation method of the thermoplastic compounds of the embodiment, includes the following steps：
Premix：By alkali formula cupric phosphate of the weight percent for 14.5%, 1% titanate coupling agent；4% is acrylic acid modified
Organosilicon etc. is first mixed into the first component；Molding：By the first component and weight percent it is 79.4% thermoplastic resin before injection
PBT be blended in 100 DEG C -115 DEG C and dries 4 hours；It coats either dusting or is granulated finished product.
Embodiments of the present invention are explained in detail above, but the present invention is not limited to described embodiments.It is right
For those skilled in the art, in the case where not departing from the principle of the invention and spirit, these embodiments are carried out more
Kind change, modification, replacement and modification, still fall in protection scope of the present invention.
Claims (9)
1. it is a kind of can laser activation high-temperature-resistant thermoplastic composition, which is characterized in that the thermoplastic compounds are according to weight
Percentage, including following components；
LDP additives：8-15%；
Thermoplasticity fire resistant resin：73.5-89.3%；
Rubber solubilising polymer：1-5%；
Surface modifier：1-5%；
Graphene：0.3-0.9%
Resistance to high temperature oxidation agent：0.3%-0.5%
Remaining is toner or high dielectric material.
2. it is according to claim 1 can laser activation high-temperature-resistant thermoplastic composition, which is characterized in that the thermoplasticity
Fire resistant resin is selected from PA, PBT, LCP, PEEK, PA base fibre reinforced materials, PBT bases fibre reinforced materials, LCP bases fiber and increases
One or more multicomponent alloy composite materials in strong material, PEEK base fibre reinforced materials.
3. it is according to claim 1 can laser activation high-temperature-resistant thermoplastic composition, which is characterized in that the LDP adds
Agent is added to be selected from spinel structure type metal mixing oxide, is Co-Ti-O and Co-AL-O [Co (AlO2)2, CAS:1345-16-0]
Mixed oxide, Co-Ti-O and Co-AL-O [Co (AlO2)2, CAS:1345-16-0] salt compounds it is one or more.
4. it is according to claim 1 can laser activation high-temperature-resistant thermoplastic composition, which is characterized in that the rubber
Solubilized polymer is organosilicon or organosilicon and one kind in General Purpose Rubber elastomer blends.
5. it is according to claim 1 can laser activation high-temperature-resistant thermoplastic composition, which is characterized in that the surface changes
Property agent be organic silicon modifying agent, one or both of organic titanium class modifying agent, the antioxidant is four [β-(3,5- bis- uncles
Butyl -4- hydroxy phenyls) propionic acid] pentaerythritol ester powder or particle.
6. it is according to claim 1 can laser activation high-temperature-resistant thermoplastic composition, which is characterized in that the graphene
For 16-20% single-layer graphenes, multi-layer graphene and graphite mixture.
7. as described in claim 1-6 is any can laser activation high-temperature-resistant thermoplastic composition preparation method, including such as
Lower step；
S1：Drying, thermoplasticity fire resistant resin is dried at 100-160 DEG C；
S2：Grain is taken out, according to weight percent, by 8-15%LDP additives, 73.5-89.3% thermoplasticity fire resistant resin, 1-
5% rubber solubilising polymer, 1-5% surface modifiers, 0.3-0.9% graphenes, 0.3%-0.5% resistance to high temperature oxidation agent exist
240-300 DEG C mixes and takes out grain, and the wherein L/D values of Granulation Equipments are controlled more than 25；
S3：Pelletizing, the pelletizing speed are 40-200RPM.
8. it is according to claim 7 can laser activation high-temperature-resistant thermoplastic composition preparation method, which is characterized in that
After the pumping grain step to it is described can the high-temperature-resistant thermoplastic composition of laser activation carry out water cooling, water cooling operation is adopts
With 50-70 DEG C of water cooling.
9. it is according to claim 8 can laser activation high-temperature-resistant thermoplastic composition preparation method, which is characterized in that
After using 50-70 DEG C of water cooling, second water cooling is carried out, the water temperature of the second water cooling is 30-45 DEG C, then uses cold water again
Carry out third road water cooling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711290535.7A CN108239388A (en) | 2017-12-08 | 2017-12-08 | It is a kind of can laser activation high-temperature-resistant thermoplastic composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711290535.7A CN108239388A (en) | 2017-12-08 | 2017-12-08 | It is a kind of can laser activation high-temperature-resistant thermoplastic composition and preparation method thereof |
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| Publication Number | Publication Date |
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| CN108239388A true CN108239388A (en) | 2018-07-03 |
Family
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| CN201711290535.7A Withdrawn CN108239388A (en) | 2017-12-08 | 2017-12-08 | It is a kind of can laser activation high-temperature-resistant thermoplastic composition and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110079076A (en) * | 2019-04-23 | 2019-08-02 | 深圳市鑫方上科技有限公司 | It is a kind of can laser activation high-temperature-resistant thermoplastic composition and preparation method thereof |
| CN114106678A (en) * | 2021-12-13 | 2022-03-01 | 国网湖南省电力有限公司 | Anti-icing coating on surface of fan blade and preparation method and application thereof |
-
2017
- 2017-12-08 CN CN201711290535.7A patent/CN108239388A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110079076A (en) * | 2019-04-23 | 2019-08-02 | 深圳市鑫方上科技有限公司 | It is a kind of can laser activation high-temperature-resistant thermoplastic composition and preparation method thereof |
| CN114106678A (en) * | 2021-12-13 | 2022-03-01 | 国网湖南省电力有限公司 | Anti-icing coating on surface of fan blade and preparation method and application thereof |
| CN114106678B (en) * | 2021-12-13 | 2022-04-22 | 国网湖南省电力有限公司 | Anti-icing coating on surface of fan blade and preparation method and application thereof |
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