CN109836775A - Preparation method suitable for Laser Direct Deposition technology epoxy resin-matrix prepreg - Google Patents
Preparation method suitable for Laser Direct Deposition technology epoxy resin-matrix prepreg Download PDFInfo
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- CN109836775A CN109836775A CN201711234824.5A CN201711234824A CN109836775A CN 109836775 A CN109836775 A CN 109836775A CN 201711234824 A CN201711234824 A CN 201711234824A CN 109836775 A CN109836775 A CN 109836775A
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Abstract
The present invention relates to the preparation methods for being suitable for Laser Direct Deposition technology epoxy resin-matrix prepreg, the prepreg manufacturing method suitable for LDS technology proposed is using epoxy resin as matrix, addition laser powder, latent curing agent, promotor, toughener prepare resin matrix, using glass fabric or quartz fiber cloth as reinforcing material, prepreg is prepared using wet process or hot melt.The present invention uses epoxy resin for main matrix resin, abundant raw material, it is cheap, the pot-life of prepreg is effectively extended using latent curing agent, it can guarantee that the article surface that prepreg is made into can be realized the problem of complicated skin-surface metallizes by laser activation, so as to use LDS technology after adding laser powder simultaneously, the application range for expanding LDS technology, provides advanced process to prepare intelligent electromagnetic window construction.
Description
Technical field
The present invention relates to a kind of preparation methods of prepreg, are related to a kind of pre- suitable for Laser Direct Deposition technology (LDS)
Soak the manufacturing method of material.
Technical background
Laser direct forming (Laser Direct Structuring is abbreviated as LDS) refers to using laser directly circuit diagram
Case is transferred on moulded plastic part surface, forms circuit interconnection architecture using the three-dimensional surface of three-dimensional workpiece.This technology is only
Suitable for adulterating the injected plastics material of specialist additive, after laser throwing shines article surface, article surface will form activated metal grain
Son, reducing agent when as electroless copper, is catalyzed the precipitating of copper metal, to form metal layer.
With the development of radome technology, a kind of novel radome mechanism is formd, i.e. electromagnetism is intelligently tied
Structure is briefly exactly some metal units of inner inclusion and circuit chip in traditional antenna cover, such as conformal antenna cover, frequency
Select radome structure etc..When preparing the electromagnetism intelligence structure of the tramp metals pattern such as conformal antenna cover, often prepreg at
Complicated metal pattern is realized on the covering of type, realizes the function of antenna or frequency choosing.The side of skin-surface metallization is carried out at present
Method is usually metal piece or copper-clad plate, or then laser ablation or machine add for plating, chemical plating or vacuum ion membrane plating,
But the metal pattern high for type face or antenna pattern complexity, dimensional accuracy can not just utilize the above conventional method.
LDS technology may be implemented to form high-precision metal pattern in any complex profile.But height common at present is thoroughly
Wave composite material is not available LDS technology, and the application of LDS technology is restricted.
Summary of the invention
Innovation and creation purpose
The purpose of the present invention is preparing a kind of prepreg for meeting LDS technology, what realization was metallized in complicated skin-surface
Problem expands the application range of LDS technology, provides advanced process to prepare intelligent electromagnetic window construction.The present invention provides
A kind of preparation method that can utilize LDS technology prepreg.
Inventive technique scheme
Prepreg manufacturing method proposed by the present invention suitable for LDS technology is to add laser using epoxy resin as matrix
Powder, latent curing agent, promotor, toughener prepare resin matrix, using glass fabric or quartz fiber cloth as reinforcing material,
Prepreg is prepared using wet process or hot melt.
Suitable for the preparation method of Laser Direct Deposition technology prepreg, realized by following steps:
Step 1: epoxy resin and toughener being stirred at 50 DEG C~120 DEG C, form component A；
Step 2: low viscosity epoxy resin being uniformly mixed with latent curing agent, promotor, laser powder at room temperature, shape
At B component；
Step 3: component A and B component being uniformly mixed at 30 DEG C~100 DEG C, form prepreg resin matrix；
Step 4: the prepreg resin matrix that step 3 is obtained is using sweat connecting machine or other equivalent of the apparatus and strengthening material
Expect that hot pressing is compound, is made into prepreg；Or after organic solvent is added in the prepreg resin matrix for obtaining step 3, using wet process
Pre- dipping machine or other equivalent ways with reinforcing material is compound is made into prepreg.
Epoxy resin described in step 1 and step 2 is bis-phenol A glycidyl ether, novolac epoxy resin and shrinks sweet
At least one of oleyl amine type epoxy resin, content of epoxy resin described in step 1 account for 40 parts~80 parts, low viscous described in step 2
The dosage of degree epoxy resin accounts for 0~40 part.
Toughener in step 1 is polyether sulfone, polysulfones, polyether-ether-ketone, polyphenylene oxide, polyphenylene sulfide, polyimide resin, gathers
At least one of phenoxy resin and nylon, toughener dosage account for 0 part~20 parts.
In the step 2 latent curing agent be dicyandiamide, modified dicyandiamine, carbamide derivative, diaminodiphenylsulfone,
At least one of Boron Trifluoride Ethylamine and imidazole curing agent, promotor are at least one of phenols, acids, amides.
Laser powder is that the organometallic polymer containing Mg, Al, Zn, Fe or metal-organic complex are at least one.
The viscosity of low viscosity epoxy resin is not more than 18000 centipoises at room temperature in step 2；Latent curing agent accounts for 10 parts
~30 parts, promotor accounts for 0~10 part, and laser powder accounts for 5 parts~10 parts.
Hybrid mode is manual mode or mechanical stirring, grinding in the step 3；Mixing can be component A and B component
The last the two of manufacture is uniformly mixed respectively, and the component of B component can also be directly added in component A, is then uniformly mixed.
Prepreg is to be prepared using hot melt or wet process in the step 4, that is, uses sweat connecting machine or other equivalent
Equipment preparation, alternatively, being prepared after adding organic solvent to prepreg resin matrix using the pre- dipping machine of wet process or other equivalent ways.
If step 4 is prepared using wet process, can be added in at least step in step 1, step 2, step 3 organic molten
The viscosity of agent, final prepreg resin matrix is not more than 10000 centipoises at normal temperature；The organic solvent is ketone, ether alcohol
It is at least one kind of in class, chlorohydrocarbon.
Reinforcing material is quartz fibre, glass fibre, basalt fibre, nylon fiber, polytetrafluoroethyl-ne in the step 4
The braided fabric of one of alkene fiber, ultra high molecular weight polyethylene fiber or one or more of the above fiber；Described
Prepreg gel content is 30%~60%.
Inventive technique effect
The present invention uses epoxy resin for main matrix resin, and abundant raw material is cheap, is had using latent curing agent
Effect extends the pot-life of prepreg, while can guarantee that the article surface that prepreg is made into can be swashed after adding laser powder
Photoactivation realizes the problem of complicated skin-surface metallizes that expand LDS technology applies model so as to use LDS technology
It encloses, provides advanced process to prepare intelligent electromagnetic window construction.
Specific embodiment
Existing and common skin-surface metallization is usually to paste sheet metal, flexibility coat copper plate, metal in skin-surface
Spraying, vacuum ion membrane plating, the modes such as magnetron sputtering.But all haves the shortcomings that obvious, such as stickup metal pattern with upper type
Mode positioning accuracy it is not high, complex-curved be difficult to cover shape；The metallic particles of metal spraying is big, coating thickness is uneven, vacuum
The problems such as ion film plating is uneven there is also coating film thickness for the product of type face complexity.And LDS technology can be in arbitrarily complicated song
Complicated metal pattern is realized on face, but LDS technology is confined at present on the product of injection molding, there is no multiple in resin base
There is application on condensation material.
The present invention uses in view of the above problems, prepare a kind of polymer matrix composites (prepreg) suitable for LDS technology
Epoxy resin is resin matrix, and using conventional fiber or braided fabric as reinforcing material, providing a kind of can satisfy the pre- of LDS technology
Soak preparation method for material.Specific embodiment is as follows:
Embodiment 1: it suitable for the preparation method of Laser Direct Deposition technology prepreg, is realized by following steps:
Step 1: by 30~40 parts of E-20 epoxy resin, 20~30 parts of E-44 epoxy resin, 10 parts of polysulfones are at 100 DEG C
Melting mixing forms the component A of uniformly one.
Step 2: by 30~40 parts of E-51 epoxy resin and 5~10 parts of dicy-curing agents, 2~8 parts of resorcinols, 5
~8 parts of organometallic polymers containing Al are mixed, and stirring rate is 100r/min~500r/min, are mixing uniformly to form
B component.
Step 3: component A and B component being subjected to mechanical stirring using 50r/min~500r/min revolving speed at 60 DEG C, formed
Prepreg resin matrix.
Step 4: resin matrix and alkali-free glass fiber cloth are prepared by prepreg using sweat connecting machine.
Embodiment 2: it is suitable for Laser Direct Deposition technology prepreg, is realized by following steps:
Step 1: by 30~40 parts of F-51 novolac epoxy resin, 20~30 parts of E-20 epoxy resin, 15 parts~20 parts
Polyimides, 100~300 parts of acetone is mixed dissolution, forms component A.
Step 2: by 20~30 parts of F-51 epoxy resin and 5~10 parts of dicy-curing agents, 2~8 parts of resorcinols, 5
~8 parts of organometallic polymers containing Zn, 200~300 parts of acetone are mixed, and stirring rate is 100r/min~500r/
Min is mixing uniformly to form B component.
Step 3: component A and B component being mixed, stirred evenly after adding 100 parts~150 parts of acetone, preimpregnation is formed
Expect resin matrix.
Step 4: resin matrix and quartz fiber cloth are prepared by prepreg using the pre- dipping machine of wet process.
Claims (10)
1. being suitable for the preparation method of Laser Direct Deposition technology prepreg, it is characterised in that: realized by following steps:
Step 1: epoxy resin and toughener being stirred at 50 DEG C~120 DEG C, form component A；
Step 2: low viscosity epoxy resin being uniformly mixed with latent curing agent, promotor, laser powder at room temperature, forms B
Component；
Step 3: component A and B component being uniformly mixed at 30 DEG C~100 DEG C, form prepreg resin matrix；
Step 4: the prepreg resin matrix that step 3 is obtained is using sweat connecting machine or other equivalent of the apparatus and reinforcing material warm
It presses compound, is made into prepreg；Or it after organic solvent is added in the prepreg resin matrix for obtaining step 3, is presoaked using wet process
Machine or other equivalent ways with reinforcing material is compound is made into prepreg.
2. preparation method as described in claim 1, it is characterised in that: epoxy resin described in step 1 and step 2 is double
At least one of phenol A glycidol ether, novolac epoxy resin and glycidyl amine type epoxy resin, wherein described in step 1
Content of epoxy resin accounts for 40 parts~80 parts, and the dosage of low viscosity epoxy resin described in step 2 accounts for 0~40 part.
3. preparation method as described in claim 1, it is characterised in that: the toughener in step 1 is polyether sulfone, polysulfones, polyethers
At least one of ether ketone, polyphenylene oxide, polyphenylene sulfide, polyimide resin, focus ratio and nylon, toughener dosage account for 0
Part~20 parts.
4. preparation method as described in claim 1, it is characterised in that: latent curing agent is dicyandiamide, modified pair in step 2
At least one of cyanamide, carbamide derivative, diaminodiphenylsulfone, Boron Trifluoride Ethylamine and imidazole curing agent, promotor are
At least one of phenols, acids, amides；Laser powder is the organometallic polymer containing Mg, Al, Zn, Fe or organic gold
It is at least one to belong to complex compound.
5. preparation method as described in claim 1, it is characterised in that: the viscosity of low viscosity epoxy resin is in room temperature in step 2
It is not more than 18000 centipoises down；Latent curing agent accounts for 10 parts~30 parts, and promotor accounts for 0~10 part, and laser powder accounts for 5 parts~10 parts.
6. preparation method as described in claim 1, it is characterised in that: hybrid mode is that manual mode or machinery stir in step 3
It mixes, grind；Mixing can manufacture respectively for component A and B component, and then the two is uniformly mixed, and can also directly add in component A
The component for adding B component, is then uniformly mixed.
7. preparation method as described in claim 1, it is characterised in that: prepreg is using hot melt or wet process system in step 4
It is standby, i.e., it is prepared using sweat connecting machine or other equivalent of the apparatus, or used after adding organic solvent to prepreg resin matrix
The pre- dipping machine of wet process or the preparation of other equivalent ways.
8. preparation method as claimed in claim 7, it is characterised in that:, can be in step 1, step if step 4 is prepared using wet process
Rapid 2, organic solvent is added in at least step in step 3, the viscosity of final prepreg resin matrix is not more than at normal temperature
10000 centipoises；The organic solvent is ketone, ether alcohol class, at least one kind of in chlorohydrocarbon.
9. preparation method as claimed in claim 7, it is characterised in that: reinforcing material is quartz fibre, glass fibers in step 4
One of dimension, basalt fibre, nylon fiber, polytetrafluoroethylene fibre, ultra high molecular weight polyethylene fiber or the above fibre
The braided fabric of one or more of dimension.
10. preparation method as claimed in claim 7, it is characterised in that: the prepreg gel content is 30%~60%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711234824.5A CN109836775A (en) | 2017-11-29 | 2017-11-29 | Preparation method suitable for Laser Direct Deposition technology epoxy resin-matrix prepreg |
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| CN201711234824.5A CN109836775A (en) | 2017-11-29 | 2017-11-29 | Preparation method suitable for Laser Direct Deposition technology epoxy resin-matrix prepreg |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110922754A (en) * | 2019-11-08 | 2020-03-27 | 南京湘珀新材料科技有限公司 | Preparation method and application of polyimide film |
| CN111961339A (en) * | 2020-07-31 | 2020-11-20 | 山东大学 | Laser direct forming thermoplastic composite material and preparation method and application thereof |
| CN112226039A (en) * | 2020-09-14 | 2021-01-15 | 江苏澳盛复合材料科技有限公司 | Resin matrix for LDS (laser direct structuring) process, preparation method and prepreg |
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| CN103756472A (en) * | 2013-12-18 | 2014-04-30 | 东莞劲胜精密组件股份有限公司 | Laser-activable LDS (Laser Direct Structuring) natural coating |
| CN104277418A (en) * | 2013-07-09 | 2015-01-14 | 上海杰事杰新材料(集团)股份有限公司 | Carbon fiber reinforced toughened epoxy resin composite material and preparation method thereof |
| CN105504686A (en) * | 2015-12-30 | 2016-04-20 | 广东生益科技股份有限公司 | Thermosetting resin composition as well as prepreg, laminated board and circuit carrier containing same |
| CN106883580A (en) * | 2017-04-07 | 2017-06-23 | 深圳市华盈新材料有限公司 | Laser direct forming PC composites and its preparation technology |
| CN106893256A (en) * | 2015-12-18 | 2017-06-27 | 比亚迪股份有限公司 | A kind of epoxy resin composition for prepreg and preparation method thereof and prepreg |
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Patent Citations (7)
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| CN103450675A (en) * | 2012-05-31 | 2013-12-18 | 金发科技股份有限公司 | Resin composition having laser direct-structuring function and its preparation method and use |
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| CN104277418A (en) * | 2013-07-09 | 2015-01-14 | 上海杰事杰新材料(集团)股份有限公司 | Carbon fiber reinforced toughened epoxy resin composite material and preparation method thereof |
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| CN106893256A (en) * | 2015-12-18 | 2017-06-27 | 比亚迪股份有限公司 | A kind of epoxy resin composition for prepreg and preparation method thereof and prepreg |
| CN105504686A (en) * | 2015-12-30 | 2016-04-20 | 广东生益科技股份有限公司 | Thermosetting resin composition as well as prepreg, laminated board and circuit carrier containing same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922754A (en) * | 2019-11-08 | 2020-03-27 | 南京湘珀新材料科技有限公司 | Preparation method and application of polyimide film |
| CN111961339A (en) * | 2020-07-31 | 2020-11-20 | 山东大学 | Laser direct forming thermoplastic composite material and preparation method and application thereof |
| CN112226039A (en) * | 2020-09-14 | 2021-01-15 | 江苏澳盛复合材料科技有限公司 | Resin matrix for LDS (laser direct structuring) process, preparation method and prepreg |
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