CN107586519A - Halogen-free flameproof black epoxy glue composition and the method with its making electromagnetic shielding film - Google Patents
Halogen-free flameproof black epoxy glue composition and the method with its making electromagnetic shielding film Download PDFInfo
- Publication number
- CN107586519A CN107586519A CN201610528594.2A CN201610528594A CN107586519A CN 107586519 A CN107586519 A CN 107586519A CN 201610528594 A CN201610528594 A CN 201610528594A CN 107586519 A CN107586519 A CN 107586519A
- Authority
- CN
- China
- Prior art keywords
- halogen
- layer
- epoxy glue
- free
- black
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Laminated Bodies (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The present invention relates to a kind of halogen-free flameproof black epoxy glue composition, and it includes each component of following mass parts：Halogen-free 12~50 parts of epoxy resin；10~40 parts of thermoplastic resin and/or synthetic rubber；2~10 parts of curing agent；Phosphorous and/or 8~40 parts of nitrogenous flame ratardant；3~70 parts of black filler；0.1~5 part of curing accelerator；The present invention also provides a kind of method that electromagnetic shielding film is made using above-mentioned halogen-free flameproof black epoxy glue composition, it uses electromagnetic shielding film made of halogen-free flameproof black epoxy glue composition to have hardening time short, cured product shows good peel strength, welding heat resistance, stable blackness, can within ten minutes rapid curing；The flame retardant rating of its black covering film prepared or electromagnetic shielding film reaches UL 94V0 levels；Case hardness can reach 1H, have good surface bond performance；And there is certain electromagnetic wave shielding characteristic.
Description
【Technical field】
The present invention relates to covering membrane technology, more particularly to a kind of quick-setting halogen-free flameproof black epoxy glue composition and
The method of electromagnetic shielding film is made with it.
【Background technology】
With the high speed development of electronics industry, volume, the size of electronic product are less and less, and power density is increasing,
Functional module is more and more, and it is one designed electronics industry to solve the problems, such as to interfere between electronic equipment, functional module
Individual huge challenge.
Electromagnetic shielding film, which is undoubtedly, solves the problems, such as one of effective means of Electromagnetic Interference, and electromagnetic shielding film is a kind of tool
There is good function of shielding, it is made up of the five-layer structure of uniqueness, is release film layer, black insulating barrier, metal level, conduction respectively
Glue-line and protection film layer composition.The operation principle of electromagnetic shielding film be need to prevent it is laminating on the wiring board of Electromagnetic Interference
Electromagnetic shielding film, external electromagnetic waves and internal electromagnetic wave when by screened film refraction, electromagnetic wave absorption to reach the work(of shielding
Energy.
It is substantial amounts of organic molten due to that can discharge in use traditionally typically using conductive silver paste as shielding carrier
Agent, environment, health are damaged, progressively by market.And during using conductive silver paste as shielding carrier, a side
Face, the Major Technology for realizing coating layer black are to add the black fillers such as nigrosine, cobalt black, carbon black in coated glue layer to make
It reaches the purpose of black；But the tinting strength, tinting power of cobalt black is poor, carbon black is easily reunited bad dispersibility, and nigrosine long-term use is to operator
The health of work produces larger harm, it is impossible to fire-retardant, the problems such as easily decomposing of being heated.On the other hand, conditional electronic material epoxy glue
Two-step method is needed to use to solidify, i.e.,：Baking makes its solvent flashing in present coater oven, and reaches semi-cured state, it
It is used as required afterwards after different technique places into baking oven (as pressed, the technique such as fitting) and carries out solidify afterwards, exists to former material
The problems such as material requires high, and energy consumption is big, and hardening time is long.In addition, epoxy glue easily causes warpage, or even volume after rapid curing
Into tubular, it is impossible to reach the requirement of flexible circuitry plate material.
【The content of the invention】
The invention aims to overcome weak point of the prior art, there is provided one kind is free of halogen and can be fire-retardant
Rapid curing halogen-free flameproof black epoxy glue composition.
Another object of the present invention is to overcome weak point of the prior art, there is provided one kind is free of halogen and energy
The method that enough fire-retardant quick-setting halogen-free flameproof black epoxy glue compositions make electromagnetic shielding film.
In order to realize foregoing invention purpose, the technical solution adopted by the present invention is：
A kind of halogen-free flameproof black epoxy glue composition, it includes each component of following mass parts：
Halogen-free 12~50 parts of epoxy resin；
10~40 parts of thermoplastic resin and/or synthetic rubber；
2~10 parts of curing agent；
Phosphorous and/or 8~40 parts of nitrogenous flame ratardant；
3~70 parts of black filler；
0.1~5 part of curing accelerator.
Preferably, the halogen-free epoxy resin be phenol type, it is biphenyl type, DSPD phenolic, bisphenol A-type, bisphenol S type, double
More than the halogen-free epoxy resin and one or both of their cyanide and halogen-free phosphorous epoxy resin of phenol F types
Combination；Wherein, the halogen-free epoxy resin refers to not include halogen atom in the molecular structure, but is wrapped in each molecule
Epoxy resin containing at least two epoxy radicals, halogen-free epoxy resin is had no particular limits, each of market sale can be used
The halogen-free epoxy resin of kind.
Preferably, the halogen-free epoxy resin is polybutene rubbers and/or acrylonitrile modified bisphenol A-type Halogen prime ring
Oxygen tree fat.
Preferably, the thermoplastic resin is polyester resin, acrylic resin, phenoxy resin and polyamidoimide
Mixture more than one or both of resin；When the thermoplastic resin and synthetic rubber are used in mixed way, described thermoplastic
Property resin account for mass parts as 0~10 part, described synthetic rubber accounts for mass parts as 15~30 parts.
Preferably, the synthetic rubber be acrylonitrile and butadiene copolymer symphysis into carboxylic acrylonitrile-butadiene
Copolymer, the carboxylic acrylonitrile-butadiene copolymer molecular end carboxylated is by including carboxyl (such as methacrylic acid)
Monomer realize, wherein, acrylonitrile content is 5~60 mass percent；Acrylonitrile content preferably 15~35 quality
Percentage, the carboxylic butadiene copolymer of acrylonitrile one can use the Related product of market sale, such as (the Zeon of Nipol 1072
Corporation), 1072CG and high-purity, the product XER-32 of low ionic impurity.
Preferably, the curing agent is to use the curing agent based on polyamines and/or the curing agent based on acid anhydrides.The backbone
The curing agent of polyamines is more than one or both of diaminodiphenylsulfone, phenylenediamine, diaminodiphenyl-methane mixed
Compound, the curing agent of the backbone acid anhydrides be such as one kind in phthalate anhydride, pyromellitic dianhydride, hexahydrophthalic anhydride or
Two or more mixtures.
Preferably, described phosphorous and/or nitrogenous flame ratardant is OP-935 and/or the one or two kinds of of aluminium hydroxide mix
Thing.
Preferably, the black filler is mixture more than one or both of carbon dust, CNT, graphene；
Wherein, it is that irregular or sheet, particle diameter are 20nm~25um that carbon nanotube filler is granular.
Preferably, the curing accelerator is one in imidazolium compounds, organic carbamide compound, quaternary ammonium salt and borofluoride
Kind or two or more mixtures；The imidazolium compounds be 2-methylimidazole, 1- methylimidazoles, 2-ethyl-4-methylimidazole,
2- ethyls -4, monomethyl imidazoles (2E4MZ), 1- cyanoethyls -2-ethyl-4-methylimidazole (2E4MZ-CN), 2- undecyl miaows
Azoles (C11Z), 1- cyanoethyls -2 one foretell one kind or two that an alkyl imidazole (C11Z-CN) or 2 heptacosane base miaows are sat in (C17Z)
The mixture of the kind above；Organic carbamide compound is C6H3Cl2-NH-CO-N (CH3) 2, C6H5-NH-CO-N (CH3) 2, H3C-
C6H3 [NH-CO-N (CH3) 2] 2 one or more kinds of mixtures；The quaternary ammonium salt is 2,4,6 13 (dimethylamino first
Base) three (diethacetic acid) salt of phenol or the oleate of 2,4,6- (methylamine ylmethyl) phenol；The borofluoride is trifluoro
Change the complex compound or borontrifluoride of boron and the complex compound of mono aminoethane, the complex compound of boron trifluoride and n-butylamine, boron trifluoride and benzylamine
Mixture more than one or both of complex compound of boron and dimethylaniline；Wherein, the preferable matter of the curing accelerator
It is 0.1~1 part to measure part.
The method that electromagnetic shielding film is made of halogen-free flameproof black epoxy glue composition, the first of the electromagnetic shielding film
Layer carrier layer is mould release membrance, and third layer metal level is screen layer, and the 4th layer of conductive adhesive layer is conductive layer, and layer 5 release layer is guarantor
Cuticula, using halogen-free flameproof black epoxy glue composition as insulation between the first layer carrier layer and third layer metal level
Layer makes second layer black epoxy glue-line, makes second layer black epoxy glue-line and comprises the following steps：
(1) each component of halogen-free flameproof black epoxy glue composition, is weighed in proportion, is placed in milling apparatus, and addition has
High shear is delivered to after solvent progress mixed grinding and is dispersed with stirring in equipment well mixed, formation halogen-free flame-retardant black insulating cement
The liquid dispersion of composition, then using coating apparatus using the dispersion be coated on as mould release membrance first layer carrier layer,
Rubberization thickness is 3~22 μm；
(2), the first layer carrier layer coated with resin combination dispersion in step (1) is removed by drying oven
Organic solvent, and dry halogen-free flame-retardant black epoxy glue composition and cause it to form the insulation of the halogen-free flame-retardant black of semi-solid preparation state
Glue composition layer, 80~180 DEG C of drying temperature, heat time are 2~10min, obtain the half of halogen-free flame-retardant black epoxy glue
Cured product；
(3), by the semi-solid preparation product of the halogen-free flame-retardant black epoxy glue of step (2) be put under high vacuum environment sputtering,
Evaporation, or metallization black insulation glue-line obtains the semi-finished product of electromagnetic shielding film in electroless plating tank；
(4) conductive glue, is passed through into drying oven on the electromagnetic shielding film semi-finished product of step (3), removed organic
Solvent simultaneously dries conducting resin composition to its semi-solid preparation, you can obtains finished product.
Further, the first layer carrier layer is PET mould release membrances, and thickness is 25~100 μm；First layer carrier layer is preferred
PET matte release films, thickness are 50~75 μm.
Further, the second layer black epoxy glue-line is halogen-free flame-retardant black epoxy glue, 3~25 μm of thickness；It is excellent
It is 5~15 μm to select halogen-free flame-retardant black epoxy glue thickness.
Further, the thickness of the 3rd metal level exists
Further, at 3~25 μm, the thickness of preferably the 4th layer conductive adhesive layer is the thickness of the 4th layer of conductive adhesive layer
3~10 μm.
The beneficial effects of the invention are as follows：
It is experimentally confirmed, halogen-free flameproof black epoxy glue composition of the present invention, case hardness can reach 1H after solidification,
Without obvious color change and there is good acid-proof alkaline with certain electromagnetic wave shielding characteristic, after wicking；Cured product
Good hardness, anti-flammability, peel strength, electrical property and welding heat resistance are shown, and it is harmful without halogen, antimonide etc.
Material element, do not pollute the environment.Its electromagnetic shielding film prepared has advantages below.
1), flame retardant rating reaches UL-94V0 levels；
2), there is higher peel strength；
3), soldering resistance, 288 DEG C of wicking 2min are not stratified, non-foaming；
4), high capability of electromagnetic shielding (>=50dB)；
5), there is good degree of blackness and surface is unglazed.
【Brief description of the drawings】
Fig. 1 is the layered structure schematic diagram of electromagnetic shielding film of the present invention.
【Embodiment】
The present invention is described further with reference to embodiment, in each embodiment involved raw material dosage and
Proportioning is percent mass proportioning, and specified otherwise makes an exception.
As shown in figure 1, the first layer carrier layer 1 of the electromagnetic shielding film is mould release membrance, third layer metal level 3 is shielding
Layer, the 4th layer of conductive adhesive layer 4 is conductive layer, and layer 5 release layer 5 is diaphragm, in the first layer carrier layer 1 and third layer
Second layer black epoxy glue-line 2 is made as insulating barrier using halogen-free flameproof black epoxy glue composition between metal level 3.
The selection of each raw material of the present invention, details are as follows：
1st, halogen-free epoxy resin
The present invention has no particular limits to halogen-free epoxy resin, using various halogen-free asphalt mixtures modified by epoxy resin on the market
Fat, such as DCPD phenol type epoxy resins have trade name DPNE-1501L (Hunan Jia Shengde Science and Technology Ltd.s, epoxide equivalent
For 254g/eq)；Biphenyl type epoxy resin has NC-3000 (Nippon Kayaku Co, LLD epoxide equivalent 280g/eq)；Bis-phenol
A epoxy resin has GELR128E (HongChang Electronic Materials Co., Ltd, epoxide equivalent 185g/eq), GBSR901 (Hong Chang bags
Sub- material limited company, epoxide equivalent 475g/eq), KET4131A70 (K0LON, epoxide equivalent 215.5g/eq),
ER1256 (Mitsubishi chemical Co., Ltd, epoxide equivalent 9052g/eq)；Bisphenol F epoxy resin has NC-2000L (Nippon
Kayaku co, Ltd epoxide equivalent 280g/eq)；Phosphorous epoxy resin has DC-G26-K70 (Ding Chuan Science and Technology Ltd.s, epoxy
Equivalent 475g/eq), DC-G2630-K70 (Ding Chuan Science and Technology Ltd.s, epoxide equivalent 380g/eq)；Polybutadiene rubber is modified
Bisphenol A type epoxy resin such as MX-257 (KANEKA Corporation, CSR content 27 mass %, epoxide equivalent 294g/eq)
Bisphenol A type epoxy resin such as HyPox RK84L (CVC Thermoset Specialties, the elasticity being modified with acrylic-nitrile rubber
The mass of the scale of construction 32%, epoxide equivalent 1350g/eq) etc..
Halogen-free epoxy resin above can be used alone, or is applied in combination with two or more different resins.
2nd, thermoplastic resin can use various thermoplastic resins on the market, and applicable thermoplastic resin has polyester tree
Fat, acrylic resin, phenoxy resin and polyamide-imide resin；It is selectable to have PP.081*lx-90 (phenoxy group trees
Fat, SABICINNOVATIVE PLASTTCS), kayaflex series (polyamide-imide resin, Nippon Kayaku Co.,
Ltd.) and KS is serial (acrylic resin containing epoxy radicals, Hitachi Chemical Co., Ltd).
3rd, synthetic rubber
Synthetic rubber can use carboxylic acrylonitrile butene rubber, and this kind of carboxylic rubber is acrylonitrile and fourth two
Rubber is drunk in alkene combined polymerization generation, and selects acrylonitrile-butadiene copolymerization of the acrylonitrile content between 5~60 mass percents
Thing；It is preferred that acrylonitrile-butadiene copolymer of the acrylonitrile content between 20~30 mass percents.These are commercially available to contain carboxylic
The specific example of base rubber have Nipol 1072 (Zeon Corporation), 1072CG (Nahtex Industry co.,
) and high-purity, the product XER-32 (JSR Corporation) of low ionic impurity Ltd.The present invention can also be contained using high-purity
The acrylonitrile butadiene rubber of carboxyl.
Thermoplastic resin and synthetic rubber can be used individually, can also the two be used in mixed way, can also two kinds with
On thermoplastic resin or two or more synthetic rubber be applied in combination.
4th, curing agent
Use of the present invention to curing agent does not have special limitation requirement, any material for being typically used as epoxy curing agent
Material can use, and be preferably based on the curing agent of polyamines and the curing agent based on acid anhydrides；Wherein, the curing agent based on polyamines can be with
That selects has diaminodiphenylsulfone, phenylene triamine, diaminodiphenyl-methane；What the curing agent of backbone acid anhydrides can be selected has
Phthalic anhydride, equal 4th acid anhydrides, hexahydrophthalic anhydride etc..Above-mentioned each curing agent can be used alone, can also
Combination of two or more uses.
5th, curing agent accelerator
The specific example of adoptable curing agent accelerator can select imidazolium compounds, such as 2-methylimidazole, 1- methyl
Imidazoles, 2-ethyl-4-methylimidazole (2E4MZ), 1- cyanoethyls -2-ethyl-4-methylimidazole (2E4Mz-CN), 2- undecyls
Imidazoles (C11Z), 1- cyanoethyl -2- undecyl imidazoles (C11Z-CN) and 2- heptadecyl imidazoles (C17Z) can also select three
Organic phosphine compound, such as triphenylphosphine, dibutyl phosphine；Quaternary ammonium salt or borofluoride etc. can also be selected.
6th, black filler
The present invention does not have special limitation requirement to black filler, and the filler of any black can use.Carbon dust, graphite
The mixture of one or more kinds of compounds in alkene, CNT, particle diameter 20nm-15um；It is preferred that carbon dust, CNT
One or both of filler mixture.
7th, antioxidant
Antioxidant used in the present invention is polynary hindered phenol type antioxidant such as antioxidant 1010, phosphite antioxidant 168,
626 grades or its mixture.
The present invention is more fully described in such as following embodiments, but the present invention is never limited by following embodiments.
Embodiment 1
Halogen-free phosphorus-containing epoxy resin DC-G2630-K70 (Ding Chuan Science and Technology Ltd.s, 450~500g/eq of epoxide equivalent) 4
Mass parts, DPNE1501 (Hunan Jia Shengde Science and Technology Ltd.s, epoxide equivalent 250g/eq) 4 mass parts, GELR128E (Hong Chang
Electronic material limited company, epoxide equivalent 185g/eq) 2 mass parts, RK-84L (CVC Thermoset
Specialties, the elastic scale of construction 32 mass %, epoxide equivalent 1350g/eq) 2 mass parts, synthetic rubber 1072CG (Nantex
Industry Co., Ltd, the mass % of acrylonitrile content 27) 37 mass parts；The mass parts of diaminodiphenylsulfone 4,1- cyanoethyls -2-
The mass parts of ethyl -4-methylimidazole (2E4MZ-CN) 0.5；The mass parts of aluminium hydroxide (Showa H42M) 15, OP-935
(Clariant, phosphorus content 23%) 10 mass parts, CNT (15 μm of average grain diameter, purity more than 98%) 10 mass parts, carbon
Powder (average grain diameter 500nm, purity 99%) 10 mass parts；Antioxidant 1010 (CIBAGEIGY Co., Ltd.s) 1.5 mass parts.
Said components are placed in sand mill, add butanone (MEK), DMF solvent, the solids content of regulation composition is
30%, then carry out the liquid dispersion that halogen-free flameproof black epoxy glue composition is made in mixed grinding.
Then, the liquid dispersion of halogen-free flameproof black epoxy gum oil/fat composition is coated in thickness as 50 μm with coating machine
Matte release film on, coating layer thickness be 10 μm, then in forced ventilation baking oven by coated coating at 150 DEG C dry
5 minutes, so that halogen-free flameproof adhesive composition coating is changed into the glue-line of semi-cured state；By metal level sputter first
The black side of secondary coating obtains second metal layer；Conducting resinl (i.e. conductive layer 4) is coated on second metal layer, obtains electromagnetism wave screen
Cover film finished product.
Embodiment 2
DC-G2630-K70 (Ding Chuan Science and Technology Ltd.s, 450~500g/eq of epoxide equivalent) 10 parts by weight mass parts,
DPNE1501L (Hunan Jia Shengde Science and Technology Ltd.s epoxide equivalents：254g/eq) 9 parts by weight mass parts, GELR128E (Hong Chang
Electronic material limited company, epoxide equivalent 185g/eq) 7 parts by weight mass parts；ER1256 (Mitsubishi chemical Co., Ltd, ring
Oxygen equivalent 9052g/eq) 5 parts by weight mass parts, synthetic rubber 1072CG (Nantex Industry Co, Ltd, acrylonitrile contains
Measure 27 mass %) 27 parts by weight mass parts, the parts by weight mass parts of diaminodiphenylsulfone 5；1- cyanoethyl -2- ethyl -4- methyl miaows
The parts by weight mass parts of azoles (2E4MZ-CN) 0.6；The parts by weight mass parts of OP-935 (Clariant, phosphorus content 23%) 9, aluminium hydroxide
(Showa H42M) 16.4 parts by weight mass parts, CNT (6~8 μm of average grain diameter, purity more than 99%) 10 parts by weight quality
Part, antioxidant 1010 (CIBA GEIGY Co., Ltd.s) 1.0 parts by weight mass parts.
Said components are placed in sand mill, add butanone solvent, the solids content of regulation composition is 40%, Ran Houjin
The liquid dispersion of halogen-free flameproof black epoxy glue composition is made in row mixed grinding.
Then, the liquid dispersion of halogen-free flameproof black epoxy gum oil/fat composition is coated in thickness as 50 μm with coating machine
Matte release film on, coating layer thickness be 10 μm, then in forced ventilation baking oven by coated coating at 150 DEG C dry
5 minutes, so that halogen-free flameproof adhesive composition coating is changed into the glue-line of semi-cured state.By metal level sputter first
The black side of secondary coating obtains second metal layer.Conducting resinl is coated on second metal layer, obtains electromagnetic shielding film finished product.
Embodiment 3
DC-G2630-K70 (Ding Chuan Science and Technology Ltd.s, 450~500g/eq of epoxide equivalent) 25 mass parts, DPNE1501L
(Hunan Jia Shengde Science and Technology Ltd.s epoxide equivalent：254g/eq) (grand prosperous electronic material share has by 10 mass parts, GELR128E
Limit company, epoxide equivalent 185g/eq) 8 mass parts；The mass of ER1256 (Mitsubishi chemical Co., Ltd, epoxide equivalent 9052g/eq) 7
Part, synthetic rubber 1072CG (Nantex Industry Co, Ltd, the mass % of acrylonitrile content 27) 15 mass parts, diaminourea
The mass parts of diphenyl sulphone (DPS) 10；1- cyanoethyls-the mass parts of 2-ethyl-4-methylimidazole (2E4MZ-CN) 0.8；CNT (average grain
6~8 μm of footpath, purity more than 99%) 15 mass parts, the mass parts of aluminium hydroxide (Showa) 8.2, antioxidant 1010 (CIBA GEIGY
Co., Ltd.) 1.0 mass parts.
Said components are placed in sand mill, add butanone solvent, the solids content of regulation composition is 40%, Ran Houjin
The liquid dispersion of halogen-free flameproof black epoxy glue composition is made in row mixed grinding.
Then, the liquid dispersion of halogen-free flameproof black epoxy gum oil/fat composition is coated in thickness as 50 μm with coating machine
Matte release film on, coating layer thickness be 10 μm, then in forced ventilation baking oven by coated coating at 150 DEG C dry
5 minutes, so that halogen-free flameproof adhesive composition coating is changed into the glue-line of solid state.By metal level sputter for the first time
The black side of coating obtains second metal layer.Conducting resinl is coated on second metal layer, obtains electromagnetic shielding film finished product.
Embodiment 4
DC-G2630-K70 (Ding Chuan Science and Technology Ltd.s, 450~500g/eq of epoxide equivalent) 10 mass parts, DPNE1501L
(Hunan Jia Shengde Science and Technology Ltd.s epoxide equivalent：254g/eq) (grand prosperous electronic material share is limited by 9 mass parts, GELR128E
Company, epoxide equivalent 185g/eq) 7 mass parts；HyPox RK84L (CVC Thermoset Specialties, the elastic scale of construction
32% mass, epoxide equivalent 1350g/eq) 5 mass parts, synthetic rubber 1072CG (Nantex Industry Co, Ltd, propylene
The mass % of nitrile content 27) 25 mass parts, OP-935 (Clariant, phosphorus content 23%) 8 mass parts, the mass parts of aluminium hydroxide 9.6,
The mass parts of diaminodiphenylsulfone 5；1- cyanoethyls-the mass parts of 2-ethyl-4-methylimidazole (2E4MZ-CN) 0.4；CNT is (flat
Equal 1~3 μm of particle diameter, purity more than 99%) 20 mass parts, antioxidant 1010 (CIBA GEIGY Co., Ltd.s) 1.0 mass parts.
Said components are placed in sand mill, add butanone solvent, the solids content of regulation composition is 40%, Ran Houjin
The liquid dispersion of halogen-free flameproof black epoxy glue composition is made in row mixed grinding.With coating machine by halogen-free flameproof black epoxy
The liquid dispersion of gum oil/fat composition is coated on the matte release film that thickness is 50 μm, and coating layer thickness is 10 μm, then strong
Coated coating is dried 5 minutes at 150 DEG C in ventilated drying oven processed, so that halogen-free flameproof adhesive composition coating turns
It is changed into the glue-line of semi-cured state.Black side of the metal level sputter in first time coating is obtained into second metal layer.By conducting resinl
Second metal layer is coated on, obtains electromagnetic shielding film finished product.
Embodiment 5
DC-G2630-K70 (Ding Chuan Science and Technology Ltd.s, 450~500g/eq of epoxide equivalent) 10 mass parts, DPNE1501L
(Hunan Jia Shengde Science and Technology Ltd.s epoxide equivalent：254g/eq) (grand prosperous electronic material share is limited by 8 mass parts, GELR128E
Company, epoxide equivalent 185g/eq) 7 mass parts；The mass of ER1256 (Mitsubishi chemical Co., Ltd, epoxide equivalent 9052g/eq) 5
Part, the mass parts of aluminium hydroxide (Showa H42M) 20, OP-935 (Clariant, phosphorus content 23%) 15 mass parts, synthetic rubber
1072CG (Nantex Industry Co, Ltd, the mass % of acrylonitrile content 27) 26.8 mass parts, the matter of diaminodiphenylsulfone 5
Measure part；1- cyanoethyls-the mass parts of 2-ethyl-4-methylimidazole (2E4MZ-CN) 0.2；Carbon dust (average grain diameter 500nm, purity
More than 98%) 3 mass parts, antioxidant 1010 (CIBA GEIGY Co., Ltd.s) 1.0 mass parts.
Said components are placed in sand mill, add butanone solvent, the solids content of regulation composition is 40%, Ran Houjin
The liquid dispersion of halogen-free flameproof black epoxy glue composition is made in row mixed grinding.
Then, the liquid dispersion of halogen-free flameproof black epoxy gum oil/fat composition is coated in thickness as 50 μm with coating machine
Matte release film on, coating layer thickness be 10 μm, then in forced ventilation baking oven by coated coating at 150 DEG C dry
5 minutes, so that halogen-free flameproof adhesive composition coating is changed into the glue-line of semi-cured state.By metal level sputter first
The black side of secondary coating obtains second metal layer.Conducting resinl is coated on second metal layer, obtains electromagnetic shielding film finished product.
Table one：Above-described embodiment and its performance for preparing electromagnetic shielding film
It is as follows with the method for testing of upper table one：
Peel strength：According to IPC-TM-650 2.4.9 method of testings, professional standard is >=0.7kgf/cm
Heat resistance：According to IPC-TM-650 2.4.13 method of testings, professional standard is that 288 DEG C of * 10s are not stratified, non-foaming
Case hardness：According to IPC-TM-650 2.4.27.2 method of testings, professional standard is >=1H anti-flammabilitys：According to
UL94 testing standards, judge.
The present invention is not limited to above-described embodiment, simple replacement based on above-described embodiment, not making creative work,
Should belong to the invention discloses scope.It is presently preferred embodiments of the present invention that embodiment described above, which is, is not limited with this
The practical range of the present invention, the equivalence changes that all principles according to the present invention are made, all should be covered by protection scope of the present invention.
Claims (14)
1. a kind of halogen-free flameproof black epoxy glue composition, it is characterised in that it includes each component of following mass parts：
Halogen-free 12~50 parts of epoxy resin；
10~40 parts of thermoplastic resin and/or synthetic rubber；
2~10 parts of curing agent；
Phosphorous and/or 8~40 parts of nitrogenous flame ratardant；
3~70 parts of black filler；
0.1~5 part of curing accelerator.
2. halogen-free flameproof black epoxy glue composition according to claim 1, it is characterised in that the halogen-free asphalt mixtures modified by epoxy resin
Fat be phenol type, biphenyl type, DSPD phenolic, bisphenol A-type, bisphenol S type, bisphenol-f type halogen-free epoxy resin and they
Combination more than one or both of cyanide and halogen-free phosphorous epoxy resin.
3. halogen-free flameproof black epoxy glue composition according to claim 2, it is characterised in that the halogen-free asphalt mixtures modified by epoxy resin
Fat is polybutene rubbers and/or the halogen-free epoxy resin of acrylonitrile modified bisphenol A-type.
4. halogen-free flameproof black epoxy glue composition according to claim 1, it is characterised in that the thermoplastic resin is
Mixture more than one or both of polyester resin, acrylic resin, phenoxy resin and polyamide-imide resin.
5. halogen-free flameproof black epoxy glue composition according to claim 1, it is characterised in that the synthetic rubber is third
Alkene nitrile and butadiene copolymer symphysis into carboxylic acrylonitrile-butadiene copolymer, the carboxylic acrylonitrile-butadiene is total to
Polymers molecular end carboxylated realized by the monomer comprising carboxyl (such as methacrylic acid), wherein, acrylonitrile content is 5~
60 mass percent.
6. halogen-free flameproof black epoxy glue composition according to claim 1, it is characterised in that the curing agent is use
Curing agent based on polyamines and/or the curing agent based on acid anhydrides.The curing agent of the backbone polyamines is diaminodiphenylsulfone, sub- benzene
Mixture more than one or both of base diamines, diaminodiphenyl-methane, the curing agent of the backbone acid anhydrides is such as benzene
Mixture more than one or both of dicarboxylic acid anhydride, pyromellitic dianhydride, hexahydrophthalic anhydride.
7. halogen-free flameproof black epoxy glue composition according to claim 1, it is characterised in that described phosphorous and/or contain
Nitrogen combustion inhibitor is one or two kinds of mixtures of OP-935 and/or aluminium hydroxide.
8. halogen-free flameproof black epoxy glue composition according to claim 1, it is characterised in that the black filler is carbon
Mixture more than one or both of powder, CNT, graphene.
9. halogen-free flameproof black epoxy glue composition according to claim 1, it is characterised in that the curing accelerator is
Mixture more than one or both of imidazolium compounds, organic carbamide compound, quaternary ammonium salt and borofluoride；The imidazoles
Compound is 2-methylimidazole, 1- methylimidazoles, 2-ethyl-4-methylimidazole, 2- ethyls -4, monomethyl imidazoles (2E4MZ), 1- cyanogen
Ethyl -2-ethyl-4-methylimidazole (2E4MZ-CN), 2- undecyl imidazoles (C11Z), 1- cyanoethyls -2 one foretell an alkyl imidazole
(C11Z-CN) or 2 heptacosane base miaows sit the mixture of one or both of (C17Z) above；Organic carbamide compound is
C6H3Cl2-NH-CO-N (CH3) 2, C6H5-NH-CO-N (CH3) 2, H3C-C6H3 [NH-CO-N (CH3) 2] 2 one or two
Mixture above；The quaternary ammonium salt is three (diethacetic acid) salt or 2,4 of 2,4,6 13 (dimethylamino methyl) phenol,
The oleate of 6- (methylamine ylmethyl) phenol；The borofluoride be the complex compound of boron trifluoride and mono aminoethane, boron trifluoride with
The complex compound of n-butylamine, the complex compound of boron trifluoride and benzylamine or one kind in the complex compound of boron trifluoride and dimethylaniline or
Two or more mixtures.
10. make electromagnetic shielding film with the halogen-free flameproof black epoxy glue composition described in claim 1-9 any one
Method, the first layer carrier layer of the electromagnetic shielding film are mould release membrance, and third layer metal level is screen layer, the 4th layer of conductive adhesive layer
For conductive layer, layer 5 release layer is diaphragm, is hindered between the first layer carrier layer and third layer metal level using Halogen
Fire black epoxy glue composition and make second layer black epoxy glue-line as insulating barrier, it is characterised in that make second layer black
Epoxy adhesive layer comprises the following steps：
(1) each component of halogen-free flameproof black epoxy glue composition, is weighed in proportion, is placed in milling apparatus, is added organic molten
High shear is delivered to after agent progress mixed grinding and is dispersed with stirring in equipment well mixed, formation halogen-free flame-retardant black insulating cement combination
The liquid dispersion of thing, then using coating apparatus using the dispersion be coated on as mould release membrance first layer carrier layer, gluing
Thickness is 3~22 μm；
(2), the first layer carrier layer coated with resin combination dispersion in step (1) is removed by drying oven organic
Solvent, and dry halogen-free flame-retardant black epoxy glue composition and cause it to form the halogen-free flame-retardant black insulating cement group of semi-solid preparation state
Compound layer, 80~180 DEG C of drying temperature, heat time are 2~10min, obtain the semi-solid preparation of halogen-free flame-retardant black epoxy glue
Product；
(3), the semi-solid preparation product of the halogen-free flame-retardant black epoxy glue of step (2) is put under high vacuum environment and sputters, be deposited,
Or the black insulation glue-line that metallized in electroless plating tank obtains the semi-finished product of electromagnetic shielding film；
(4) conductive glue, is passed through into drying oven on the electromagnetic shielding film semi-finished product of step (3), removes organic solvent
And conducting resin composition is dried to its semi-solid preparation, you can obtain finished product.
11. the method that halogen-free flameproof black epoxy glue composition according to claim 10 makes electromagnetic shielding film, its
It is characterised by, the first layer carrier layer is PET mould release membrances, and thickness is 25~100 μm.
12. the method that halogen-free flameproof black epoxy glue composition according to claim 10 makes electromagnetic shielding film, its
It is characterised by, the second layer black epoxy glue-line is halogen-free flame-retardant black epoxy glue, 3~25 μm of thickness.
13. the method that halogen-free flameproof black epoxy glue composition according to claim 10 makes electromagnetic shielding film, its
It is characterised by, the thickness of the 3rd metal level exists
14. the method that halogen-free flameproof black epoxy glue composition according to claim 10 makes electromagnetic shielding film, its
It is characterised by, the thickness of the 4th layer of conductive adhesive layer is at 3~25 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610528594.2A CN107586519A (en) | 2016-07-06 | 2016-07-06 | Halogen-free flameproof black epoxy glue composition and the method with its making electromagnetic shielding film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610528594.2A CN107586519A (en) | 2016-07-06 | 2016-07-06 | Halogen-free flameproof black epoxy glue composition and the method with its making electromagnetic shielding film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107586519A true CN107586519A (en) | 2018-01-16 |
Family
ID=61045812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610528594.2A Pending CN107586519A (en) | 2016-07-06 | 2016-07-06 | Halogen-free flameproof black epoxy glue composition and the method with its making electromagnetic shielding film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107586519A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109161350A (en) * | 2018-09-18 | 2019-01-08 | 江西华莲欣科技有限公司 | A kind of highly-breathable is suitable for the electromagnetic shielding film and preparation method thereof of 5G |
| CN110684472A (en) * | 2019-10-10 | 2020-01-14 | 常州斯威克光伏新材料有限公司 | Halogen-free flame-retardant epoxy resin adhesive film |
| WO2021175138A1 (en) * | 2020-03-06 | 2021-09-10 | 欧菲光集团股份有限公司 | Display module and electronic device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921557A (en) * | 2010-08-30 | 2010-12-22 | 新高电子材料（中山）有限公司 | Halogen-free flame-retardant adhesive composition and flexible copper-clad plate using same |
| CN102558765A (en) * | 2010-12-15 | 2012-07-11 | 新高电子材料（中山）有限公司 | Halogen-free fire-retardant high heat conducting insulating resin composition and heat dissipation metal-base copper clad plate |
| CN105491786A (en) * | 2015-12-18 | 2016-04-13 | 苏州城邦达力材料科技有限公司 | Electromagnetic shielding film applicable to high-frequency signal and manufacturing process thereof |
| CN205249699U (en) * | 2015-09-15 | 2016-05-18 | 东莞市万丰纳米材料有限公司 | Electromagnetic shield membrane |
-
2016
- 2016-07-06 CN CN201610528594.2A patent/CN107586519A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921557A (en) * | 2010-08-30 | 2010-12-22 | 新高电子材料（中山）有限公司 | Halogen-free flame-retardant adhesive composition and flexible copper-clad plate using same |
| CN102558765A (en) * | 2010-12-15 | 2012-07-11 | 新高电子材料（中山）有限公司 | Halogen-free fire-retardant high heat conducting insulating resin composition and heat dissipation metal-base copper clad plate |
| CN205249699U (en) * | 2015-09-15 | 2016-05-18 | 东莞市万丰纳米材料有限公司 | Electromagnetic shield membrane |
| CN105491786A (en) * | 2015-12-18 | 2016-04-13 | 苏州城邦达力材料科技有限公司 | Electromagnetic shielding film applicable to high-frequency signal and manufacturing process thereof |
Non-Patent Citations (3)
| Title |
|---|
| 《中国工程物理研究院科技年报》编辑部: "《2014年版中国工程物理研究院科技年报》", 30 November 2014, 中国原子能出版社 * |
| 周冀: "《高分子材料基础》", 31 July 2007, 国防工业出版社 * |
| 贾瑛等: "《轻质碳材料的应用》", 30 November 2013, 国防工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109161350A (en) * | 2018-09-18 | 2019-01-08 | 江西华莲欣科技有限公司 | A kind of highly-breathable is suitable for the electromagnetic shielding film and preparation method thereof of 5G |
| CN110684472A (en) * | 2019-10-10 | 2020-01-14 | 常州斯威克光伏新材料有限公司 | Halogen-free flame-retardant epoxy resin adhesive film |
| WO2021175138A1 (en) * | 2020-03-06 | 2021-09-10 | 欧菲光集团股份有限公司 | Display module and electronic device |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102558765B (en) | Halogen-free fire-retardant high heat conducting insulating resin composition and heat dissipation metal-base copper clad plate | |
| CN1865382B (en) | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate using same | |
| CN101875825B (en) | Halogen-free flame retardant adhesive composition and flexible copper-clad plate using same | |
| CN101280093B (en) | Halogen-free flame-retardant epoxy resin composition, flexible copper clad laminate made therefrom and preparation of the flexible copper clad laminate | |
| CN103045143A (en) | Halogen-free epoxy adhesive and cover film prepared by using halogen-free epoxy adhesive | |
| US20060234045A1 (en) | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate using same | |
| CN101921557B (en) | Halogen-free flame-retardant adhesive composition and flexible copper-clad plate using same | |
| US7524563B2 (en) | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate using same | |
| CN107586520A (en) | Halogen-free flameproof cover layer conducting resin composition and the method with its making electromagnetic shielding film | |
| US20050196619A1 (en) | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate using same | |
| CN102010569B (en) | Halogen-free flame retardant epoxy resin composition and high-flexibility coating film prepared by same | |
| CN101851480A (en) | Halogen-free and phosphorous-free flame-retardant synthetic resin adhesive used for flexible copper clad laminate | |
| CN101314705A (en) | Fire retardant adhesive composition and covering layer film using the same | |
| US20060264538A1 (en) | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate using same | |
| CN105175995A (en) | Epoxy resin composition for copper-clad plate and application thereof | |
| CN102977829B (en) | Zero-halogen and flame-retardation epoxy resin composition, adhesive tape and preparation method of adhesive tape | |
| CN101831144B (en) | Halogen-free epoxy resin composition and high-flexibility flexible copper clad laminate prepared from same | |
| CN103074019A (en) | Halogen-free epoxy adhesive and flexible copper-clad plate prepared from same | |
| CN103073844A (en) | Halogen-free flame-retardant epoxy resin composition and cover film produced by halogen-free flame-retardant epoxy resin composition | |
| CN102093667B (en) | Epoxy resin composite and covering film prepared from same | |
| CN107586519A (en) | Halogen-free flameproof black epoxy glue composition and the method with its making electromagnetic shielding film | |
| JP2009108144A (en) | Flexible halogen-free epoxy resin composition, metallic foil with resin, cover-lay film, prepreg, laminate for printed wiring board, metal-clad flexible laminate | |
| JP2006342333A (en) | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate plate, using the same | |
| JP2005248134A (en) | Flame retardant adhesive composition, and cover lay film and flexible copper clad laminate plate by using the same | |
| CN105733485B (en) | A kind of resin combination and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20180116 |