CN104999740A - Preparation method for high-CTI halogen-free type CEM-3 copper-clad plate - Google Patents
Preparation method for high-CTI halogen-free type CEM-3 copper-clad plate Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
- B32B17/04—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments bonded with or embedded in a plastic substance
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/08—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the cooling method
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/16—Drying; Softening; Cleaning
- B32B38/164—Drying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
- B32B2037/243—Coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
Abstract
The invention belongs to the technical field of copper-clad plate production and relates to a preparation method for a high-CTI halogen-free type CEM-3 copper-clad plate. According to the prepared copper-clad plate, halogen-free epoxy resin is used for being combined with aluminum hydroxide, so that the comparative tracking index (CTI) of the copper-clad plate is improved, nitrogenous phenolic resin is used for solidifying phosphorous-contained epoxy resin, in addition, an organophosphorous fire retardant is added, so that the nitrogen-phosphorous synergistic flame-retardant effect is achieved, and the UL certification FV0 grade is reached. The copper-clad plate prepared by the preparation method for the high-CTI halogen-free type CEM-3 copper-clad plate meets the halogen-free environmental requirement, the peeling strength of copper foil and a base material is improved, it is guaranteed that the copper-clad plate can be used in environments in high damp and hot, high pollution and high voltage conditions, the service life of the copper-clad plate is prolonged, and the production cost is reduced.
Description
Technical field
The present invention relates to a kind of copper-clad plate, particularly relate to the preparation method of a kind of high CTI, halogen-free type CEM-3 copper-clad plate, belong to copper-clad plate production technical field.
Background technology
Copper-clad plate is widely used in and manufactures all kinds of household electrical appliance, electronics and IT products and industrial electronics printed circuit board used (being called for short PCB).It is as the baseplate material of printed circuit board, and the three zones play carrying dress connection electronic devices and components, forming conductive circuit pattern and insulate between interlayer and circuit is a kind of important basic electronic material.
The anti-flammability of copper-clad plate is one of important security performance of electronic product.Halogen fire proofing (containing Cl, Br) is with its economy and reliability; apply for many years in printed circuit base material industry; but; along with growing to even greater heights of global environmental protection cry; the carrying capacity of environment of halogen fire proofing and just closely receiving publicity on the impact of health, the organisations and institutions of existing many countries detect the carcinogen such as bioxin (Dioxin), dibenzofurans (Dibenzofuran) in succession in the combustion product of Halogen product.The Halogen product in combustion amount of being fuming is very large, can discharge extremely toxic substance hydrogen halides, serious threat health.Therefore research and develop and apply halogen-free type fire proofing, production environment-friendly type printed circuit base material, has become the new trend of copper-clad plate technical development in recent years.
Current halogen-free type CEM-3 copper-clad plate, be utilize the pure phosphorous epoxy systems of dicyandiamide cure to make glass cloth resin, CTI is on the low side, and peel strength is little, and due to the price of phosphorous epoxy resin higher, thus production cost is raised the cost height.
Summary of the invention
The present invention is directed to the deficiency that above-mentioned prior art exists, the preparation method of a kind of high CTI, halogen-free type CEM-3 copper-clad plate is provided.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: the preparation method of a kind of high CTI, halogen-free type CEM-3 copper-clad plate, and step is as follows:
(1) glass cloth resin emulsion is prepared: 45-65 part halogen-free epoxy resin, 1-2 part dicyandiamide, 24-33 part aluminium hydroxide and 8-25 part dimethyl formamide are added reactor successively, 5-8h is stirred at 20-40 DEG C, then utilize high-speed emulsifying machine to carry out emulsification 1.5-2.5h, finally place slaking 12-16h at reactor;
(2) glassine paper or glass felt resin emulsion is prepared: 35-50 part phosphorous epoxy resin, 10-15 part Nitrogen-containing Phenolic Resins, 13-20 part aluminium hydroxide, 5-15 part talcum powder, 5-10 part phosphate and 10-15 part dimethyl formamide are added reactor successively, 5-8h is stirred at 20-40 DEG C, then utilize high-speed emulsifying machine to carry out emulsification 1.5-2.5h, finally place slaking 12-16h at reactor;
(3) the glass cloth resin emulsion that step (1) is obtained is coated in E-glass cloth two-sided, under 160 DEG C of conditions, dries 1min, controlling gel content is 50 ± 1%, and fluidity is 10 ± 1%, obtained glass cloth impregnation tablet;
(4) by glassine paper obtained for step (2) or glass felt resin emulsion is coated in glassine paper or glass felt is two-sided, 1min is dried under 160 DEG C of conditions, controlling gel content is 50 ± 1%, and fluidity is 10 ± 1%, obtained glassine paper or glass felt impregnation tablet;
(5) the obtained glassine paper of several steps (4) is got or glass felt impregnation tablet is superimposed, thereon, lower two sides respectively superposes the glass cloth impregnation tablet of step (3) gained, finally be covered with a Copper Foil at single or double, hot pressing 90-130min under 10-15MPa, 170-180 DEG C of condition, cooling, obtained CEM-3 copper-clad plate.
The invention has the beneficial effects as follows: the copper-clad plate that the present invention obtains, utilize halogen-free epoxy resin combining hydrogen oxidation aluminium, improve the tracking resistance index (CTI) of copper-clad plate, Nitrogen-containing Phenolic Resins is utilized to solidify phosphorous epoxy resin, and add organic phosphorus flame retardant, make nitrogen phosphorus cooperative flame retardant, reach UL certification FV
0level.The copper-clad plate that the present invention obtains reaches halogen-free environmental requirement, improves the peel strength of Copper Foil and base material, ensures the use of the environment such as it is damp and hot at height, high pollution, high voltage, extends its service life, and reduce production cost.
On the basis of technique scheme, the present invention can also do following improvement.
Further, the epoxide equivalent of the halogen-free epoxy resin described in step (1) is 400-450g/eq.
Further, described halogen-free epoxy resin is bisphenol A type epoxy resin.
Further, the epoxide equivalent of the phosphorous epoxy resin described in step (2) is 350-450g/eq, and phosphorus content is 2-4%.
Further, the nitrogen content of the Nitrogen-containing Phenolic Resins described in step (2) is 15-20%.
Further, the phosphate described in step (2) is triphenyl phosphate, tricresyl phosphate, tricresyl phosphate (dimethylbenzene) ester, propyl benzene system phosphate or butylbenzene system phosphate.
Further, the talcous particle diameter described in step (2) is 1-3 μm.
Further, the particle diameter of described aluminium hydroxide is 1-5 μm.
Further, described gel content refers to that the pure solid of impregnation resin emulsion accounts for the percentage of impregnation tablet weight; Described fluidity refers to that impregnation resin emulsion is at 70 ± 5kg/cm
2pressure, the weight that flows out at 160 ± 2 DEG C account for the percentage of impregnation resin emulsion gross weight.
Detailed description of the invention
Be described principle of the present invention and feature below in conjunction with example, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment 1
A preparation method for high CTI, halogen-free type CEM-3 copper-clad plate, step is as follows:
(1) glass cloth resin emulsion is prepared: 45 parts of halogen-free epoxy resins (epoxide equivalent is 400g/eq), 1 part of dicyandiamide, 32 parts of aluminium hydroxides and 22 parts of dimethyl formamides are added reactor successively, 8h is stirred at 20 DEG C, then utilize high-speed emulsifying machine to carry out emulsification 2.5h, finally place slaking 12h at reactor;
(2) glassine paper resin emulsion is prepared: 35 parts of phosphorous epoxy resins (epoxide equivalent is 450g/eq), 10 parts of Nitrogen-containing Phenolic Resins, 20 parts of aluminium hydroxides, 15 parts of talcum powder, 5 portions of triphenyl phosphates and 15 parts of dimethyl formamides are added reactor successively, 8h is stirred at 20 DEG C, then utilize high-speed emulsifying machine to carry out emulsification 2.5h, finally place slaking 12h at reactor;
(3) the glass cloth resin emulsion that step (1) is obtained is coated in E-glass cloth two-sided, under 160 DEG C of conditions, dries 1min, controlling gel content is 50 ± 1%, and fluidity is 10 ± 1%, obtained glass cloth impregnation tablet;
(4) the glassine paper resin emulsion that step (2) is obtained is coated in glassine paper two-sided, under 160 DEG C of conditions, dries 1min, controlling gel content is 50 ± 1%, and fluidity is 10 ± 1%, obtained glassine paper impregnation tablet;
(5) the glassine paper impregnation tablet getting 5 steps (4) obtained is superimposed, thereon, lower two sides respectively superposes the glass cloth impregnation tablet of step (3) gained, finally respectively be covered with a Copper Foil two-sided, hot pressing 130min under 10MPa, 180 DEG C of conditions, cooling, obtained CEM-3 copper-clad plate.
Embodiment 2
A preparation method for high CTI, halogen-free type CEM-3 copper-clad plate, step is as follows:
(1) glass cloth resin emulsion is prepared: 55 parts of halogen-free epoxy resins (epoxide equivalent is 450g/eq), 2 parts of dicyandiamides, 28 parts of aluminium hydroxides and 15 parts of dimethyl formamides are added reactor successively, 5h is stirred at 40 DEG C, then utilize high-speed emulsifying machine to carry out emulsification 1.5h, finally place slaking 16h at reactor;
(2) glass felt resin emulsion is prepared: 42 parts of phosphorous epoxy resins (epoxide equivalent is 350g/eq), 15 parts of Nitrogen-containing Phenolic Resins, 15 parts of aluminium hydroxides, 10 parts of talcum powder, 8 parts of tricresyl phosphates and 10 parts of dimethyl formamides are added reactor successively, 5h is stirred at 40 DEG C, then utilize high-speed emulsifying machine to carry out emulsification 1.5h, finally place slaking 16h at reactor;
(3) the glass cloth resin emulsion that step (1) is obtained is coated in E-glass cloth two-sided, under 160 DEG C of conditions, dries 1min, controlling gel content is 50 ± 1%, and fluidity is 10 ± 1%, obtained glass cloth impregnation tablet;
(4) the glass felt resin emulsion that step (2) is obtained is coated in glass felt two-sided, under 160 DEG C of conditions, dries 1min, controlling gel content is 50 ± 1%, and fluidity is 10 ± 1%, obtained glass felt impregnation tablet;
(5) the glass felt impregnation tablet getting 8 steps (4) obtained is superimposed, thereon, lower two sides respectively superposes the glass cloth impregnation tablet of step (3) gained, finally be covered with a Copper Foil at one side, hot pressing 90min under 15MPa, 170 DEG C of conditions, cooling, obtained CEM-3 copper-clad plate.
Embodiment 3
A preparation method for high CTI, halogen-free type CEM-3 copper-clad plate, step is as follows:
(1) glass cloth resin emulsion is prepared: 65 parts of halogen-free epoxy resins (epoxide equivalent is 400g/eq), 1 part of dicyandiamide, 24 parts of aluminium hydroxides and 10 parts of dimethyl formamides are added reactor successively, 6h is stirred at 30 DEG C, then utilize high-speed emulsifying machine to carry out emulsification 2.0h, finally place slaking 15h at reactor;
(2) glassine paper resin emulsion is prepared: 50 parts of phosphorous epoxy resins (epoxide equivalent is 350g/eq), 12 parts of Nitrogen-containing Phenolic Resins, 13 parts of aluminium hydroxides, 5 parts of talcum powder, 5 parts of tricresyl phosphate (dimethylbenzene) esters and 15 parts of dimethyl formamides are added reactor successively, 6h is stirred at 30 DEG C, then utilize high-speed emulsifying machine to carry out emulsification 2.0h, finally place slaking 15h at reactor;
(3) the glass cloth resin emulsion that step (1) is obtained is coated in E-glass cloth two-sided, under 160 DEG C of conditions, dries 1min, controlling gel content is 50 ± 1%, and fluidity is 10 ± 1%, obtained glass cloth impregnation tablet;
(4) the glassine paper resin emulsion that step (2) is obtained is coated in glassine paper two-sided, under 160 DEG C of conditions, dries 1min, controlling gel content is 50 ± 1%, and fluidity is 10 ± 1%, obtained glassine paper impregnation tablet;
(5) the glassine paper impregnation tablet getting 10 steps (4) obtained is superimposed, thereon, lower two sides respectively superposes the glass cloth impregnation tablet of step (3) gained, finally respectively be covered with a Copper Foil two-sided, hot pressing 100min under 12MPa, 170 DEG C of conditions, cooling, obtained CEM-3 copper-clad plate.
Comparative example 1
A preparation method for CEM-3 copper-clad plate, step is as follows:
(1) glass cloth resin emulsion is prepared: 70 parts of phosphorous epoxy resins (epoxide equivalent is 400g/eq), 2 parts of dicyandiamides, 18 parts of aluminium hydroxides and 10 parts of dimethyl formamides are added reactor successively, 8h is stirred at 20 DEG C, then utilize high-speed emulsifying machine to carry out emulsification 2.5h, finally place slaking 12h at reactor;
(2) glassine paper resin emulsion is prepared: 50 parts of phosphorous epoxy resins (epoxide equivalent is 400g/eq), 0.5 part of dicyandiamide, 25 parts of aluminium hydroxides, 25 parts of talcum powder and 9.5 parts of dimethyl formamides are added reactor successively, 8h is stirred at 20 DEG C, then utilize high-speed emulsifying machine to carry out emulsification 2.5h, finally place slaking 12h at reactor;
(3) the glass cloth resin emulsion that step (1) is obtained is coated in E-glass cloth two-sided, under 160 DEG C of conditions, dries 1min, controlling gel content is 50 ± 1%, and fluidity is 10 ± 1%, obtained glass cloth impregnation tablet;
(4) the glassine paper resin emulsion that step (2) is obtained is coated in glassine paper two-sided, under 160 DEG C of conditions, dries 1min, controlling gel content is 50 ± 1%, and fluidity is 10 ± 1%, obtained glassine paper impregnation tablet;
(5) the glassine paper impregnation tablet getting 5 steps (4) obtained is superimposed, thereon, lower two sides respectively superposes the glass cloth impregnation tablet of step (3) gained, finally respectively be covered with a Copper Foil two-sided, hot pressing 130min under 10MPa, 180 DEG C of conditions, cooling, obtained CEM-3 copper-clad plate.
Table 1 is the properties data of the properties table of comparisons of embodiment 1 and comparative example 1 gained sample and embodiment 2, embodiment 3.
Table 1
| Sequence number | Index name | Unit | Embodiment 1 | Comparative example 1 | Embodiment 2 | Embodiment 3 |
| 1 | Peel strength | N/mm | 1.7 | 1.41 | 1.72 | 1.74 |
| 2 | Resistance to immersed solder/288 DEG C | s | 60 | 48 | 55 | 57 |
| 3 | Anti-flammability | s | Fv 0 | Fv 0 | Fv 0 | Fv 0 |
| 4 | Punching | — | 5—4—5 | 5—4—5 | 5—4—5 | 5—4—5 |
| 5 | CTI | ---- | 0 grade | 2 grades | 0 grade | 0 grade |
| 7 | Chlorine (Cl) | ％ | 0.032 | 0.041 | 0.027 | 0.035 |
| Bromine (Br) | ％ | 0.015 | 0.014 | 0.015 | 0.017 | |
| Chlorine, bromine total content | ％ | 0.047 | 0.055 | 0.042 | 0.052 |
As can be seen from Table 1, the copper-clad plate that the present invention obtains possesses good peel strength, resistance to immersed solder, anti-flammability and punching performance, and CTI value is higher, and content of halogen is extremely low, reduces the pollution to environment.。
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a preparation method for high CTI, halogen-free type CEM-3 copper-clad plate, it is characterized in that, step is as follows:
(1) glass cloth resin emulsion is prepared: 45-65 part halogen-free epoxy resin, 1-2 part dicyandiamide, 24-33 part aluminium hydroxide and 8-25 part dimethyl formamide are added reactor successively; 5-8h is stirred at 20-40 DEG C; then utilize high-speed emulsifying machine to carry out emulsification 1.5-2.5h, finally place slaking 12-16h at reactor;
(2) glassine paper or glass felt resin emulsion is prepared: 35-50 part phosphorous epoxy resin, 10-15 part Nitrogen-containing Phenolic Resins, 13-20 part aluminium hydroxide, 5-15 part talcum powder, 5-10 part phosphate and 10-15 part dimethyl formamide are added reactor successively; 5-8h is stirred at 20-40 DEG C; then utilize high-speed emulsifying machine to carry out emulsification 1.5-2.5h, finally place slaking 12-16h at reactor;
(3) the glass cloth resin emulsion that step (1) is obtained is coated in E-glass cloth two-sided, under 160 DEG C of conditions, dries 1min, controlling gel content is 50 ± 1%, and fluidity is 10 ± 1%, obtained glass cloth impregnation tablet;
(4) by glassine paper obtained for step (2) or glass felt resin emulsion is coated in glassine paper or glass felt is two-sided, under 160 DEG C of conditions, dry 1min, controlling gel content is 50 ± 1%, and fluidity is 10 ± 1%, obtained glassine paper or glass felt impregnation tablet;
(5) the obtained glassine paper of several steps (4) is got or glass felt impregnation tablet is superimposed, thereon, lower two sides respectively superposes the glass cloth impregnation tablet of step (3) gained, finally be covered with a Copper Foil at single or double, hot pressing 90-130min under 10-15MPa, 170-180 DEG C of condition, cooling, obtained CEM-3 copper-clad plate.
2. preparation method according to claim 1, is characterized in that, the epoxide equivalent of the halogen-free epoxy resin described in step (1) is 400-450g/eq.
3. preparation method according to claim 1, is characterized in that, the epoxide equivalent of the phosphorous epoxy resin described in step (2) is 350-450g/eq, and phosphorus content is 2-4%.
4. preparation method according to claim 1, is characterized in that, the nitrogen content of the Nitrogen-containing Phenolic Resins described in step (2) is 15-20%.
5. preparation method according to claim 1, is characterized in that, the phosphate described in step (2) is triphenyl phosphate, tricresyl phosphate, tricresyl phosphate (dimethylbenzene) ester, propyl benzene system phosphate or butylbenzene system phosphate.
6. preparation method according to claim 1, is characterized in that, the talcous particle diameter described in step (2) is 1-3 μm.
7. preparation method according to claim 1, is characterized in that, the particle diameter of described aluminium hydroxide is 1-5 μm.
8. preparation method according to claim 1, is characterized in that, described gel content refers to that the pure solid of impregnation resin emulsion accounts for the percentage of impregnation tablet weight; Described fluidity refers to that impregnation resin emulsion is at 70 ± 5kg/cm
2pressure, the weight that flows out at 160 ± 2 DEG C account for the percentage of impregnation resin emulsion gross weight.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106218136A (en) * | 2016-07-27 | 2016-12-14 | 重庆德凯实业股份有限公司 | The preparation method of environment-friendly type CEM 3 copper-clad plate |
| CN106515132A (en) * | 2016-11-26 | 2017-03-22 | 山东金宝科创股份有限公司 | Method for preparing copper-clad laminate |
| CN106626683A (en) * | 2016-11-26 | 2017-05-10 | 山东金宝科创股份有限公司 | Manufacturing method of halogen-free, phosphorus-free, environment-friendly and flame-retardant paper-based copper clad laminate |
| CN106739376A (en) * | 2016-11-26 | 2017-05-31 | 山东金宝科创股份有限公司 | A kind of high-peeling strength, the preparation method of the copper-clad plates of halogen-free type CEM 1 |
| CN110511538A (en) * | 2019-07-30 | 2019-11-29 | 苏州万润绝缘材料有限公司 | The glue of 0.6mm epoxy resin board |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1861682A (en) * | 2006-04-29 | 2006-11-15 | 广东生益科技股份有限公司 | Halogenless fire retarded epoxy resin composition |
| CN101096442A (en) * | 2007-06-20 | 2008-01-02 | 招远金宝电子有限公司 | Resin combination and method for producing environmental friendly highly-durable dip welding flame-resistant paper-based copper-coated board |
| JP2009215494A (en) * | 2008-03-12 | 2009-09-24 | Shin Etsu Chem Co Ltd | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate plate using the same |
| CN102093670A (en) * | 2010-12-23 | 2011-06-15 | 广东生益科技股份有限公司 | Halogen-free flame retardant epoxy resin composition and copper clad plate prepared from same |
| CN102975430A (en) * | 2012-11-27 | 2013-03-20 | 上海南亚覆铜箔板有限公司 | Flame-retarding copper clad laminate coated with solid content containing phosphorous and no halogen and preparation method thereof |
| CN105086365A (en) * | 2015-08-03 | 2015-11-25 | 广东生益科技股份有限公司 | Epoxy resin composition for copper-clad board and application thereof |
-
2015
- 2015-07-24 CN CN201510444556.4A patent/CN104999740B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1861682A (en) * | 2006-04-29 | 2006-11-15 | 广东生益科技股份有限公司 | Halogenless fire retarded epoxy resin composition |
| CN101096442A (en) * | 2007-06-20 | 2008-01-02 | 招远金宝电子有限公司 | Resin combination and method for producing environmental friendly highly-durable dip welding flame-resistant paper-based copper-coated board |
| JP2009215494A (en) * | 2008-03-12 | 2009-09-24 | Shin Etsu Chem Co Ltd | Flame retardant adhesive composition, and adhesive sheet, coverlay film and flexible copper-clad laminate plate using the same |
| CN102093670A (en) * | 2010-12-23 | 2011-06-15 | 广东生益科技股份有限公司 | Halogen-free flame retardant epoxy resin composition and copper clad plate prepared from same |
| CN102975430A (en) * | 2012-11-27 | 2013-03-20 | 上海南亚覆铜箔板有限公司 | Flame-retarding copper clad laminate coated with solid content containing phosphorous and no halogen and preparation method thereof |
| CN105086365A (en) * | 2015-08-03 | 2015-11-25 | 广东生益科技股份有限公司 | Epoxy resin composition for copper-clad board and application thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106218136A (en) * | 2016-07-27 | 2016-12-14 | 重庆德凯实业股份有限公司 | The preparation method of environment-friendly type CEM 3 copper-clad plate |
| CN106515132A (en) * | 2016-11-26 | 2017-03-22 | 山东金宝科创股份有限公司 | Method for preparing copper-clad laminate |
| CN106626683A (en) * | 2016-11-26 | 2017-05-10 | 山东金宝科创股份有限公司 | Manufacturing method of halogen-free, phosphorus-free, environment-friendly and flame-retardant paper-based copper clad laminate |
| CN106739376A (en) * | 2016-11-26 | 2017-05-31 | 山东金宝科创股份有限公司 | A kind of high-peeling strength, the preparation method of the copper-clad plates of halogen-free type CEM 1 |
| CN106739376B (en) * | 2016-11-26 | 2018-11-02 | 山东金宝科创股份有限公司 | A kind of high-peeling strength, halogen-free type CEM-1 copper-clad plates preparation method |
| CN110511538A (en) * | 2019-07-30 | 2019-11-29 | 苏州万润绝缘材料有限公司 | The glue of 0.6mm epoxy resin board |
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