CN105058927A - High heat-resistance composite base copper clad laminate preparation method - Google Patents
High heat-resistance composite base copper clad laminate preparation method Download PDFInfo
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- CN105058927A CN105058927A CN201510445636.1A CN201510445636A CN105058927A CN 105058927 A CN105058927 A CN 105058927A CN 201510445636 A CN201510445636 A CN 201510445636A CN 105058927 A CN105058927 A CN 105058927A
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/18—Layered products comprising a layer of metal comprising iron or steel
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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
-
- 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
- B32B17/061—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 metal
-
- 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
- B32B17/10005—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 laminated safety glass or glazing
- B32B17/10009—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 laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10018—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 laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
- B32B17/10027—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 laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet the glass sheet not being an outer layer
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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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- 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
- B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
-
- 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
-
- 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
-
- 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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- Laminated Bodies (AREA)
Abstract
The present invention belongs to the technical field of copper clad laminate production, and relates to a high heat-resistance composite base copper clad laminate preparation method. According to the present invention, a variety of epoxy resins and a variety of curing agents with different types are matched to prepare the resin emulsion, the novel resin system is used to prepare the composite base copper clad laminate, the heat resistance of the prepared composite base copper clad laminate is increased to more than or equal to 3 min/288 DEG C and is substantially improved, the high-temperature lead-free reflux welding is met when the composite base copper clad laminate is used to produce the circuit board, and the composite base copper clad laminate can further be used for producing the high-temperature environment circuit board.
Description
Technical field
The present invention relates to a kind of copper-clad plate, particularly relate to a kind of preparation method of high heat-resisting composite-based copper clad plate, belong to copper-clad plate production technical field.
Background technology
Copper-clad plate is the important materials of printed circuit board industry.Along with the development of electronic industry, data operation Capability Requirement is more and more higher, cause circuit board integrated level more and more higher, lead leg density on chip is increasing, this just requires that, on the circuit board of identical size, wiring density will double above, and solution normally adopts the method for aperture, fine rule Small Distance, multilayer, this just has higher requirement to copper-clad plate, especially proposes challenge to the heat resistance of copper-clad plate.Along with the enforcement of the unleaded instruction of European Union, circuit-board industry develops lead-free solder, and its eutectic point comparatively conventional solder exceeds more than 30 DEG C, peak demand 240-260 DEG C, and in this respect, copper-clad plate industry and the research of resin to heat resistance become focus.After raising copper-clad plate heat resistance, can be used for making the circuit board such as LED lamp and hot environment electrical instrumentation.Current high heat-resistant copper-clad panel mainly concentrates on the copper-clad plate of glass fabricbase, and its cost is high, machining property is poor (can only hole can not punching).
Composite-based copper clad plate in mechanical performance and manufacturing cost between epoxy glass fiber fabric base and paper-based copper-coated board.It can punching processing, is also suitable for machine drilling.Improve composite-based copper clad plate heat resistance and substitute the copper-clad plate of high-heat-resisting glass glass fabricbase, obtain in the world at present adopting very widely.
At present, the making of composite-based copper clad plate mainly utilizes low brominated epoxy/dicyandiamide cure system, and heat resistance is not high, be only 30-50 second/288 DEG C of glass fabricbase heat resistances are at 3-5 minute/288 DEG C.
Summary of the invention
The present invention is directed to the deficiency that above-mentioned prior art exists, a kind of preparation method of high heat-resisting composite-based copper clad plate is provided.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of preparation method of high heat-resisting composite-based copper clad plate, and step is as follows:
(1) resin emulsion is prepared: 45-65 part low brominated epoxy, 20-25 part novolac epoxy resin, 8-20 part phenolic resins and 5-15 part acid anhydrides are added reactor successively, 5-8h is stirred under 20-40 DEG C of condition, then utilize high-speed emulsifying machine to carry out emulsification 1.5-2.5h, finally place slaking 12-16h at reactor;
(2) resin emulsion that step (1) is obtained is coated in E-glass paper or glass felt and glass cloth two-sided, 1min is dried under 160 DEG C of conditions, controlling gel content is 50 ± 1%, fluidity is 10 ± 1%, obtained glass cloth impregnation tablet, glassine paper or glass felt impregnation tablet;
(3) the obtained glassine paper of several steps (2) is got or glass felt impregnation tablet is superimposed, thereon, lower two sides respectively superposes the glass cloth impregnation tablet of step (2) 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 composite-based copper clad plate.
The invention has the beneficial effects as follows: the present invention is mutually arranged in pairs or groups by the curing agent of multiple epoxy resin and number of different types and makes resin emulsion, a kind of new type resin system is used to make composite-based copper clad plate, obtained its heat resistance of copper-clad plate is increased to 3 minutes/more than 288 DEG C, heat resistance improves greatly, meet copper-clad plate high-temp leadless reflow soldering when making circuit board, and hot environment circuit board can be made.
On the basis of technique scheme, the present invention can also do following improvement.
Further, described in step (1), the epoxide equivalent of low brominated epoxy is 450-500g/eq, and brominated amount is 19-23%; Described novolac epoxy resin is one or more mixing in difunctionality, trifunctional, four senses, multifunctional novolac epoxy resin or special type phenolic epoxy resin; Described phenolic resins is one or both mixing in high adjacent position phenolic resin or orthoresol type phenolic resins; Described acid anhydrides is tung oil acid anhydride, glutaric anhydride, poly-azelaic acid acid anhydride, poly-icosane dicarboxylic anhydride or span come in dicarboxylic anhydride one or both mixing or three kinds of mixing.
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 heat-resisting composite-based copper clad plate, step is as follows:
(1) resin emulsion is prepared: 45 parts of low brominated epoxy (epoxide equivalent is 450g/eq), 20 part of four sense novolac epoxy resin, 20 parts of high adjacent position phenolic resins and 15 parts of poly-azelaic acid acid anhydrides are added reactor successively, 8h is stirred under 20 DEG C of conditions, then utilize high-speed emulsifying machine to carry out emulsification 2.5h, finally place slaking 12h at reactor;
(2) resin emulsion obtained for step (1) is coated in E-glass paper and glass cloth two-sided, 1min is dried under 160 DEG C of conditions, controlling gel content is 50 ± 1%, and fluidity is 10 ± 1%, obtained glass cloth impregnation tablet, glassine paper impregnation tablet;
(3) the glassine paper impregnation tablet getting 5 steps (2) obtained is superimposed, thereon, lower two sides respectively superposes the glass cloth impregnation tablet of step (2) gained, finally respectively be covered with a Copper Foil two-sided, hot pressing 130min under 10MPa, 180 DEG C of conditions, cooling, obtained composite-based copper clad plate.
Embodiment 2
A preparation method for high heat-resisting composite-based copper clad plate, step is as follows:
(1) resin emulsion is prepared: 55 parts of low brominated epoxy (epoxide equivalent is 500g/eq), 25 part of two sense novolac epoxy resin, 10 parts of orthoresol type novolac epoxy resins and 10 parts of glutaric anhydrides are added reactor successively, 5h is stirred under 40 DEG C of conditions, then utilize high-speed emulsifying machine to carry out emulsification 1.5h, finally place slaking 16h at reactor;
(2) resin emulsion obtained for step (1) is coated in E-glass felt and glass cloth two-sided, 1min is dried under 160 DEG C of conditions, controlling gel content is 50 ± 1%, and fluidity is 10 ± 1%, obtained glass cloth impregnation tablet, glass felt impregnation tablet;
(3) the glass felt impregnation tablet getting 5 steps (2) obtained is superimposed, thereon, lower two sides respectively superposes the glass cloth impregnation tablet of step (2) gained, finally respectively be covered with a Copper Foil two-sided, hot pressing 90min under 15MPa, 170 DEG C of conditions, cooling, obtained composite-based copper clad plate.
Embodiment 3
A preparation method for high heat-resisting composite-based copper clad plate, step is as follows:
(1) resin emulsion is prepared: 65 parts of low brominated epoxy (epoxide equivalent is 450g/eq), 22 parts of tri-functional phenols formaldehyde epoxy resins, 8 parts of high adjacent position phenolic resins and 5 parts of poly-icosane dicarboxylic anhydrides are added reactor successively, 6h is stirred under 30 DEG C of conditions, then utilize high-speed emulsifying machine to carry out emulsification 2.0h, finally place slaking 15h at reactor;
(2) resin emulsion obtained for step (1) is coated in E-glass paper and glass cloth two-sided, 1min is dried under 160 DEG C of conditions, controlling gel content is 50 ± 1%, and fluidity is 10 ± 1%, obtained glass cloth impregnation tablet, glassine paper impregnation tablet;
(3) the glassine paper impregnation tablet getting 5 steps (2) obtained is superimposed, thereon, lower two sides respectively superposes the glass cloth impregnation tablet of step (2) gained, finally be covered with a Copper Foil at one side, hot pressing 130min under 10MPa, 180 DEG C of conditions, cooling, obtained composite-based copper clad plate.
Comparative example 1
A preparation method for composite-based copper clad plate, step is as follows:
(1) resin emulsion is prepared: 97 parts of low brominated epoxy (epoxide equivalent is 450g/eq) and 3 parts of dicyandiamides are added reactor successively, 8h is stirred under 20 DEG C of conditions, then utilize high-speed emulsifying machine to carry out emulsification 2.5h, finally place slaking 12h at reactor;
(2) resin emulsion obtained for step (1) is coated in E-glass paper and glass cloth two-sided, 1min is dried under 160 DEG C of conditions, controlling gel content is 50 ± 1%, and fluidity is 10 ± 1%, obtained glass cloth impregnation tablet, glassine paper impregnation tablet;
(3) the glassine paper impregnation tablet getting 5 steps (2) obtained is superimposed, thereon, lower two sides respectively superposes the glass cloth impregnation tablet of step (2) gained, finally respectively be covered with a Copper Foil two-sided, hot pressing 130min under 10MPa, 180 DEG C of conditions, cooling, obtained composite-based copper clad plate.
Comparative example 2
A preparation method for high heat-resisting composite-based copper clad plate, step is as follows:
(1) resin emulsion is prepared: 80 parts of low brominated epoxy (epoxide equivalent is 450g/eq) and 20 parts of linear phenol-aldehyde resins are added reactor successively, 8h is stirred under 20 DEG C of conditions, then utilize high-speed emulsifying machine to carry out emulsification 2.5h, finally place slaking 12h at reactor;
(2) resin emulsion obtained for step (1) is coated in E-glass paper and glass cloth two-sided, 1min is dried under 160 DEG C of conditions, controlling gel content is 50 ± 1%, and fluidity is 10 ± 1%, obtained glass cloth impregnation tablet, glassine paper impregnation tablet;
(3) the glassine paper impregnation tablet getting 5 steps (2) obtained is superimposed, thereon, lower two sides respectively superposes the glass cloth impregnation tablet of step (2) gained, finally respectively be covered with a Copper Foil two-sided, hot pressing 130min under 10MPa, 180 DEG C of conditions, cooling, obtained composite-based copper clad plate.
Table 1 is the properties table of comparisons of embodiment 1-3 and comparative example 1-2 gained sample.
Table 1
As can be seen from Table 1, compare with comparative example 2 with comparative example 1, the composite-based copper clad plate that the present invention obtains possesses good peel strength, anti-flammability and punching performance, and especially resistance to immersed solder performance improves greatly, is applicable to manufacture hot environment circuit board.
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 (3)
1. a preparation method for high heat-resisting composite-based copper clad plate, it is characterized in that, step is as follows:
(1) resin emulsion is prepared: 45-65 part low brominated epoxy, 20-25 part novolac epoxy resin, 8-20 part phenolic resins and 5-15 part acid anhydrides are added reactor successively, 5-8h is stirred under 20-40 DEG C of condition, then utilize high-speed emulsifying machine to carry out emulsification 1.5-2.5h, finally place slaking 12-16h at reactor;
(2) resin emulsion that step (1) is obtained is coated in E-glass paper or glass felt and glass cloth two-sided, 1min is dried under 160 DEG C of conditions, controlling gel content is 50 ± 1%, fluidity is 10 ± 1%, obtained glass cloth impregnation tablet, glassine paper or glass felt impregnation tablet;
(3) the obtained glassine paper of several steps (2) is got or glass felt impregnation tablet is superimposed, thereon, lower two sides respectively superposes the glass cloth impregnation tablet of step (2) 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 composite-based copper clad plate.
2. preparation method according to claim 1, is characterized in that, described in step (1), the epoxide equivalent of low brominated epoxy is 450-500g/eq, and brominated amount is 19-23%; Described novolac epoxy resin is one or more mixing in difunctionality, trifunctional, four senses, multifunctional novolac epoxy resin or special type phenolic epoxy resin; Described phenolic resins is one or both mixing in high adjacent position phenolic resin or orthoresol type phenolic resins; Described acid anhydrides is tung oil acid anhydride, glutaric anhydride, poly-azelaic acid acid anhydride, poly-icosane dicarboxylic anhydride or span come in dicarboxylic anhydride one or both mixing or three kinds of mixing.
3. 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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| CN201510445636.1A CN105058927B (en) | 2015-07-24 | 2015-07-24 | High heat-resistance composite base copper clad laminate preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106739390A (en) * | 2016-11-26 | 2017-05-31 | 山东金宝科创股份有限公司 | A kind of preparation method of heat-resisting CEM 1 high copper-clad plates |
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| CN103057213A (en) * | 2012-12-31 | 2013-04-24 | 金安国纪科技股份有限公司 | Environment-friendly copper clad laminate for LED monochrome display, glue solution and preparation method |
| CN103802394A (en) * | 2013-12-02 | 2014-05-21 | 上海南亚覆铜箔板有限公司 | Copper-clad plate suitable for lead-free process and preparation method of copper-clad laminate |
| CN104002538A (en) * | 2014-04-18 | 2014-08-27 | 南通诺德电子有限公司 | Making method for super-thick copper foil and high heat-conducting copper clad laminate |
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2015
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| CN101578010A (en) * | 2009-06-10 | 2009-11-11 | 陕西生益科技有限公司 | Method for preparing high phase ratio electric leakage resistant tracking index leadless compatible CEM-3 copper-clad laminate |
| CN103057213A (en) * | 2012-12-31 | 2013-04-24 | 金安国纪科技股份有限公司 | Environment-friendly copper clad laminate for LED monochrome display, glue solution and preparation method |
| CN103802394A (en) * | 2013-12-02 | 2014-05-21 | 上海南亚覆铜箔板有限公司 | Copper-clad plate suitable for lead-free process and preparation method of copper-clad laminate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106739390A (en) * | 2016-11-26 | 2017-05-31 | 山东金宝科创股份有限公司 | A kind of preparation method of heat-resisting CEM 1 high copper-clad plates |
| CN106739390B (en) * | 2016-11-26 | 2018-10-19 | 山东金宝科创股份有限公司 | A kind of preparation method of high heat-resisting CEM-1 copper-clad plates |
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Address after: 265400 No.268, Guoda Road, Zhaoyuan City, Yantai City, Shandong Province Patentee after: Shandong Jinbao Electronics Co.,Ltd. Address before: No. 128, Wenquan Road, Zhaoyuan, Yantai, Shandong 265200 Patentee before: SHANDONG JINBAO ELECTRONICS Co.,Ltd. |
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