CN101921457B - Material and production process for producing copper-clad plate - Google Patents
Material and production process for producing copper-clad plate Download PDFInfo
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- CN101921457B CN101921457B CN 201010216425 CN201010216425A CN101921457B CN 101921457 B CN101921457 B CN 101921457B CN 201010216425 CN201010216425 CN 201010216425 CN 201010216425 A CN201010216425 A CN 201010216425A CN 101921457 B CN101921457 B CN 101921457B
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Abstract
The invention discloses a material for producing a copper-clad plate, which comprises a glass cloth, an epoxy resin and a copper foil, wherein the epoxy resin is a phosphorus/nitrogen epoxy resin, an inorganic flame retardant is added in the epoxy resin, and the inorganic flame retardant contains aluminum hydroxide powder and silicon powder; and the glass cloth is formed by weaving untwisted opened glass fibers. By using the superfine aluminum hydroxide powder and the super soft silicon powder as flame retardant materials in the epoxy resin in the copper-clad plate material to replace brominated resin and other halogens used as the flame retardant materials in the prior art, the invention solves the problem that dioxin substances harmful to humans and environment are produced in the burning process of bromides because the flame retardant system of a common copper-clad plate is a bromine-containing resin system.
Description
Technical field
The present invention relates to a kind of copper-clad plate, be specifically related to a kind of material and production technique that is used for the production copper-clad plate.
Background technology
Copper-clad plate is mainly used in the making printed circuit board, is used for production such as various military electronics, signal equipment, computer, automotive electronics, household electrical appliance.Along with the development of global electronic information industry, the demand of copper-clad plate is increased fast, got into the high-speed developing period.Meanwhile, domestic electronics and information industry simultaneous growth, copper-clad plate market growth speed surpasses the average speedup in the world, presents vigorous growth for many years.
Along with the development of copper-clad plate technology and the raising of people's living standard, to electronic product require increasingly high.WEEE (Waste ofElectricand Electronic Equipment) and RoHS (Restriction of Hazardous Substances) two that European Union implemented from July 1st, 2006 instruct greatly, and environmentally friendly electronic substrate receives publicity day by day.Because the flame-retardant system of coventional type copper-clad plate is brominated resin system; The bromide burning produces human and the deleterious dioxin material of environment; Seek the ideal flame-retardant system and replace the halogen thing; The copper-clad plate of the friendly type Halogen of production and manufacturing environment is to promote the electronic industry development, the prerequisite of protection environment for human survival.
The Halogen copper-clad plate also need have excellent dielectric properties under the prerequisite of the fundamental property that must keep common copper-clad plate, excellent anti-ion transport and high CTI property are used more extensively, and finally are applied to the digitizing liquid-crystal display.
Environmentally friendly high density interconnect is the major reason of this type of copper-clad plate of development with the heavy demand of copper-clad plate.And ultra-thin copper-clad plate is used to make microwell plate HDI.The HDI printed circuit board comes across early 1990s, and its appearance is the milestone in the printed circuit board technology development course, on the HDI multi-ply wood, up-to-date PCB technology is embodied most vividly.Its prominent feature is: micropore, fine rule, thin layerization, environmental protection.Be that modern electronic product such as mobile phone and flat-panel monitor are to inevitable requirement thin, light, little development.
Modern electronics improves constantly the requirement of miniaturized, lightweight, high performance, multifunction, low power consumption and cost degradation and is urgent day by day.Portable electron devices such as mobile phone are the exemplary that embodies these requirements.The demand of modern electronics promotes the microelectronics integrated technology and develops rapidly, and System on Chip/SoC (SoC), system in package (SIP), mcm (MCM), high density interconnect new technologies and methods such as (HDI) continue to bring out.High-density interconnect technology can also be made high-quality integrated passive components, comprises resistor, electrical condenser, inducer and various transmission line.Not only size is little for multi-layered high density interconnected structure, interconnection density is high, and has excellent high frequency performance.
Though preparation technology's comparative maturity of copper-clad plate generally uses the brominated epoxy resin system to be fire retardant in the prior art, and the bromide high-temp combustion decomposes the easy dioxin toxic substance that produces.Therefore, those skilled in the art press for develop a kind of environmentally friendly, copper-clad plate that high density interconnect is used and corresponding production technique.
Summary of the invention
The objective of the invention is to overcome defective of the prior art, a kind of material that is used for the production copper-clad plate is provided, employed material can thoroughly be eliminated after heating human and the deleterious dioxin material of environment in this copper-clad plate.Second purpose of the present invention is to design a kind of production technique of producing above-mentioned copper-clad plate material, and this production technique reaches simply again product instruction and is significantly improved.
For realizing above-mentioned purpose; The technical scheme that the present invention adopts is a kind of material that is used for the production copper-clad plate; Said material comprises glasscloth, epoxy resin and Copper Foil, it is characterized in that, said epoxy resin is that phosphorus/nitrogen is epoxy resin; In above-mentioned epoxy resin, be added with inorganic combustion inhibitor, in said inorganic combustion inhibitor, include aluminium-hydroxide powder and silicon powder; Described glasscloth is opened fiber/glass fiber braiding and is formed by non-twist.
In order to guarantee the quality of copper-clad plate, and make it have snappiness preferably, preferable technical scheme is that said aluminium-hydroxide powder and silicon particles of powder degree are controlled at 2800 orders～3500 orders.
Since white lake have Heat stability is good, nontoxic, do not produce advantages such as corrosive gases, the amount of being fuming are few; And aboundresources, low price; Preferable technical scheme also has; The weight percent content of inorganic combustion inhibitor is 20%～30% in said epoxy resin, and the weight percent content of aluminium-hydroxide powder is 75%～80% in said inorganic combustion inhibitor.
In order to adapt to the needs of modern electronic product to copper-clad plate each item performance, preferable technical scheme also has, and is 65%～70% at the weight percent content of epoxy resin described in the said copper-clad plate.The thickness of said copper-clad plate is smaller or equal to 0.05mm.
A kind of production technique of copper-clad plate is characterized in that, said technology comprises following process step:
The first step, glue; Solidifying agent is being dissolved more than 45 ℃ with epoxy resin; Add then additive through abundant dissolving with fully mix after, let glue slaking some hrs, let each component have enough and be in contact with one another, interpenetrate; Make colloid reach a stability through for some time, described additive is aluminium-hydroxide powder and silicon powder;
Second step, impregnation oven dry adopt the back of the body to be coated with the mode of soaking entirely that adds, at twice with glasscloth with unidirectional mobile gumming device impregnation, dry then to prepreg;
The 3rd step, superimposed and lamination, adopts dustless be equipped with to put from fold with the vacuum hotpressing device said plate cured sheets is fitted over from fold with Copper Foil, in said vacuum hotpressing device, be provided with heat-conducting oil heating parts and wet cleaner;
The 4th step, adopt automatic trimming machine, thickness measurement online machine, automatic packing machine that the work in-process of seeing off in the 3rd one are carried out trimming, check, packing.
Optimized technical scheme is that described epoxy resin is bisphenol A type epoxy resin.
Optimized technical scheme also comprises, before said impregnation step, needs once more glue fully to be stirred.
The generation of bubble in the glue when reducing impregnation; Optimized technical scheme comprises that also described unidirectional mobile gumming device includes steeping vat, is respectively equipped with glue-feeder and overflow groove at the edge of said steeping vat; Described glue-feeder is a little more than said overflow groove; In said steeping vat, be provided with live roll, on said steeping vat, be provided with driving roll, said driving roll is a pair roller; Said glasscloth gets into steeping vat by said steeping vat epimere, passes said live roll and passes said driving roll again.
Optimized technical scheme also comprises, said prepreg is the copper-clad plate substrate through said a pair roller, with the clearance control between the said roll in said copper-clad plate substrate thickness ± 2 mu m ranges.
Optimized technical scheme also comprises, described bake out temperature is controlled at 160 ± 0.05 ℃, or is controlled at 180 ± 0.05 ℃.
Advantage of the present invention and beneficial effect are: because in the epoxide resin material in this copper-clad plate material; With ultra fine aluminium hydroxide end and ultra-soft silicon powder for as the fire retardant raw material; Replaced in the prior art using halogen such as brominated resins as the fire retardant raw material; Thereby solved because the flame-retardant system of coventional type copper-clad plate is brominated resin system, the bromide burning produces human and the deleterious dioxin material of environment problem.On the other hand because in the production technique of copper-clad plate; Selected the gumming device that has overflow groove for use; Thereby eliminated the bubble in the glue basically; Guaranteed that glasscloth soaks with resin uniformly, the uniformity of bubble and resin flows does not appear in prepreg, is effectively to reach the guarantee that quality product requires.
Description of drawings
Fig. 1 is the technological process of production figure of copper-clad plate of the present invention;
Fig. 2 is a unidirectional mobile gumming device structural representation among Fig. 1.
Among the figure: 1, steeping vat; 2, glue-feeder; 3, overflow groove; 4, live roll; 5, driving roll; 6, glasscloth.
Embodiment
Below in conjunction with accompanying drawing and embodiment, specific embodiments of the invention further describes.Following examples only are used for technical scheme of the present invention more clearly is described, and can not limit protection scope of the present invention with this.
The present invention is a kind of material that is used for the production copper-clad plate; This material comprises glasscloth, epoxy resin and Copper Foil; This epoxy resin is that phosphorus/nitrogen is epoxy resin, in above-mentioned epoxy resin, is added with inorganic combustion inhibitor, in inorganic combustion inhibitor, includes aluminium-hydroxide powder and silicon powder; Wherein, glasscloth is opened fiber/glass fiber braiding and is formed by non-twist.
On the basis of embodiment 1; In order to guarantee the quality of copper-clad plate; And making it have snappiness preferably, preferred embodiment of the present invention is that aluminium-hydroxide powder and silicon particles of powder degree are controlled at 3000 orders; Promptly select the silicon powder of a kind of superfine aluminium-hydroxide powder and ultra-soft for use, the technical scheme of all the other and embodiment 1 is identical.
On the basis of embodiment 2; Since white lake have Heat stability is good, nontoxic, do not produce advantages such as corrosive gases, the amount of being fuming are few; And aboundresources, low price, preferred embodiment of the present invention also has, and the weight percent content of inorganic combustion inhibitor is 25% in epoxy resin; The weight percent content of aluminium-hydroxide powder is 75% in inorganic combustion inhibitor, and the technical scheme of all the other and embodiment 2 is identical.
Embodiment 4
On the basis of embodiment 3, in order to adapt to the needs of modern electronic product to copper-clad plate each item performance, preferred embodiment of the present invention also has, and the weight percent content of epoxy resin is 65% in copper-clad plate.The thickness of copper-clad plate is smaller or equal to 0.05mm, and the technical scheme of all the other and embodiment 3 is identical.
As shown in Figure 1, a kind of production technique of copper-clad plate, this technology comprises following process step:
The first step, glue; Solidifying agent is being dissolved more than 45 ℃ with epoxy resin; Add then additive through abundant dissolving with fully mix after, let glue slaking some hrs, let each component have enough and be in contact with one another, interpenetrate; Make colloid reach a stability through for some time, described additive is aluminium-hydroxide powder and silicon powder;
Second step, impregnation oven dry adopt the back of the body to be coated with the mode of soaking entirely that adds, at twice with glasscloth with unidirectional mobile gumming device impregnation, dry then to prepreg;
The 3rd step, superimposed and lamination, adopts dustless be equipped with to put from fold with the vacuum hotpressing device said plate cured sheets is fitted over from fold with Copper Foil, in said vacuum hotpressing device, be provided with heat-conducting oil heating parts and wet cleaner;
The 4th step, adopt automatic trimming machine, thickness measurement online machine, automatic packing machine that the work in-process of seeing off in the 3rd one are carried out trimming, check, packing.
On the basis of embodiment 5, the preferred embodiment of the invention is that epoxy resin can be selected bisphenol A type epoxy resin for use.And before said impregnation step, need fully to stir glue once more, the technical scheme of all the other and embodiment 5 is identical.
Embodiment 7
On the basis of embodiment 6, as shown in Figure 2, the generation of bubble in the glue when reducing impregnation; The preferred embodiment of the invention comprises that also unidirectional mobile gumming device includes steeping vat 1, is respectively equipped with glue-feeder 2 and overflow groove 3 at the edge of steeping vat 1; Glue-feeder 2 is a little more than overflow groove 3; In steeping vat 1, be provided with live roll 4, on steeping vat 1, be provided with driving roll 5, said driving roll is a pair roller; Glasscloth 6 gets into steeping vat 1 by steeping vat 1 upper end, passes live roll 4 and passes driving roll 5 again, thereby accomplish the gluing process, and the technical scheme of all the other and embodiment 6 is identical.
Embodiment 8
On the basis of embodiment 7; Preferred embodiment of the invention case also comprises; Prepreg is the copper-clad plate substrate through a pair roller, and in copper-clad plate substrate thickness ± 2 mu m ranges, the technical scheme of all the other and embodiment 7 is identical with the clearance control between the roll.
Embodiment 9
On the basis of embodiment 5, optimized technical scheme of the present invention also comprises, with bake out temperature be controlled at 160 ± 0.05 ℃, or be controlled at 180 ± 0.05 ℃, the technical scheme of all the other and embodiment 5 is identical.
The prescription of epoxy resin and blending process are in the present invention:
In actual production, adopt aluminum oxide and ultra-soft silicon as inorganic fire-retarded additive, this technical scheme has successfully solved many Technology problems, compliance with environmental protection requirements.Aluminum oxide have Heat stability is good, nontoxic, do not produce advantages such as corrosive gases, the amount of being fuming are few, and aboundresources, low price are so good name is " a totally fire retardant ".Producing the resin blending process that uses is a physical mixing processes, and epoxy resin and solidifying agent, additive, solvent are got final product after passing through the physical mixed slaking, is easy to control.This technology with bisphenol A type epoxy resin more than 45 ℃ solidifying agent dissolving back added additive through abundant dissolving with fully mix after; Let glue slaking some hrs; Let each component have enough and be in contact with one another, interpenetrate and the reaction times, make system reach a stability.Have reaction along with solidifying agent and promotor add epoxy-resin systems, molecular weight changes, and along with the prolongation of shelf-time, the resin gel time (GT) of glue can shorten gradually, and glue has certain restriction storage period.It should be noted that when the glue storage period for preparing is long, particularly use epoxy resin adhesive liquid, can produce a concentration gradient from top to bottom, should start stirring before using, come into operation again after making it return to certain state for the environmental protection copper-clad plate.
The prepreg ME is in the present invention:
Glass cloth gum dipping process adopts the unidirectional mobile gum dipping process technology of company's independent development exploitation; In glass fiber fabric base plate production process; (" B rank " are meant that the existing considerable part of polymer is crosslinked to strongthener through cement dipping machine gluing and oven dry to " B rank "; But this moment material still part be in solvable, fusible state) work in-process be called prepreg (Prepreg), be commonly called as bonding sheet, or the PP sheet.The prepreg technical indicator mainly comprises resin content (RC%), resin gel time (GT), resin flow (RF%), volatile content (VC%) etc.Can the roll seam precision be controlled at the high-precision measuring roller of the thickness ± 2 μ m of prepreg in the present invention; Control resin content with this; Control the consistence of resin gel time through the permanent sticking glue system of constant temperature; Through temperature control precision is the consistence that the drying system of 160 ± 0.5 ℃ or 180 ± 0.5 ℃ guarantees resin flow, stores through online detection and air-conditioning to guarantee than low volatile content.Glass cloth is taked to carry on the back to be coated with and is added the secondary dipping technology of soaking entirely and make prepreg, to improve the impregnability of resin.Guaranteed the workmanship of prepreg through above technology and technology.
Pressing process is in the present invention:
Continuous roll extrusion technology is adopted in the pressing of this project.The hot pressing recombination process can reduce forming pressure, prevents the resin flow prepreg displacement of becoming estranged, and reduces distortion, improves thickness uniformity coefficient and product percent of pass, is one of visual plant technology of producing ultra-thin glass fiber fabric base plate.And adopt and dustlessly join technology, vacuum hot pressing technique, heat-conducting oil heating technology and wet-cleaned technology from fold.Adopt dustlessly can fit over prepreg and Copper Foil together from fold according to the requirement of glass fiber fabric base plate gauge lattice, improve product surface quality and level of automation from the fold technology of joining.Adopt vacuum hot pressing technique, help the discharge of volatile matter in the pressing process, improved the planeness of glass fiber fabric base plate.
Adopt heat-conducting oil heating technology, compare with steam heating and improved the stability of temperature in the pressing process, reduced the surface temperature error of hot plate.Adopt online wet-cleaned technology, improved the degree of cleaning of template, thereby improved the surface quality of glass fiber fabric base plate.
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from know-why of the present invention; Can also make some improvement and retouching, these improvement and retouching also should be regarded as protection scope of the present invention.
Claims (5)
1. the production technique of a copper-clad plate is characterized in that, said technology comprises following process step:
The first step, glue; Solidifying agent is being dissolved more than 45 ℃ with epoxy resin; Add then additive through abundant dissolving with fully mix after, let glue slaking some hrs, let each component have enough and be in contact with one another, interpenetrate; Make colloid reach a stability through for some time, described additive is aluminium-hydroxide powder and silicon powder;
Second step, impregnation oven dry adopt the back of the body to be coated with the mode of soaking entirely that adds, at twice with glasscloth with unidirectional mobile gumming device impregnation, dry then to prepreg; Described unidirectional mobile gumming device includes steeping vat; Be respectively equipped with glue-feeder and overflow groove at the edge of said steeping vat, described glue-feeder is provided with live roll a little more than said overflow groove in said steeping vat; On said steeping vat, be provided with driving roll, said driving roll is a pair roller; Said glasscloth gets into steeping vat by said steeping vat epimere, passes said live roll and passes said driving roll again;
The 3rd step, superimposed and lamination, adopts dustless be equipped with to put from fold with the vacuum hotpressing device said prepreg and Copper Foil are fitted over from fold, in said vacuum hotpressing device, be provided with heat-conducting oil heating parts and wet cleaner;
The 4th step, the automatic trimming machine of employing, thickness measurement online machine, automatic packing machine carry out trimming with the work in-process of seeing off in the 3rd step, check, packing.
2. according to the production technique of the said copper-clad plate of claim 1, it is characterized in that described epoxy resin is bisphenol A type epoxy resin.
3. according to the production technique of the said copper-clad plate of claim 2, it is characterized in that, before said impregnation step, need once more glue fully to be stirred.
4. the production technique of copper-clad plate according to claim 3 is characterized in that, said prepreg is the copper-clad plate substrate through said a pair roller, with the clearance control between the said roll in said copper-clad plate substrate thickness ± 2 mu m ranges.
5. the production technique of copper-clad plate according to claim 1 is characterized in that, described bake out temperature is controlled at 160 ± 0.05 ℃, or is controlled at 180 ± 0.05 ℃.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104999682A (en) * | 2015-08-10 | 2015-10-28 | 苏州市博奥塑胶电子有限公司 | Preparing method for glass-fiber reinforced polypropylene series resin flake |
| CN105235318B (en) * | 2015-09-22 | 2018-07-06 | 金安国纪科技（珠海）有限公司 | A kind of preparation method of big dielectric constant copper-clad plate |
| CN105965710B (en) * | 2016-06-28 | 2019-03-22 | 常州大学 | A kind of preparation method and application of silicon rod gold steel wire cutting resin plate |
| CN106675482A (en) * | 2016-12-31 | 2017-05-17 | 铜陵华科电子材料有限公司 | Formula for additive materials for polytetrafluoroethylene high-frequency microwave copper-clad plates |
| CN106634753A (en) * | 2016-12-31 | 2017-05-10 | 铜陵华科电子材料有限公司 | Additive material formula for CAF (conductive anodic filament)-resistant copper-clad plate with high CTI (comparative tracking index) value |
| CN106832776A (en) * | 2017-02-09 | 2017-06-13 | 合肥英索莱特新材料科技有限公司 | Flame-retardant environment-friendly epoxy electronic encapsulating material |
| CN108943198A (en) * | 2018-08-20 | 2018-12-07 | 湖州韵高木业有限公司 | A kind of wood veneer production technology |
| CN109233209B (en) * | 2018-09-30 | 2021-03-30 | 陕西生益科技有限公司 | Halogen-containing antimony-free resin composition, prepreg using same, laminated board and printed circuit board |
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| JPH05318653A (en) * | 1992-05-23 | 1993-12-03 | Toshiba Chem Corp | Manufacture of flame-retardant copper-clad laminate |
| CN101415296B (en) * | 2008-11-24 | 2010-06-09 | 广东汕头超声电子股份有限公司覆铜板厂 | Structure for covering copper plate |
| CN101457012B (en) * | 2008-12-31 | 2011-06-15 | 广东生益科技股份有限公司 | Resin composition and copper clad laminate prepared by metal foil coated with resin composition |
| CN101578010B (en) * | 2009-06-10 | 2011-02-16 | 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 |
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