CN100569505C - A kind of non-halogen epoxide glass cloth base copper coated foil plate and preparation method thereof - Google Patents
A kind of non-halogen epoxide glass cloth base copper coated foil plate and preparation method thereof Download PDFInfo
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- CN100569505C CN100569505C CNB2006100256865A CN200610025686A CN100569505C CN 100569505 C CN100569505 C CN 100569505C CN B2006100256865 A CNB2006100256865 A CN B2006100256865A CN 200610025686 A CN200610025686 A CN 200610025686A CN 100569505 C CN100569505 C CN 100569505C
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Abstract
The invention belongs to non-halogen material technology field, be specially a kind of non-halogen epoxide glass cloth base copper coated foil plate and preparation method thereof.This copper foil plate is a substrate by the gluing multilayer woven glass fabric of halogen-free epoxy resin adhesive, is covered with Copper Foil again, prepares through hot pressing then.Preparation process comprises the mixing impregnation, gluing, system prepreg, steps such as composing, hot pressing.Copper-clad plate of the present invention has good flame-retarding characteristic, and belongs to environment-friendly type, can be widely used as the printed circuit board (PCB) of computer, mobile phone etc.
Description
Technical field
The invention belongs to non-halogen material technology field, be specifically related to epoxide glass cloth base copper coated foil plate of a kind of Halogen and preparation method thereof.
Technical background
The development of non-halogen base material originates from 20th century the mid-80, and real industrialization is about 1997, and related standards begins issue by JPCA earlier and carries out.As far back as in November, 1998, Japanese Toshiba chemistry just provides in the world the notebook computer of use Halogen base material the earliest to put on market.
Bromo element has fire-retardant or difficult combustion characteristic in the halogens, can be used for preventing to avoid fire to take place.But can produce carcinogenic bioxin when human discovery polybromide is being lower than 1000 ℃ of burnings after, people consider usually to replace with other yuan this function of halogen when selecting ignition-proof element.
In fire proofing, except halogen, also have materials commonly used such as Phosphorus and nitrogen class, inorganic hydroxide also is the additive of using always simultaneously, these technology have been applied to (CCL is the copper-clad plate industry) among the exploitation of CCL.
Usually, the burning industry is all adopted contain phosphorus, nitrogen, inorganic metal or hydroxide and substitute halogen materials such as the more bromine of consumption, chlorine to reach fire-retardant.No matter what dvielement reaches fire retardation, the fire-retardant and condensed phase of gas phase is fire-retardant to be people's two kinds of fire-retardant patterns of generally acknowledging for a long time.
Phosphorus material is in when burning, in condensed phase, have dehydration, crosslinked, become effect such as carbon, can improve carbon forming rate.This means that less substance is burned.Generally speaking, carbon forming rate during up to 40-50% oxygen fire burning index (LOT) can be higher than 30%, resulting product can reach the standard of UL 94V0.Carbon be created in thermal decomposition the time can reduce and generate flammable volatile matter, can influence next step thermal degradation, form the insulation carbon-coating on the material surface, and the LOT of carbon itself is up to 65%, the generation of water can be diluted fuel gas, simultaneously can take away or absorb heat, generate phasphorus-containing polymer, can increase substantially the LOT index.
In the general industry, according to fire retardant mechanism, adopting the resin of phosphor-containing structure is main resin, makes assisted resin with the resin that contains N structure, to avoid the many disadvantages of the sort of pure additive flame retardant in the past.
Summary of the invention:
The object of the present invention is to provide a kind of non-halogen epoxide glass cloth base copper coated foil plate and preparation method thereof.
The non-halogen epoxide glass cloth base copper coated foil plate that the present invention proposes is that the gluing multilayer woven glass fabric of main adhesive is a substrate by halogen-free epoxy resin, is covered with Copper Foil again, prepares through hot pressing, and its thickness is 0.05-3.2mm, and wherein, copper thickness is HOZ-3OZ.
The preparation method of above-mentioned non-halogen epoxide glass cloth base copper coated foil plate is as follows:
(1) mixes impregnation
Colloid is formed weight share and is counted:
Halogen-free epoxy resin: 133
Dimethyl formamide: 26-30,
Dicyandiamide: 3-4,
Methylimidazole: 0.060-0.078,
Magnesium hydroxide (as inorganic filler): 8-13,
Said components is mixed;
(2) gluing, the system prepreg;
With the glass fabric gluing, oven dry, 160～215 ℃ of oven temperatures,
Prepreg gluing speed: 12-15m/min,
Prepreg control parameter:
Gel time: 95-120sec,
Resin content: 41.5-43.5%,
Resin flow: 19-22.5%,
Fugitive constituent:＜0.75%
(3) set type compacting:
To open superimposedly through the semi-solid preparation glass fiber sheets 4-10 of above-mentioned processing, and be covered with Copper Foil again, and carry out hot pressing, actual conditions is:
Vacuum :-0.095～-0.099MPa
Pressure: 280-460psi
Temperature of heat plate: 135～205 ℃, 90-100 minute pressing plate time,
Hardening time: 45-60 minute.
Non-halogen epoxide glass fiber cloth matrix copper-clad laminate of the present invention can have plurality of specifications, for example, and 36 * 48,40 * 48,42 * 48,37 * 49,41 * 49,43 * 49,36.5 * 48.5,40.5 * 48.5,42.5 * 48.5, (unit is an inch).Glass fabric can adopt the E level, and its specification is 7628,1500,2116,2313,1080 and 106 etc.The thickness of electrolytic copper foil is HOZ, 1OZ, 2OZ or 3OZ.
Copper coated foil plate of the present invention, the content of chlorine in its substrate (Cl) and bromine (Br) is respectively less than 0.09% (weight ratio).
Halogen base material of the present invention is mainly based on Phosphorus and P-N type, phosphorous multifunctional when burning decomposes generate and gather sour phosphorus partially, have high dehydrated, make the macromolecule resin surface form carbonized film, isolated resin burning surface contacts with air, thereby fire is extinguished, reach resistance alkene effect, flame retardant rating is: 94V-0, and belong to environment-friendly type, can be widely used as the printed circuit board (PCB) of computer, mobile phone etc.
The specific embodiment
Raw material:
The E grade fiberglass cloth
Component:
| SiO 2 | 55.2 | Na 2O and K 2O | 0.5 |
| AL 2O 3 | 14.8 | B 2O 3 | 7.3 |
| CaO | 18.6 | Fe 2O 3 | 0.3 |
| MgO | 3.3 |
Performance indications
| Project name | Specification requirement |
| Thickness (mm) | 0.18±0.018 |
| Weight (g/m 2) | 203±5 |
| Warp count (root/cm) | 17.5±1 |
| Weft count (root/cm) | 12.2±1 |
| The warp-wise fracture strength | ≥295N/2.5cm |
| The broadwise fracture strength | ≥250N/2.5cm |
| Combustible loss rate (%) | 0.10-0.26 |
| Alkali metal oxide content (%) | ≤0.8 |
Glass bridal veil fibre tensile strength height, electrical insulation capability is good, dimensionally stable, high temperature resistant, is good reinforced insulation material.
2, halogen-free epoxy resin (phosphorous)
Chemical composition: phosphorus-containing flame-retardant epoxy resin (75%)+butanone (25%)
The resin specification:
| Project | Specification |
| Epoxide equivalent EEW (g/eq) | 290～320 |
| Hydrolyzable chlorine (ppm) | 300Max |
| Solid (wt%) | 74～76 |
| Viscosity (mPas/25 ℃) | 1500～3500 |
| P containing ratio (wt%) | 2.0～4.0 |
| Solvent | MEK (butanone) |
Reference formulation:
| Project | Weight |
| Halogen-free epoxy resin (phosphorous) | 133phr |
| Dicyandiamide | 3.4phr |
| 2-MI | 0.07phr |
| Solvent | 27.5phr |
| Solid | 63.2％ |
| Varnish Gel Time(171℃，s) | 200～300 |
| Prepreg Gel Time(171℃，s) | 50～150 |
This specification halogen-free epoxy resin characteristic is easily to flow, and is good with the glass fibre impregnation, and sclerosis then property is good, and the resin kinematic viscosity changes little, processing temperature wide ranges in the hot pressing, hardening is complete.Easy operating and stay in grade.
C, electrolytic copper foil
Performance indications (HOZ):
| Indicated weight | g/m 2 | 155.4 |
| Ra | um | 0.23 |
| Rz | um | 4.65 |
| Peel strength | N/mm | 1.48 |
| Tensile strength | Mpa | 344.8 |
| Percentage elongation | ％ | 4.5 |
| Oxidisability | 200℃/0.5h | Pass |
Because the heat that advances in pressing of multilayer board can make Copper Foil that crystalline polamer again takes place, the same high-elongation in the time of need also having with normal temperature when high temperature is to guarantee the driffractive ring phenomenon not occur in the printed board manufacturing process.
The important technological parameters of product:
This Halogen substrate has superior mechanical intensity, mechanical properties, anti-electrification, flame resistance, anti-UV characteristic etc., is applicable to that PCB and multi-layer sheet machine make processing.
Embodiment 1
1 impregnation prescription:
Halogen-free epoxy resin: dimethyl formamide: dicyandiamide: methylimidazole: magnesium hydroxide (inorganic filler)
133∶27.5∶3.4∶0.065∶8
2 gluings oven dry:
Oven temperature is provided with: 168～210 ℃
Prepreg gluing speed: 14.8m/min
3 control parameter requests: gel time: 100sec, resin content: 43.0%,
Resin flow: 22.0%, fugitive constituent: 0.25%.
4 plates row flaggy number: 8 7628 prepregs (1.6mm plate)
5 pressing plate parameters: vacuum :-0.097MPa,
Pressure: 290-430psi,
Temperature of heat plate: 135～205 ℃,
Hardening time: 50 minutes.
6 substrate performance parameters:
Embodiment 2
1 impregnation prescription:
Halogen-free epoxy resin: dimethyl formamide: dicyandiamide: methylimidazole: magnesium hydroxide (inorganic filler)
133∶27.5∶3.4∶0.070∶10
2 gluings oven dry:
Oven temperature is provided with: 165～205 ℃,
Prepreg gluing speed: 14.2m/min.
3 control parameter requests: gel time: 108sec, resin content: 42.8%,
Resin flow: 21.5%, fugitive constituent: 0.30%.
4 plates row flaggy number: 8 7628 prepregs (1.6mm plate)
5 pressing plate parameters: vacuum :-0.098MPa,
Pressure: 300-440psi,
Temperature of heat plate: 135～205 ℃,
Hardening time: 55 minutes.
6 substrate performance parameters:
Embodiment 3
1 impregnation prescription:
Halogen-free epoxy resin: dimethyl formamide: dicyandiamide: methylimidazole: magnesium hydroxide (inorganic filler)
133∶27.5∶3.4∶0.075∶13
2 gluings oven dry:
Oven temperature is provided with: 160～200 ℃,
Prepreg gluing speed: 13.8m/min.
3 control parameter requests: gel time: 118sec, resin content: 42.5%,
Resin flow: 19.8%, fugitive constituent: 0.32%.
4 plates row flaggy number: 8 7628 prepregs (1.6mm plate)
5 pressing plate parameters: vacuum :-0.098MPa,
Pressure: 310-450psi,
Temperature of heat plate: 135～205 ℃,
Hardening time: 60 minutes.
6 substrate performance parameters:
Claims (2)
1, a kind of preparation method of non-halogen epoxide glass cloth base copper coated foil plate is characterized in that concrete steps are as follows:
(1) mixes impregnation
Colloid is formed weight share and is counted:
Halogen-free epoxy resin: 133
Dimethyl formamide: 26-30,
Dicyandiamide: 3-4,
Methylimidazole: 0.060-0.078,
Magnesium hydroxide: 8-13,
Said components is mixed; Wherein, halogen-free epoxy resin is based on Phosphorus or P-N type;
(2) gluing, the system prepreg:
With the glass fabric gluing, oven dry, 160～215 ℃ of oven temperatures,
Prepreg gluing speed: 12-15m/min,
The prepreg parameter:
Gel time: 95-120sec,
Resin content: 41.5-43.5%,
Resin flow: 19-22.5%,
Fugitive constituent:＜0.75%
(3) set type compacting:
To open superimposedly through the semi-solid preparation glass fiber sheets 4-10 of above-mentioned processing, and be covered with Copper Foil again, and carry out hot pressing, actual conditions is:
Vacuum :-0.095～-0.099MPa,
Pressure: 280-460psi,
Temperature of heat plate: 135～205 ℃, 90-100 minute pressing plate time,
Hardening time: 45-60 minute.
2, a kind of non-halogen epoxide glass cloth base copper coated foil plate for preparing by the described method of claim 1, its thickness is 0.05-3.2mm, wherein, copper thickness is HOZ-3OZ.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100256865A CN100569505C (en) | 2006-04-13 | 2006-04-13 | A kind of non-halogen epoxide glass cloth base copper coated foil plate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100256865A CN100569505C (en) | 2006-04-13 | 2006-04-13 | A kind of non-halogen epoxide glass cloth base copper coated foil plate and preparation method thereof |
Publications (2)
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| CN1868735A CN1868735A (en) | 2006-11-29 |
| CN100569505C true CN100569505C (en) | 2009-12-16 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101654005B (en) * | 2008-08-22 | 2012-07-25 | 金安国纪科技股份有限公司 | Method for manufacturing halogen-free FR-4 copper-clad laminate |
| CN102198745A (en) * | 2010-03-24 | 2011-09-28 | 常州中英科技有限公司 | Production process of polyfluortetraethylene fiber glass copper layer-cladding pressure plate |
| CN102173131A (en) * | 2010-12-30 | 2011-09-07 | 上海南亚覆铜箔板有限公司 | Copper foil-coated plate with high electricity leakage tracking index and preparation method thereof |
| CN102179973A (en) * | 2011-03-18 | 2011-09-14 | 江阴市明康绝缘玻纤有限公司 | Halogen-free flame retardant epoxy glass cloth copper foil coated laminated board |
| CN102390145B (en) * | 2011-08-05 | 2014-06-11 | 金安国纪科技（珠海）有限公司 | Environment-friendly copper clad laminate and preparation method thereof |
| CN102566537B (en) * | 2011-12-23 | 2013-08-14 | 广东生益科技股份有限公司 | Copper-clad plate glue water mixing control system |
| CN103540103A (en) * | 2013-09-22 | 2014-01-29 | 重庆德凯覆铜板有限公司 | Epoxy resin composition and method for preparing adhesive by using same |
| CN104015461B (en) * | 2014-05-27 | 2016-06-15 | 铜陵浩荣华科复合基板有限公司 | A kind of Halogen Tg130 method for manufacturing cover clad laminate |
| CN110126372A (en) * | 2019-06-05 | 2019-08-16 | 河源广工大协同创新研究院 | A kind of preparation method of multiple layer metal layers of foil structure copper-clad plate |
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Address after: Shanghai city Chang Cheung Road 201802 Jiading Nanxiang Town, No. 158 Patentee after: South Asia new materials Polytron Technologies Inc Address before: Shanghai city Chang Cheung Road 201802 Jiading Nanxiang Town, No. 158 Patentee before: Shanghai Nanya Copper Clad Laminate Co., Ltd. |
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