CN102632654A - Copper-clad laminate and preparation method thereof - Google Patents
Copper-clad laminate and preparation method thereof Download PDFInfo
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- CN102632654A CN102632654A CN2011104406612A CN201110440661A CN102632654A CN 102632654 A CN102632654 A CN 102632654A CN 2011104406612 A CN2011104406612 A CN 2011104406612A CN 201110440661 A CN201110440661 A CN 201110440661A CN 102632654 A CN102632654 A CN 102632654A
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Abstract
The invention relates to a distributing procedure for preparing glue liquor for a copper-clad laminate. The distributing procedure includes an operating procedure for controlling the sequence of adding single items such as epoxy resin, curing agent, solvent, packing, accelerant and the like in distribution. The operating procedure mainly includes a packing pretreatment procedure and an epoxy resin adding procedure. The packing pretreatment procedure includes the steps: firstly adding the solvent for preparing mixed glue liquor; starting continuous stirring and adding the packing; continuing stirring for 30 minutes after adding the packing; completely wetting the packing by the aid of the solvent; adding the resin; adding the needed epoxy resin during stirring; adding the accelerant after stirring for 120 minutes; testing reactivity of the glue liquor by means of sampling after continuing stirring for 360-420 minutes; and using the glue liquor after the glue liquor is qualified. The prepared glue liquor is better in stability, and the packing is more uniformly dispersed.
Description
Technical field
The present invention relates to a kind of copper clad foil substrate that in the printed circuit board (PCB) industry, uses and preparation method thereof; Relate generally to the copper clad foil substrate that fiberglass-based epoxy resin is made; Be applicable to that to various types of copper-clad plates especially inorganic compounding filler adding proportion is the copper-clad plate of 10%-50%.
Background technology
According to printed circuit handbook (Claire (Coombs) editor; 3 editions; Mike Lao Xier books company (McGraw-Hill Book Co.) published in 1988) to the classification of copper-clad plate (being copper clad foil substrate), it is divided into FR-2, FR-3, FR4, CEM-1 etc.FR-2 refers to paper-based phenolic resin making copper-clad plate, and FR-3 refers to paper substrate epoxy resin making copper-clad plate, and FR-4 refers to glass basic ring epoxy resins type making copper-clad plate.
In this composite of copper-clad plate, adding filler serves as filler, fire retardant etc. and before early, just is being suggested.The adding of filler can improve the mechanical performance and the electric property of material.Just propose to add filler in No. 5264065, the United States Patent (USP), in order to reduce the thermal coefficient of expansion of copper-clad plate.And the reliability of copper-clad plate thermal coefficient of expansion when reducing follow-up making printed circuit board (PCB) improves a lot.In addition, No. 222950, Japan Patent, No. 97633, Japan Patent, Japan Patent all have announcement No. 120330, add filler and are used to limit resin flows and improvement punching property.Disclose in No. 4960634, the United States Patent (USP) and use zinc oxide as a kind of additive of improveing thermal conductivity.Disclose in No. 133440, the Japan Patent, heating talcum powder to 1000 ℃-2000 ℃, remove the crystallization water after, add in the copper-clad plate dimensional stability with improvement sheet material.No. 6322885, United States Patent (USP) discloses, and uses talcum powder to be used to improve the characteristics such as thermal coefficient of expansion, boring of copper-clad plate, does not reduce the electrical strength of copper-clad plate simultaneously.
Nearly 2 years,, hear resistance, the mechanical performance of copper-clad plate have been made higher requirement along with the unleaded implementation of electron trade.High glass transition temperature (refer to about 150 ℃ or higher), low-expansion copper-clad plate then can adapt to this requirement preferably, and use amount increases sharply.But also there are some problems in this type of copper-clad plate, and is more crisp such as resin, and with the peel strength decline of Copper Foil, hardness further increases behind interpolation inorganic filler such as the silica.When so just having caused punching during making printed circuit board (PCB), cutting, boring, the white edge phenomenon takes place, dust is more, stamping knife, drill point serious wear.To the problems referred to above; Carried out a lot of correlative studys in the industry, but found that various inorganic fillers respectively have pluses and minuses, for example the silica advantage is significantly not reduce the characteristics such as Copper Foil peel strength of copper-clad plate; But its hardness is very big, and the drill point wearing and tearing when making boring increase very fast.The talcum powder advantage is the boring excellent performance, but can reduce the Copper Foil peel strength of copper-clad plate.Aluminium hydroxide has outstanding fire retardation, but its heat resistance is poor, also can reduce the Copper Foil peel strength of copper-clad plate simultaneously.
Compound silica flour is a kind of composite of uniqueness, is select for use several inorganic minerals to smelt fusion to process.Silica comprises 58%-62% wherein, alundum (Al accounts for 28%-32%, and other oxides such as diboron trioxide of 9-11%.Compound silica flour is mainly used in the composite filling material of each electronic product, wherein to the west of BIC Corp's trade mark be that the properties of product of G2-C are preferable.
Along with each inorganic composite type filler is introduced into the production of copper-clad plate, its characteristic that in copper-clad plate, is shown receives much concern.In order to improve the joint capacity of inorganic composite type filler and organic epoxy resin, further promote the performance of copper-clad plate, we have introduced a kind of silane coupler; One end of this kind coupling agent has inorganic group, be prone to well engage with inorganic filler, and the other end has epoxide group; With epoxy resin can intimate engagement; Through this media, inorganic filler is well engaged together with epoxy resin, strengthen the hear resistance and the machining property of product.
Summary of the invention
The object of the invention provides a kind of copper clad foil substrate and preparation method thereof, with the heat resistance and the machining property of further lifting product.
The present invention seeks to realize like this:
A kind of copper clad foil substrate; Form by prepreg and Copper Foil compacting; Add silane coupler in the glue of prepreg (content of inorganic composite type filler is 10%-50% in the glue) processing, this silane coupler is the epoxy type silane coupler, and addition is the 0.4%-0.6% of filler and solvent total amount in the glue system; Prepare copper-clad plate with this glue, can improve its many-sided performance.
Said epoxy type silane coupler; With DOW CORNING Z6040 is representative; Coupling agent purity is more than 98.0%, and these coupling agent two ends have an inorganic group and an epoxy type group respectively, between the inorganic composite type filler of glue and epoxy resin, forms a media; Strengthened the engaging force of inorganic compounding filler and epoxy resin, made inorganic filler fused more stable in epoxy resin.
The preparation method of said copper clad foil substrate may further comprise the steps:
(1) preparation of glue: under the room temperature, in proportion container, add the solvent of preparation glue earlier, adding filler in the situation that continues to stir again; After fully stirring 15-30min; Add coupling agent, continue to stir 30-60min, (basic material is meant that preparation does not contain the required raw material of glue of inorganic filler to add all the other required basic materials of glue then; Basic material for different copper clad foil substrate preparation glues is different; As for the halogen-free flameproof copper clad foil substrate, the basic material of preparation glue comprises the special composition in solvent, curing agent, epoxy resin, fire retardant, curing accelerator and other prescription, and this is a known technology); Stirred again 4 ~ 8 hours; The gel time of sampling and testing glue (171 ℃ of hot plates), gel time is controlled through the addition of curing accelerator, and its gel time should be controlled between 200～350 second second;
(2) impregnation: the adhesive plaster that will soak glue through control wind-warm syndrome and furnace temperature, makes prepreg through vertical or horizontal type impregnation machine;
(3) compacting: after the prepreg that cuts and Copper Foil combined, put into the vacuum hotpressing machine, obtain copper clad foil substrate in certain temperature, pressure, time and vacuum condition pressed.
Should note in the present invention:
(1) adding of filler: in proportion container, add the solvent of preparation glue earlier, under the situation that continues stirring, filler is added,, stir 15 ~ 30min uniform filling is dispersed in the solvent to prevent that filler from directly sinking to container bottom and causing blocking pipeline.
(2) adding of coupling agent: filler stirs 15 ~ 30min in solvent after, coupling agent is added container according to 0.4% ~ 0.6% of filler and solvent total amount, stir 30 ~ 60min, coupling agent is fully engaged with filler earlier.
(3) adding of basic material: after treating that (1), (2) are accomplished; Basic materials such as the needed epoxy resin of glue are added; Stirred 4 ~ 8 hours, the other end (epoxide group) of coupling agent is engaged with epoxy resin, to reach the fused of inorganic filler and epoxy resin.
(4) the adding mode of curing agent and curing accelerator: before use, should earlier curing agent and curing accelerator be dissolved in solvent, be mixed with solution, for use.
(5) solvent: with dimethyl formamide DMF, cyclohexanone, butanone, propylene glycol monomethyl ether, propylene glycol monomethyl ether amyl acetate etc. or its combination as dicyandiamide solution, with acetone, butanone or its combination as diluent.
(6) gelation time is regulated: the gelation time of the glue of preparing can be regulated with the addition of curing accelerator.
Gelation time: through adjustment, the gelation time of glue all can prepare sheet material through gluing machine and press in 200～300 seconds scope.
Solid content: the solid content of general glue is at 50% ~ 70%wt.
Storage period: the glue of being prepared can at room temperature be stored 5 ~ 15 days.
After adopting such scheme, theory analysis of the present invention:
Because the ratio of filler is increasingly high in the copper-clad plate now, how solving filler becomes urgent problem with engaging of epoxy resin.The filler that is used for copper-clad plate at first now is mainly inorganic fillers such as SiO2, ATH, and the glue system of resin is organic, and this filler that just causes now being added just simply is dispersed in the glue, does not well engage with resin.Once more, because inorganic filler does not well engage with epoxy resin, the copper-clad plate of institute's output filler in process can drop, and more serious dry linting phenomenon occurs.Simultaneously, inorganic filler adds glue, just simply is suspended in the glue, and As time goes on, filler can cause difficulty to subsequent handling because the slowly sedimentation of influence of self gravitation causes filler in glue, to occur disperseing uneven phenomenon.
Now also have in glue, directly to add the filler of handling through active, improve the purpose that inorganic filler engages with epoxy resin to reach, but through after active the processing; The surface tension of filler can become greatly, when in glue, adding, can waft on the glue surface, sneaks into glue with mechanical force (stirring) again; Because the surface has active group; Tend to occur the autohemagglutination phenomenon, cause the filler caking, the phenomenon that is difficult to disperse occurs.
Comprehensive above situation; The present invention is at first with in inorganic filler dispersion and the solvent; Handle at the adding silane coupler then; Fused with epoxy resin more at last, this measure had both solved the problem that engages when inorganic filler is directly fused with epoxy resin, had also avoided direct use active filler autohemagglutination to occur and the problem of luming.
The present invention possesses following some beneficial effect:
One, the inorganic compounding filler is through the processing of silane coupler, strengthened itself and the engaging of epoxy resin, and makes it more stable in glue;
Two, the inorganic compounding filler is through the processing of silane coupler, and the premium properties that makes filler in copper-clad plate, shown is more outstanding, and reliability is better;
Three, the inorganic compounding filler is through the processing of silane coupler, and filler has obtained reinforcement with engaging of epoxy resin, can prevent effectively that filler separates with epoxy resin in mechanical processing process, has well improved the dry linting phenomenon of copper-clad plate in machining.
Figure of description
Fig. 1, photo is used in the contrast of the glue fillers dispersed property of embodiment one;
Fig. 2, photo is used in the contrast of the glue fillers dispersed property of embodiment two;
Fig. 3, the situation photo after the substrate of embodiment one is hit;
Fig. 4, the situation photo after the substrate of embodiment two is hit.
The specific embodiment
1, specific embodiment prescription
Halogen prescription (more than Tg140 ℃, proportion of filler 20%)
One of embodiment GEBR589K75 (halogen-free epoxy resin that Hong Chang produces; Possess the Tg more than 140 ℃ after the curing) 55.5%; Curing agent dicyandiamide (curing agent that Daiei is produced) 1.35%, solvent DMF 16.0%, curing accelerator 2-ethyl-4-methylimidazole 0.3%; G2-C (gram company in Thebe produces compound silica flour) 20%, silane coupler (Z6040 of DOW CORNING production) 0.18%.
Two (comparative example) GEBR589K75 of embodiment (halogen-free epoxy resin that Hong Chang produces; Possess the Tg more than 140 ℃ after the curing) 55.5%; Curing agent dicyandiamide (curing agent that Daiei is produced) 1.35%; Solvent DMF 16.0%, curing accelerator 2-ethyl-4-methylimidazole 0.3%, G2-C (gram company in Thebe produces compound silica flour) 20%.
2, the preparation technology of glue
One of embodiment
1) solvent is added (DMF solvent, because of curing agent has used DMF solvent in advance, this step adds solvent curing agent solution in the lump) in the proportion container;
2) continue to stir and to add filler down, fully stir 15-30min after, add coupling agent, continue to stir 30-60min;
3) add resin list article and all the other raw materials;
4) continue to stir 4-8 hour, the gel time of sampling and testing glue (171 ℃ of constant temperature hot plates), the control gel time is in 200-350 second.
Two (comparative examples) of embodiment
1) solvent is added (DMF solvent, because of curing agent has used DMF solvent in advance, this step adds solvent curing agent solution in the lump) in the proportion container;
2) continue to stir adding filler down, fully stir 15-30min;
3) add resin list article and all the other raw materials;
4) continue to stir 4-8 hour, the gel time of sampling and testing glue (171 ℃ of constant temperature hot plates), the control gel time is in 200-350 second.
3, impregnation
The adhesive plaster that will soak the halogen-free flameproof glue through conditions such as control squeegee roller speed, linear speed, wind-warm syndrome and furnace temperature, makes prepreg through vertical or horizontal type impregnation machine.
With vertical impregnation machine is example:
The proportion of glue: 1.10～1.20;
Squeegee roller speed :-1.8～-2.5 ± 0.1 M/min;
Main line speed: 5～14 M/min;
Wind-warm syndrome: 130～160 ℃;
Furnace temperature: 140～180 ℃.
Make prepreg through above condition.
4, compacting
After the prepreg that cuts and Copper Foil combined, put into the vacuum hotpressing machine, obtaining substrate by the follow procedure compacting.
Temperature program(me): 130 ℃/30min+160 ℃/30min+180 ℃/20min+210 ℃/180min
Pressure program: 20Kgf.cm-2/30min+50Kgf.cm-2/15min+95Kgf.cm-2/150min+20Kgf.cm-2/65min
Vacuum is set: 30mmHg/130min+760mmHg/130min
5, be the contrast properties of two embodiment below:
(1) allot the contrast of glue fillers dispersed property:
See from Fig. 1, fillers dispersed proterties condition shown in Figure 2: the good uniformity of one of embodiment is in two of embodiment.
(2) institute's production substrate processing characteristics contrast:
Falling sphere experiment (height 20in is with circular iron ball vertical impact substrate surface) is confirmed the situation after substrate is hit, substrate thickness 1.2mm.
See from the figure of the impact of Fig. 3, Fig. 4: one of embodiment is significantly " ten " word, and it is less to explain that its filler comes off, better with engaging of resin, and two " ten " words of embodiment are not obvious.
Claims (3)
1. copper clad foil substrate; Form by prepreg and Copper Foil compacting; It is characterized in that: in processing the glue of prepreg (containing 10%-50% inorganic composite type filler), add silane coupler, addition is the 0.4-0.6% of filler and solvent total amount in the glue system.
2. a kind of copper clad foil substrate as claimed in claim 1 is characterized in that: silane coupler is the epoxy type coupling agent, and it is represented as DOW CORNING Z6040.
3. a kind of copper clad foil substrate as claimed in claim 1, it is characterized in that: the preparation method may further comprise the steps:
(1) preparation of glue: under the room temperature, in proportion container, add the solvent of preparation glue earlier, adding filler in the situation that continues to stir again; After fully stirring 15-30min; Add coupling agent, continue to stir 30-60min, add all the other required basic materials of glue then; Stirred 4-8 hour, the gel time of sampling and testing glue also was controlled at 200～350 seconds again;
(2) impregnation: the adhesive plaster that will soak glue through control wind-warm syndrome and furnace temperature, makes prepreg through vertical or horizontal type impregnation machine;
(3) compacting: after the prepreg that cuts and Copper Foil combined, put into the vacuum hotpressing machine, suppress obtaining copper clad foil substrate.
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| CN2011104406612A CN102632654A (en) | 2011-12-26 | 2011-12-26 | Copper-clad laminate and preparation method thereof |
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| CN2011104406612A CN102632654A (en) | 2011-12-26 | 2011-12-26 | Copper-clad laminate and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107603149A (en) * | 2017-08-28 | 2018-01-19 | 南亚新材料科技股份有限公司 | One kind examines electron level filler fish purpose method |
| CN108116027A (en) * | 2017-12-28 | 2018-06-05 | 广州云普电子科技有限公司 | A kind of method for manufacturing cover clad laminate that can improve production efficiency |
| CN110588116A (en) * | 2019-09-04 | 2019-12-20 | 重庆德凯实业股份有限公司 | Flame-retardant heat-resistant copper foil-coated epoxy glass fiber cloth-based laminated board and preparation method thereof |
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| JPS60240703A (en) * | 1984-05-14 | 1985-11-29 | Hitachi Chem Co Ltd | Photocurable composition |
| JPH03257890A (en) * | 1990-03-07 | 1991-11-18 | Toshiba Chem Corp | Copper clad laminate |
| CN1121942C (en) * | 1999-04-29 | 2003-09-24 | 北京化工大学 | Composite base laminated board covered with copper foil and its production method |
| CN101368077A (en) * | 2008-10-09 | 2009-02-18 | 腾辉电子（苏州）有限公司 | Epoxy resin adhesive liquid |
| CN101547558B (en) * | 2009-04-21 | 2011-04-13 | 无锡宏仁电子材料科技有限公司 | Copper clad base plate and preparation method thereof |
-
2011
- 2011-12-26 CN CN2011104406612A patent/CN102632654A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60240703A (en) * | 1984-05-14 | 1985-11-29 | Hitachi Chem Co Ltd | Photocurable composition |
| JPH03257890A (en) * | 1990-03-07 | 1991-11-18 | Toshiba Chem Corp | Copper clad laminate |
| CN1121942C (en) * | 1999-04-29 | 2003-09-24 | 北京化工大学 | Composite base laminated board covered with copper foil and its production method |
| CN101368077A (en) * | 2008-10-09 | 2009-02-18 | 腾辉电子（苏州）有限公司 | Epoxy resin adhesive liquid |
| CN101547558B (en) * | 2009-04-21 | 2011-04-13 | 无锡宏仁电子材料科技有限公司 | Copper clad base plate and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107603149A (en) * | 2017-08-28 | 2018-01-19 | 南亚新材料科技股份有限公司 | One kind examines electron level filler fish purpose method |
| CN108116027A (en) * | 2017-12-28 | 2018-06-05 | 广州云普电子科技有限公司 | A kind of method for manufacturing cover clad laminate that can improve production efficiency |
| CN110588116A (en) * | 2019-09-04 | 2019-12-20 | 重庆德凯实业股份有限公司 | Flame-retardant heat-resistant copper foil-coated epoxy glass fiber cloth-based laminated board and preparation method thereof |
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Application publication date: 20120815 |