CN102002208B - Epoxy resin composition and adhesive sheet and substrate made by same - Google Patents
Epoxy resin composition and adhesive sheet and substrate made by same Download PDFInfo
- Publication number
- CN102002208B CN102002208B CN200910168188XA CN200910168188A CN102002208B CN 102002208 B CN102002208 B CN 102002208B CN 200910168188X A CN200910168188X A CN 200910168188XA CN 200910168188 A CN200910168188 A CN 200910168188A CN 102002208 B CN102002208 B CN 102002208B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- component
- composition epoxy
- composition
- sericite powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to an epoxy resin composition and an adhesive sheet and a substrate made by the same. The epoxy resin composition comprises component A: epoxy resin, component B: a hardening agent, component C: an accelerator, component D: a packing material namely sericite powder, wherein, the sericite powder contains 55%+/-3% of silicon dioxide, and the hardness of the sericite powder is mohs' hardnees 2-3. Therefore, the adhesive sheet/substrate made by dipping in epoxy resin composition glue solution has better processibility.
Description
Technical field
The present invention relates to a kind of composition epoxy resin, refer to a kind of composition epoxy resin that is added with the sericite powder especially.
Background technology
Printed substrate is by impregnation film (PP), or contain copper clad laminate (Copper clad laminate, CCL) or a plurality of films such as Copper Foil utilize the abundant pressing of hot pressing program; And this impregnation film is that glasscloth impregnated in the epoxy resin adhesive liquid, and carries out subsequent techniques such as drying and form a kind of slim film.Along with the execution of environmental protection act (like RoHS, WEEE), lead-free solder technology is substituted with the technology of lead solder, has improved 30 to 40 degree and will assemble temperature, and its thermotolerance to substrate requires significantly to improve.
Current trends are that stiffening agent is big by original polarity, as to be prone to suction DICY stiffening agent changes the resol stiffening agent of the difficult suction that contains benzene ring structure into, and add a large amount of inorganic silicon micropowder fillers, to improve the thermotolerance of substrate.Yet the interpolation of above-mentioned inorganic silicon micropowder filler but causes occurring the bad phenomenon of sheet material hardening, and makes it be difficult to carry out mechanical workout; Bad phenomenon such as for example, during the manufacturing of printed substrate, when substrate carries out bore process, may cause substrate layering, laminated plates to crack, drill point ruptures or drill point wearing and tearing are excessive.
In other words, be added with the higher filler of hardness in the prior resin glue, up to seven silicon-dioxide, and the processibility of made film/substrate be restricted like Mohs' hardness.
Therefore, the inventor proposes a kind of reasonable in design and effectively improve the invention of above-mentioned defective to above-mentioned defective.
Summary of the invention
Main purpose of the present invention is to provide a kind of composition epoxy resin, utilizes the sericite powder to be the inorganic fillings in the resin adhesive liquid, to improve the processibility of film/substrate.In addition, the present invention also with regard to the discussion that experimentizes of the composition of sericite powder and particle diameter, avoids the sericite powder that chemical property, the physical properties of resin adhesive liquid are exerted an influence, and therefore, adds thermotolerance and water-absorbent etc. that the sericite powder can keep film/substrate.
The present invention provides a kind of composition epoxy resin, comprising: component A: epoxy resin, and this epoxy resin is: brominated phenols formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, four functional group's epoxy resin or above-mentioned two or more mixed resin; B component: stiffening agent; Component C: promotor; Component D: stopping composition, it is the sericite powder, the silicon-dioxide that wherein has 55 ± 3% weight in the composition of this sericite powder, the hardness of this sericite powder is Mohs' hardness 2 to 3, the particle diameter of this sericite powder is 3 ± 1um.
The present invention also provides a kind of this glasscloth impregnated in the above-mentioned composition epoxy resin, and after curing, drying and other steps, and the film (prepreg) that forms.
The present invention also provides a kind of substrate that utilizes above-mentioned film through the made printed substrate of process for pressing.
The present invention has following useful effect: the present invention utilizes the lower sericite in powder material of hardness as mineral filler, to increase the boring processibility of made substrate.The present invention limits for the silicon-dioxide in the sericite powder composition, with the hardness of adjustment sericite powder and reduce it to the reactive influence of resin adhesive liquid; In addition, the present invention further limits for the particle diameter specification of sericite powder again, also can further reduce the reactive impact effect for resin adhesive liquid.
For enabling further to understand characteristic of the present invention and technology contents, see also following relevant detailed description of the present invention, yet it only provides reference and explanation usefulness, is not to be used for the present invention is limited.
Embodiment
The present invention provides a kind of composition epoxy resin; The inorganic fillings that contains the sericite powder in this composition epoxy resin; The inorganic fillings of this sericite powder can make glasscloth through the hardened speed of reaction that is increased after impregnation (dipping) step, and improves the glass transition temperature (Tg) of made substrate; And the hardness of this sericite powder is lower, can make made substrate have preferable processibility.
In other words, the sericite powder that the present invention is lower with hardness makes an addition in the composition epoxy resin, utilizes the soft characteristic of sericite powder, makes processed and applied such as made substrate is more suitable for holing; And the present invention also controls the insulation characterisitic of sericite powder with reactive, reacts with the acid generation of resin combination to avoid composition such as aluminum oxide, Natural manganese dioxide etc. in the sericite powder, and causes the rotten of composition epoxy resin glue.
Below will carry out the collocation of many group embodiment, and select the parameter such as moity, size of sericite powder with explanation and reach best film characteristic to above-mentioned composition epoxy resin.In view of the above, the present invention mainly provides a kind of composition epoxy resin, comprising: component A: epoxy resin; B component: stiffening agent; Component C: promotor; Component D: stopping composition, it is the sericite powder.Please refer to the experimental data of table 1:
Table 1
Table 1 shows the composition epoxy resin that multiple heterogeneity is formed; Wherein main resin (being the epoxy resin of component A) is 100 amount parts; And this epoxy resin can be: epoxy resin is brominated phenols formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, four functional group's epoxy resin (FR4 epoxy resin) or above-mentioned two or more mixed resin, but does not exceed with above-mentioned; B component: stiffening agent is then selected the phenolic aldehyde stiffening agent for use, bisphenol-A phenolic stiffening agent for example, and its consumption is 30 parts of this component A, and in other words, the consumption of bisphenol-A phenolic stiffening agent is 30 parts, and it is the weight part with respect to the epoxy resin of component A.
In the present embodiment, the component C of composition epoxy resin: promotor is a kind of 2-ethyl-4-methylimidazole, and its consumption is 0.06 part of this component A; In addition; This composition epoxy resin also further comprises: component F: solvent; The consumption of the solvent of this component F is 60 parts of this component A; In this specific embodiment, solvent can comprise butanone (MEK), propylene glycol monomethyl ether (PM), pimelinketone or the mixture of two or more above-mentioned solvent arbitrarily.
In addition, this composition epoxy resin also further comprises: component E: additive, for example this additive can be one or more interfacial agent, for example coupler or other additive or the like.In this specific embodiment; It is 0.04 silane coupling agent (Silane coupling agent) that this composition epoxy resin is added with relative quantity part; This silane coupling agent is the interfacial agents that is applied to resin and inorganic fillings; It has the surface-active function of the inorganic fillings of increasing, thereby increases the rerum natura of matrix material, like intensity, wear resistance or the like.With regard to chemical structure; This silane coupling agent has organic Silicone monomer of different reactive group more than two in molecule; One of them is and inorganic fillings bonded reactive group that another is and organic resin material bonded reactive group, so it can make inorganic fillings combine with organic resin material; With film (prepreg, release prepreg), flame resistivity and the processibility of improving moulding.
And the embodiment 1 of table 1, reference examples 1 to 3 mainly are the conditions that changes the sericite powder; Reference examples 4 then is as inorganic fillings with traditional silica powder; And after utilizing the different composition epoxy resin glues of forming to process film; Again with eight film up and down respectively with the 1Oz Copper Foil, hot pressing is to carry out the various characteristics analytical test behind the copper-clad base plate.
Wherein, water-absorbent (rate) can be called water absorbability again, and it mainly is to judge the water absorption character of copper-clad base plate, because copper-clad base plate can receive temperature and humidity effect and the dilatational strain or the absorption aqueous vapor of environment.And under the too high situation of copper-clad base plate water cut, packed moisture, be prone to produce the problem of plate bursting or defective of other circuit card or the like, so absorptive characteristic is one of important feature of film/copper-clad base plate.Traditionally, can carry out IR spectroscopic analysis or hot weight loss method analysis to this material, to confirm the water-absorbent of this copper-clad base plate.
Thermotolerance: promptly float the tin result, heat-resistant experiment is according to industry standard IPC-TM-650 Method2.4.13.1, and copper-clad base plate is soaked in 288 ℃ of tin stove to plate bursting required times (branch).
Flame resistivity: i.e. flame retardancy, measure according to UL 94 methods, be meant the test of plastic material flame resistivity, it confirms the anti-combustion grade of plastic material with the spontaneous combustion time of plastic material standard test piece behind flame, spontaneous combustion speed, the graininess that drops.And good and bad according to anti-combustion grade, be HB, V-2, V-1, V-0 successively, be up to the 5V grade.And UL 94 testing method are meant that plastic material burns on flame with vertical mode.With per ten seconds be a test period, its step is following: step 1: put in the flame test piece into ten seconds and remove again, measure remove after this test piece burn away the time (T1); Step 2: after waiting the test piece fray-out of flame, put in the flame ten seconds again into and remove again, measure again remove after this test piece burn away the time (T2); Step 3: repeat repeatedly to test and get its MV; Step 4: the summation of calculating T1+T2.And the requirement of UL 94 V-0 grades to be the average neither of average and T2 at test piece single combustion time of T1 must surpass 10 seconds, and the summation of its T1 and T2 is must not be above 50 seconds square meet UL 94 V-0 requirements.
Embodiment 1 is a most preferred embodiment of the present invention; In the composition of embodiment 1; Silica weight in this sericite powder composition is 55 ± 3%; And the particle diameter of this sericite powder is 3 ± 1um, and from the data of table 1, resinifying glue time, stripping strength and the water-intake rate of this copper-clad base plate all can satisfy the specification of substrate; And glass transition temperature (Tg) is 141 ℃, representes that its reactivity is also good; And can learn that the film/copper-clad base plate that carries out making after the operation of glasscloth dipping through composition epoxy resin glue proposed by the invention has higher thermotolerance, so required time of plate bursting length and meet test specification; Simultaneously; The boring roughness of this substrate can reduce and reaches 0.9mil; So add the splitting of sericite powder (Mohs' hardness 2 to 3) in the time of can reducing the profile punching of soft; And improve the gluing power of the resin layer contact with the multi-layer wiring board internal layer circuit, improving the problem that internal layer comes off, and then the processibility and the quality product of raising substrate; On the other hand; In order to improve silicon-dioxide and the compatibility of resin in the sericite powder composition; The present invention utilizes silane coupling agent earlier silicon-dioxide to be carried out upgrading; Generating the silicon-dioxide (silanized silica) of silylanization, improving the consistency of silicon-dioxide and resin, and then could improve the rerum natura of the film/copper-clad base plate of manufacturing.
And reference examples 1 is with embodiment 1 difference, and reference examples 1 uses that silica composition weight is 55 ± 3%, particle diameter is less than the sericite powder of 2um.Show according to the experimental result shown in the table 1; Made film/the copper-clad base plate of the resin combination of reference examples 1 has obviously long gel time (resinifying glue time); This is because the particle diameter of sericite powder is little, and forms bigger powder specific surface area, causes the reactivity between sericite powder and the resin adhesive liquid to increase; And influence the voltinism of resin adhesive liquid, and reduce the reactivity of promotor and stiffening agent.Therefore, though the boring roughness of this copper-clad base plate can be reduced to 0.85mil, the physical property of film/copper-clad base plate can't satisfy the specification requirement of product.
In addition, reference examples 2 is that with embodiment 1 difference reference examples 2 is used the higher sericite powder of silica compositions, that is reference examples 2 is used, and silica compositions are 63%, particle diameter is the sericite powder of 3 ± 1um.Show that according to the experimental result shown in the table 1 the boring roughness of this copper-clad base plate rises to 1.02mil, its reason is the increase of silica composition, makes the hardness of sericite powder rise, and then causes the workability of copper-clad base plate to reduce.
Moreover reference examples 3 is that with embodiment 1 difference reference examples 3 is used the lower sericite powder of silica compositions, that is reference examples 3 is used, and silica compositions are 49%, particle diameter is the sericite powder of 3 ± 1um.Show according to the experimental result shown in the table 1, because other oxide components improves the reactivity between powder and the resin than increasing (like aluminum oxide, Natural manganese dioxide) relatively in the sericite powder; Cause the resin reaction voltinism to be affected; Therefore, from experimental data, visible resinifying glue time lengthening; Therefore made film/copper-clad base plate reactive not enough causes the requirement that falls short of specifications of rerum naturas such as copper-clad base plate thermotolerance low (float tin time shorter) and water-absorbent raising.
And reference examples 4 is with embodiment 1 difference; Reference examples 4 uses general silicon-dioxide commonly used to be mineral filler; The rerum natura of forming made copper-clad base plate with the resin of this reference examples 4 can satisfy product specification; But its boring roughness reaches more than the 1.2mil, and in other words, traditional mineral filler can't improve the workability of copper-clad base plate.
The present invention also further proposes a kind of method of above-mentioned composition epoxy resin manufacturing film and film of made moulding of using.This method is used above-mentioned composition epoxy resin, and it comprises component A: epoxy resin; B component: stiffening agent; Component C: promotor; Component D: stopping composition, it is the sericite powder, has the silicon-dioxide of 55 ± 3% weight in the composition of this sericite powder, the hardness of this sericite powder is Mohs' hardness 2 to 3.Glasscloth is flooded (dipping) in the glue of this composition epoxy resin; With the impregnation film (PP) of processing preferable anti-combustion and heat-resistant quality or contain copper clad laminate (Copper clad laminate; CCL) or other film; And above-mentioned film can be used the substrate (like the copper-clad base plate among the embodiment) of processing use in printed circuit board, and this substrate can have quite good processibility through bore process the time.
In sum, the present invention has following all advantage:
1. the present invention mainly utilizes the sericite powder of Mohs' hardness below 3 as the mineral filler in the resin combination, to improve the workability of using the made film/substrate of this resin adhesive liquid.
2. on the other hand, the present invention also further limits proportion of composing, the size of sericite powder, produces unnecessary reaction to avoid sericite powder and resin adhesive liquid.Therefore, the present invention can take into account the specification requirement such as low water absorbable and thermotolerance of film/substrate.
Only the above is merely preferred embodiment of the present invention, non-ly is intended to limit to scope of patent protection of the present invention, so the equivalence variation of using description of the present invention to do such as all in like manner all is contained in the rights protection scope of the present invention, closes and gives Chen Ming.
Claims (14)
1. a composition epoxy resin is characterized in that, comprising:
Component A: epoxy resin, this epoxy resin is: brominated phenols formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, four functional group's epoxy resin or above-mentioned two or more mixed resin;
B component: stiffening agent;
Component C: promotor;
Component D: stopping composition, it is the sericite powder, the silicon-dioxide that wherein has 55 ± 3% weight in the composition of this sericite powder, the hardness of this sericite powder is Mohs' hardness 2 to 3, the particle diameter of this sericite powder is 3 ± 1um.
2. composition epoxy resin as claimed in claim 1 is characterized in that: with respect to the component A of 100 weight parts, the consumption of this sericite powder of this component D is 30 parts.
3. composition epoxy resin as claimed in claim 2 is characterized in that: this B component: stiffening agent is a kind of phenolic aldehyde stiffening agent.
4. composition epoxy resin as claimed in claim 3 is characterized in that: this phenolic aldehyde stiffening agent is the bisphenol-A phenolic stiffening agent.
5. composition epoxy resin as claimed in claim 5 is characterized in that: with respect to the component A of 100 weight parts, the consumption of this bisphenol-A phenolic stiffening agent is 30 parts.
6. composition epoxy resin as claimed in claim 2 is characterized in that: component C: promotor is 2-ethyl-4-methylimidazole.
7. composition epoxy resin as claimed in claim 6 is characterized in that: with respect to the component A of 100 weight parts, the consumption of this 2-ethyl-4-methylimidazole is 0.06 part.
8. composition epoxy resin as claimed in claim 2 is characterized in that: also further comprise: component E: additive.
9. composition epoxy resin as claimed in claim 8 is characterized in that: this additive comprises interfacial agent.
10. composition epoxy resin as claimed in claim 9 is characterized in that: this interfacial agent is a silane coupling agent, and with respect to the component A of 100 weight parts, its consumption is 0.04 part.
11. composition epoxy resin as claimed in claim 2 is characterized in that: also further comprise: component F: solvent, with respect to the component A of 100 weight parts, the consumption of the solvent of this component F is 60 parts.
12. composition epoxy resin as claimed in claim 11 is characterized in that: the solvent of this component F comprises butanone, propylene glycol monomethyl ether, pimelinketone or the mixture of two or more aforementioned solvents arbitrarily.
13. one kind impregnated in the claim 1 to 12 film of made in each described composition epoxy resin with the glass adhesive plaster.
14. an application rights requires the substrate of the made printed substrate of 13 described films.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910168188XA CN102002208B (en) | 2009-09-03 | 2009-09-03 | Epoxy resin composition and adhesive sheet and substrate made by same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910168188XA CN102002208B (en) | 2009-09-03 | 2009-09-03 | Epoxy resin composition and adhesive sheet and substrate made by same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102002208A CN102002208A (en) | 2011-04-06 |
| CN102002208B true CN102002208B (en) | 2012-06-27 |
Family
ID=43809930
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910168188XA Active CN102002208B (en) | 2009-09-03 | 2009-09-03 | Epoxy resin composition and adhesive sheet and substrate made by same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102002208B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102286191B (en) * | 2011-05-04 | 2013-06-12 | 扬州润友复合材料有限公司 | High-temperature-resistant insulating composite material sheet and preparation method thereof |
| CN103118507A (en) * | 2013-01-31 | 2013-05-22 | 明光瑞智电子科技有限公司 | Production method of multilayer printed circuit board |
| CN103254463A (en) * | 2013-05-09 | 2013-08-21 | 明光新盈统大新材料有限公司 | Inorganic filler capable of improving drilling performance of copper-clad plate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1207401A (en) * | 1997-08-01 | 1999-02-10 | 无锡市化工研究设计院 | Process for preparing reinforced epoxy molding compound for commutator |
-
2009
- 2009-09-03 CN CN200910168188XA patent/CN102002208B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1207401A (en) * | 1997-08-01 | 1999-02-10 | 无锡市化工研究设计院 | Process for preparing reinforced epoxy molding compound for commutator |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102002208A (en) | 2011-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4697144B2 (en) | Epoxy resin composition for prepreg, prepreg, multilayer printed wiring board | |
| JP5293598B2 (en) | Resin composition, prepreg, laminate, multilayer printed wiring board, and semiconductor device | |
| CN103642446A (en) | Lead-free high heat-resisting copper-clad board and preparation method thereof | |
| CN102633990A (en) | Epoxy resin composition and prepreg and copper-clad laminate manufactured using it | |
| WO2011118584A1 (en) | Epoxy resin composition for prepreg, prepreg, and multilayer printed circuit board | |
| CN104559068A (en) | Thermosetting resin composition as well as preparation method and application thereof | |
| CN104559888A (en) | Copper-clad plate applicable to production of high multi-layer PCB (printed circuit board) and preparation method of copper-clad plate | |
| JP2010254819A (en) | Epoxy resin composition, prepreg, laminate and multilayer board | |
| CN103788576A (en) | Epoxy resin composition and preparation method thereof | |
| CN102002208B (en) | Epoxy resin composition and adhesive sheet and substrate made by same | |
| CN106751507B (en) | A kind of high heat epoxy and combinations thereof and application | |
| CN102260402A (en) | Epoxy resin composition and prepreg and printed circuit board made therefrom | |
| CN102040801A (en) | Epoxy resin composition and its film and substrate | |
| KR101289369B1 (en) | Epoxy resin composition, prepreg, laminate board and multilayer board | |
| CN106433124A (en) | Halogen-free resin composition containing ester curing agent for high-frequency and high-speed printed-circuit board | |
| CN106364122B (en) | A kind of production method of the unleaded low dielectric type copper coated foil plates of high Tg | |
| JP2009246026A (en) | Paste-like adhesive, and method of manufacturing substrate incorporating electronic components using the same | |
| CN101831139B (en) | Epoxy resin composition and film and substrate made thereof | |
| TWI423741B (en) | An epoxy resin composition and a film and a substrate made of the epoxy resin composition | |
| JP4858359B2 (en) | Epoxy resin composition for prepreg, prepreg, laminate and printed wiring board using the same | |
| JP4501475B2 (en) | Metal foil with insulating layer and multilayer printed wiring board | |
| JP2005048036A (en) | Prepreg and metal foil-clad laminate board using the same | |
| CN104341720B (en) | A kind of high-density printed circuit board resin coated copper foil halogen-free resin composition and its preparation method and application method | |
| JP2006036936A (en) | Epoxy resin composition, prepreg, and multilayer printed wiring board | |
| CN102477211A (en) | Halogen-free epoxy resin composition and film and substrate thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |