CN102088820A - Copper clad laminate and impregnation liquid for making same - Google Patents
Copper clad laminate and impregnation liquid for making same Download PDFInfo
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- CN102088820A CN102088820A CN2009102526631A CN200910252663A CN102088820A CN 102088820 A CN102088820 A CN 102088820A CN 2009102526631 A CN2009102526631 A CN 2009102526631A CN 200910252663 A CN200910252663 A CN 200910252663A CN 102088820 A CN102088820 A CN 102088820A
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- oxide
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Abstract
The invention relates to a copper clad laminate comprising a glass fiber substrate and at least one copper foil combined on at least one side surface of the glass fiber substrate, wherein the glass fiber substrate is formed by the steps of impregnating a piece of glass fiber cloth in an impregnation liquid to prepare a half-solid film and then combining the half-solid film with the copper foils to prepare the copper clad laminate through pressuring and heating, wherein the impregnation liquid comprises a resin and a filler of 5-80 PHR (Parts per Hundreds of Resin), and the filler is a non-crystalline net-structured composite material which is co-constituted by silicon dioxide and one or more of IIA or IIIA metallic oxides. The copper clad laminate has appropriate hardness and linear expansion coefficient.
Description
Technical field
The present invention is relevant with electronic circuit, is meant a kind of copper clad laminate in more detail and is used for making that this copper clad laminate is employed contains immersion liquid.
Background technology
(printed circuit board PCB) for having the substrate of scheduled circuit layout (pattern), can be equiped with various electronic building brick, to reach intended function to printed circuit board (PCB) on it.The quality of printed circuit board (PCB) not only influences the reliability of electronic product, also influences the performance of electronic product integral body.Copper clad laminate (copper clad laminate, CCL) then be the basic material of making printed circuit board (PCB), be to utilize insulating paper, glass fabric or other fiber material to soak with epoxy resin or phenolic resin adhesive, drying, cutting, coinciding forms, single or double is covered with Copper Foil then, makes at heating and pressurizing condition compacted under.With the glass fibre is the copper clad laminate of substrate, owing to have favorable mechanical character, has become the main flow of copper clad laminate.
In known technology, there is the people to add some fillers to improve the engineering properties of substrate at the glass fibre copper clad laminate, modal filler is a silicon dioxide.The tetrahedron network structure type crystallization meeting of silicon dioxide improves the hardness and the linear expansion coefficient that reduces substrate of substrate.The substrate of high rigidity has on-deformable advantage, yet when needs were holed, the degree of difficulty of bore process was than higher, and the loss of drill bit also therefore improves.In addition, the process of boring produces too much break flour, also makes fraction defective improve.In addition, because the difference of the linear expansion coefficient of substrate and other material, high linear expansion coefficient can cause the generation of internal stress.Under the technology that colds and heat succeed each other, cause substrate fine fisssure and line broken circuit easily.Though the substrate that with silicon dioxide is filler has lower coefficient of linear expansion,, the improvement of aforesaid substrate fine fisssure and line broken circuit will be helped more if can make that the coefficient of linear expansion of substrate is lower.
Summary of the invention
The object of the present invention is to provide a kind ofly to contain immersion liquid and produced copper clad laminate thereof in order to what make copper clad laminate, this copper clad laminate is the substrate with suitable hardness and coefficient of linear expansion.
For achieving the above object, copper clad laminate provided by the present invention includes at least one side that a glass fibre substrate and at least one Copper Foil be incorporated into this glass fibre substrate; Wherein this glass fibre substrate is to be contained by a glass fabric to be dipped in one and to contain in the immersion liquid, consolidate film to make half, partly consolidate film then and after pressurized, heated, make this copper clad laminate in conjunction with Copper Foil, wherein this contains the filler that immersion liquid includes resin and 5-80PHR, wherein this filler is to have silicon dioxide and at least a IIA or IIIA family metal oxide to be total to the amorphism network structure composite material that constitutes, and has suitable hardness and coefficient of linear expansion with this produced copper clad laminate.
Description of drawings
Fig. 1 is for making the process schematic representation of copper clad laminate.
Fig. 2 is bore process ability and the drill bit loss comparison sheet of copper clad laminate numbering A.
Fig. 3 is bore process ability and the drill bit loss comparison sheet of copper clad laminate numbering B.
Fig. 4 is bore process ability and the drill bit loss comparison sheet of copper clad laminate numbering C.
Fig. 5 is bore process ability and the drill bit loss comparison sheet of copper clad laminate numbering D.
Fig. 6 is bore process ability and the drill bit loss comparison sheet of copper clad laminate numbering E.
Primary clustering symbol description in the accompanying drawing
10 glass fabrics 12 contain immersion trough
14 heaters, 16 cutters
18 half solid film 20 Copper Foils
22 hot moulding film-makings 24 are pruned
26 copper clad laminates
Embodiment
Fig. 1 shows the technology of general making glass fibre copper clad laminate, comprising having: glass fabric 10 is delivered to one contain in the immersion trough 12, the immersion liquid of containing is wherein arranged.After a heater 14 heating, be cut into preliminary dimension with cutter 16 afterwards, film 18 is standby admittedly to form some half.Then, half of predetermined quantity is consolidated film 18 with predetermined fiber orientation storehouse together, and one Copper Foil 20 respectively is set, carry out hot moulding film-making 22 and do at end face and bottom surface.Plate after the hot moulding, after suitable pruning 24, can obtain central authorities all have Copper Foil for glass fibre substrate both sides copper clad laminate 26, whole copper clad laminate 26 structures consolidate film 18 by half of majority and at least one Copper Foil 20 is constituted, and wherein respectively being somebody's turn to do partly admittedly, film 18 is constituted by glass fabric 10 and impregnation material (liquid-solidization of impregnation back).
Of the present invention to the effect that at copper clad laminate and contain the composition of immersion liquid.The Main Ingredients and Appearance that the present invention contains immersion liquid is resin (the present invention adopt be epoxy resin), and (that is the percentage by weight of resin and filler is=100: 5-80) to be added with the filler of 5-80PHR (PerHundred Resin) in addition.The Main Ingredients and Appearance of this filler includes silicon dioxide (SiO
2), alundum (Al (Al
2O
3), diboron trioxide (B
2O
3), calcium oxide (CaO), magnesium oxide (MgO), strontium oxide strontia (SrO) and barium monoxide (BaO), and this filler is the amorphism network structure composite wood that mentioned component is total to formation. Wherein the ratio of this filler of silica comprises is 50wt%～80wt%, is 20wt%～50wt% and this each metal oxide accounts for the ratio of this filler altogether.
The main component of filler of the present invention is a silicon dioxide, its function as previously mentioned, by the hardness of tetrahedron network structure type crystallization can the raising substrate of silicon dioxide with reduce linear expansion coefficient.All the other compositions of filler of the present invention are roughly metal oxide, and the metal of aforesaid metal oxide can be selected from periodic table IIA family's element or IIIA family element.Infiltrate by metal oxide in the network structure of silicon dioxide, make metallic atom occupy the position of silicon atom in the original network structure, cause the tetrahedron network structure destroyed, and form the metal oxide of noncrystalline shape and the composite material of silicon dioxide.Because this composite material is a non-crystalline type, compare with powdered quartz, non-crystalline type composite material of the present invention has lower hardness; Even compare with non-crystalline type silicon dioxide, the present invention also has lower hardness.
Experimental result according to the present invention learns that metal oxide is selected from the element alundum (Al (Al as IIIA family as the aforementioned
2O
3), diboron trioxide (B
2O
3) or the combination of wherein a kind of or above any two (or two or more) metal oxides of IIA family element calcium oxide (CaO), magnesium oxide (MgO), strontium oxide strontia (SrO) and barium monoxide (BaO), it can reduce hardness, makes the proportion of goods damageds of drill bit reduce; And, learn through experiment, in above-mentioned metal oxide, if add the IIIA element alundum (Al (Al of family
2O
3), diboron trioxide (B
2O
3) or during the combination of wherein a kind of or above any two (or two or more) metal oxides of IIA family element calcium oxide (CaO), magnesium oxide (MgO), have more the effect that reduces coefficient of linear expansion.
Therefore, in the application of copper clad laminate, with the above-mentioned IIIA element alundum (Al (Al of family
2O
3), diboron trioxide (B
2O
3) or the composition of the metal oxide of IIA family element calcium oxide (CaO), magnesium oxide (MgO) be best, considering other character, as chemical durability or have under the lower conditions such as dielectric constant, the preferable weight proportion relation of filler of the present invention is: silicon dioxide (SiO
2) 50-62%, alundum (Al (Al
2O
3) 11-19%, diboron trioxide (B
2O
3) 4-13%, calcium oxide (CaO) 6-27%, magnesium oxide (MgO)＜6%, strontium oxide strontia (SrO)＜1.5% and barium monoxide (BaO)＜0.1%.
With above-mentioned proportion relation serves as the basis down, the present invention adopts filler, its with commonly use filler be the copper clad laminate of silicon dioxide being compared as follows aspect coefficient of linear expansion and the boring:
Example one
Numbering A: known resinous principle when not filled is as follows:
The glass cloth that uses during impregnation is 7628, after the impregnation when 170 degree C solidify 3 minutes, repeatedly behind 5 layers of the structures, half film two-sided admittedly coated with 1/2oz/ft
2Copper Foil and be heated to 170 degree C and solidified one hour, a copper clad laminate thickness be 0.95mm.
Carry out following test with above-mentioned copper clad laminate, its result is as follows:
Numbering B: if add silica filler in above-mentioned resinous principle, its proportioning is as follows:
After same repeatedly structure and Copper Foil hot pressing, it is as follows to test its characterization result:
Relatively the two data can be known understanding, and behind the adding 2um silicon dioxide, Tg increases and coefficient of linear expansion reduces.
Numbering C: keeping and numbering identical the containing under immersion liquid (resin the is filled) ratio of B, if above-mentioned filler changes the metal oxide composite (D50=2um) of following composition into:
After same repeatedly structure and Copper Foil hot pressing, it is as follows to test its characterization result:
By on can get conclusion:
When being filler with the metal oxide composite wood in this example, can be when the being filler lower coefficient of expansion with silicon dioxide.
Example two
Numbering D: as above the change of the component ratio of filler is as follows:
After same repeatedly structure and Copper Foil hot pressing, it is as follows to test its characterization result:
Numbering E: keeping and numbering identical the containing under immersion liquid (resin the is filled) ratio of D, if above-mentioned filler changes the metal oxide composite (D50=2um) of following composition into
After same repeatedly structure and Copper Foil hot pressing, it is as follows to test its characterization result:
Relatively go up example, proportion of filler is higher, and Tg is higher, and the coefficient of expansion is lower, and its effect is more obvious when using the metal oxide composite wood as filler.
Example three
The copper clad laminate of made numbering A, B, C, D and E carry out borehole test simultaneously in above-mentioned two examples, as following table:
At the silicon dioxide composition, metal oxide composite wood composition, the same two examples of the technology of impregnation and Copper Foil hot pressing, borehole conditions is as follows:
Bore process ability and the drill bit loss comparison sheet of the copper clad laminate that obtains numbering A, B, C, D and E represent with Fig. 2, Fig. 3, Fig. 4, Fig. 5 and Fig. 6 respectively, wherein the bore process ability is defined as: the back mean place is an initial point to hole, X-axis and Y-axis are the bound specification with positive and negative 2mm, calculate the bore process ability; Drill bit loss situation is then observed the order of severity of drill bit loss by drill bit image.
By Fig. 2, Fig. 3, Fig. 4, Fig. 5 and Fig. 6 the bore process ability of copper clad laminate numbering A, B, C, D and E of expression out of the ordinary and drill bit loss comparison sheet can know and find out, no matter resin formula how, the boring number is healed when high, the loss that can be found out drill bit by drill bit image increases, thereby drill bit waves greatly, the precision variation causes the technological ability variation of boring, and the Cpk value diminishes.
If add single silica filler, because the hardness height of silicon dioxide causes the degree of difficulty of boring to increase, the loss of above-mentioned drill bit is more obvious, and when height boring number, its precision also worsens rapidly.The addition of silicon dioxide the more, this kind phenomenon is more serious.
If add the metal oxide composite wood among the present invention, because itself belongs to the network structure of non-crystalline type, hardness is low, compared to single silicon dioxide, when height boring number, so drill bit loss and very nearly the same when not filled is still can keep well holing precision and bore process ability preferably.When proportion of filler heals when high and single silicon dioxide is compared, the metal oxide composite wood among the present invention more can manifest its low drill bit loss and the better characteristic of bore process ability.
The above only is the preferable possible embodiments of the present invention, uses the equivalent structure variation that specification of the present invention and interest field are done such as, ought to be included in the claim scope of the present invention.
Claims (14)
1. immersion liquid that contains in order to the making copper clad laminate, for the glass fiber sheets impregnation, consolidate film to make half, partly consolidate film then and after pressurized, heated, make copper clad laminate in conjunction with Copper Foil, the filler that includes resin and 5-80PHR, wherein this filler is to have silicon dioxide and at least a metal oxide to be total to the amorphism network structure composite wood that constitutes, wherein the ratio of this filler of silica comprises is 50wt%～80wt%, is 20wt%～50wt% and metal oxide accounts for the ratio of this filler.
2. as claimed in claim 1 in order to make the immersion liquid that contains of copper clad laminate, wherein, this metal oxide is selected from the oxide of periodic table IIA family element.
3. as claimed in claim 1 in order to make the immersion liquid that contains of copper clad laminate, wherein, the metal in this metal oxide is a periodic table IIIA family element.
4. as claimed in claim 1 in order to make the immersion liquid that contains of copper clad laminate, wherein, the metal of this metal oxide is to be selected from the oxide of periodic table IIA family element or the oxide of periodic table IIIA family element.
5. as claimed in claim 1 in order to make the immersion liquid that contains of copper clad laminate, wherein, the metal of this metal oxide is the combination that is selected from the oxide of the oxide of periodic table IIA family element and periodic table IIIA family element.
6. as claimed in claim 5 in order to make the immersion liquid that contains of copper clad laminate, wherein, the metal oxide of IIIA family element be selected from alundum (Al, diboron trioxide wherein one or more, the metal oxide of IIA family element be selected from calcium oxide, magnesium oxide, strontium oxide strontia and barium monoxide wherein one or more.
7. as claimed in claim 6 in order to make the immersion liquid that contains of copper clad laminate, wherein, this filler contains silicon dioxide 50-62wt%, alundum (Al 11-19wt%, diboron trioxide 4-13wt%, calcium oxide 6-27wt%, magnesium oxide＜6wt%, strontium oxide strontia＜1.5wt% and barium monoxide＜0.1wt%.
8. copper clad laminate includes at least one side that a glass fibre substrate and at least one Copper Foil be incorporated into this glass fibre substrate; Wherein this glass fibre substrate is by being made of a glass fabric and an impregnation material, wherein this impregnation material includes the filler of resin and 5-80PHR, and this filler has silicon dioxide and at least a metal oxide is total to the amorphism network structure composite wood that constitutes.
9. copper clad laminate as claimed in claim 8, wherein, this metal oxide is selected from the oxide of periodic table IIA family element.
10. copper clad laminate as claimed in claim 8, wherein, the metal in this metal oxide is a periodic table IIIA family element.
11. copper clad laminate as claimed in claim 8, wherein, the metal of this metal oxide is to be selected from the oxide of periodic table IIA family element or the oxide of periodic table IIIA family element.
12. copper clad laminate as claimed in claim 8, wherein, the metal of this metal oxide is the combination that is selected from the oxide of the oxide of periodic table IIA family element and periodic table IIIA family element.
13. copper clad laminate as claimed in claim 12, wherein, the metal oxide of IIIA family element be selected from alundum (Al, diboron trioxide wherein one or more, the metal oxide of IIA family element be selected from calcium oxide, magnesium oxide, strontium oxide strontia and barium monoxide wherein one or more.
14. copper clad laminate as claimed in claim 13, wherein, this filler contains silicon dioxide 50-62wt%, alundum (Al 11-19wt%, diboron trioxide 4-13wt%, calcium oxide 6-27wt%, magnesium oxide＜6wt%, strontium oxide strontia＜1.5wt% and barium monoxide＜0.1wt%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102526631A CN102088820B (en) | 2009-12-03 | 2009-12-03 | Copper clad laminate and impregnation liquid for making same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102526631A CN102088820B (en) | 2009-12-03 | 2009-12-03 | Copper clad laminate and impregnation liquid for making same |
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| CN102088820A true CN102088820A (en) | 2011-06-08 |
| CN102088820B CN102088820B (en) | 2012-07-04 |
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| CN102936097A (en) * | 2011-08-16 | 2013-02-20 | 苏州锦艺新材料科技有限公司 | Glass micropowder and preparation method thereof |
| CN102942304A (en) * | 2011-08-16 | 2013-02-27 | 苏州锦艺新材料科技有限公司 | Soft glass micro-powder and preparation method thereof |
| CN103304144A (en) * | 2012-03-09 | 2013-09-18 | 重庆市锦艺硅材料开发有限公司苏州分公司 | Micro glass powder and preparation method thereof |
| CN103304144B (en) * | 2012-03-09 | 2015-07-15 | 重庆市锦艺硅材料开发有限公司 | Micro glass powder and preparation method thereof |
| CN103359944A (en) * | 2012-03-26 | 2013-10-23 | 重庆市锦艺硅材料开发有限公司苏州分公司 | Soft glass micro powder and preparation method thereof |
| CN103359944B (en) * | 2012-03-26 | 2015-07-22 | 重庆市锦艺硅材料开发有限公司 | Soft glass micro powder and preparation method thereof |
| CN103360621A (en) * | 2013-07-02 | 2013-10-23 | 连云港东海硅微粉有限责任公司 | Packing in metal-clad foil plate with low thermal expansion coefficient and preparation method of packing |
| CN103360621B (en) * | 2013-07-02 | 2016-05-25 | 江苏联瑞新材料股份有限公司 | Filler in a kind of clad with metal foil plate with low thermal coefficient of expansion and preparation method thereof |
| CN106003935A (en) * | 2015-03-25 | 2016-10-12 | 松下知识产权经营株式会社 | Film material, electronic component using film material, and method for producing electronic component |
| CN106003935B (en) * | 2015-03-25 | 2019-10-01 | 松下知识产权经营株式会社 | Membrane material and used it electronic component and electronic component manufacturing method |
| CN106207447A (en) * | 2016-07-01 | 2016-12-07 | 杨浩昕 | A kind of resonant aerial |
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|---|---|
| CN102088820B (en) | 2012-07-04 |
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