CN102088820B - 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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- CN102088820B CN102088820B CN2009102526631A CN200910252663A CN102088820B CN 102088820 B CN102088820 B CN 102088820B CN 2009102526631 A CN2009102526631 A CN 2009102526631A CN 200910252663 A CN200910252663 A CN 200910252663A CN 102088820 B CN102088820 B CN 102088820B
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- silicon dioxide
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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 whole performance of electronic product.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; Through drying, cutting, coinciding forms, single or double is covered with Copper Foil then, processes at heating and pressurizing condition compacted under.With the glass fiber 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 fiber 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, if can make that the coefficient of linear expansion of substrate is lower, with the improvement that more helps aforesaid substrate fine fisssure and line broken circuit.
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.
Be to realize above-mentioned purpose, copper clad laminate provided by the present invention includes at least one side that a glass fiber substrate and at least one Copper Foil be incorporated into this glass fiber substrate; Wherein this glass fiber substrate is to be contained by a glass fabric to be dipped in one and to contain in the immersion liquid; Consolidate film to process half; Partly consolidating film then combines Copper Foil after pressurized, heated, to process this copper clad laminate; Wherein this contains the filler that immersion liquid includes resin and 5-80PHR, and 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 fiber 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 subsequent use 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 fiber substrate both sides copper clad laminate 26; Whole copper clad laminate 26 structures consolidate film 18 by half of majority and 20 of at least one Copper Foils constitute, 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).
The composition that to the effect that is directed against copper clad laminate and contains immersion liquid of the present invention.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), magnesia (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 to be 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 is learnt, is selected from the element alundum (Al (Al like IIIA family like aforesaid metal oxide
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), magnesia (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), magnesia (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), magnesia (MgO) be best; Considering other character; Like 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%, magnesia (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, it is following aspect coefficient of linear expansion and boring of the copper clad laminate of silicon dioxide with commonly using filler:
Example one
Numbering A: known resinous principle when not filled is following:
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 admittedly the two-sided of film cover 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 following:
Numbering B: if in above-mentioned resinous principle, add silica filler, its proportioning is following:
After same repeatedly structure and Copper Foil hot pressing, it is following 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 following 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 following 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 following 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, like 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 following:
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 axle and Y axle 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 bore process ability and the drill bit loss comparison sheet of copper clad laminate numbering A, B, C, D and E of expression out of the ordinary can know and find out; No matter resin formula how, the boring number is healed when high, can be found out that by drill bit image the loss of drill bit 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 of silicon dioxide is high, cause 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 is merely 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 (2)
1. the immersion liquid that contains in order to the making copper clad laminate supplies the glass fiber sheets impregnation, consolidates film to process half; Partly consolidating film then combines Copper Foil after pressurized, heated, to process copper clad laminate; The filler that includes resin and 5-80PHR, wherein this filler is by silicon dioxide 50-62wt%, alundum (Al 11-19wt%; Diboron trioxide 4-13wt%; Calcium oxide 6-27wt%, magnesia＜6wt%, strontium oxide strontia＜1.5wt% and barium monoxide＜0.1wt% are total to the amorphism network structure composite wood that constitutes.
2. copper clad laminate includes at least one side that a glass fiber substrate and at least one Copper Foil be incorporated into this glass fiber substrate; Wherein this glass fiber substrate is by being made up of a glass fabric and an impregnation material; Wherein this impregnation material includes the filler of resin and 5-80PHR, and this filler is by silicon dioxide 50-62wt%, alundum (Al 11-19wt%; Diboron trioxide 4-13wt%; Calcium oxide 6-27wt%, magnesia＜6wt%, strontium oxide strontia＜1.5wt% and barium monoxide＜0.1wt% are total to the amorphism network structure composite wood that constitutes.
Priority Applications (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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|---|---|---|---|
| CN2009102526631A CN102088820B (en) | 2009-12-03 | 2009-12-03 | Copper clad laminate and impregnation liquid for making same |
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| Publication Number | Publication Date |
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| CN102088820A CN102088820A (en) | 2011-06-08 |
| CN102088820B true CN102088820B (en) | 2012-07-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| US9902880B2 (en) * | 2015-03-25 | 2018-02-27 | Panasonic Intellectual Property Management Co., Ltd. | Film material, electronic component using film material, and method for producing electronic component |
| CN106207447A (en) * | 2016-07-01 | 2016-12-07 | 杨浩昕 | A kind of resonant aerial |
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| CN101113323A (en) * | 2007-08-02 | 2008-01-30 | 刘光文 | Foam heat storage and method for preparing the same |
| CN101220160A (en) * | 2007-12-07 | 2008-07-16 | 广东生益科技股份有限公司 | Prepreg applied for multi-layer board of printed electronic circuit |
| CN101343402A (en) * | 2008-08-27 | 2009-01-14 | 南亚塑胶工业股份有限公司 | Resin composition with high-heat, high-glass transition temperature for printed circuit board, prepreg and coating substance |
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2009
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113323A (en) * | 2007-08-02 | 2008-01-30 | 刘光文 | Foam heat storage and method for preparing the same |
| CN101220160A (en) * | 2007-12-07 | 2008-07-16 | 广东生益科技股份有限公司 | Prepreg applied for multi-layer board of printed electronic circuit |
| CN101343402A (en) * | 2008-08-27 | 2009-01-14 | 南亚塑胶工业股份有限公司 | Resin composition with high-heat, high-glass transition temperature for printed circuit board, prepreg and coating substance |
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