CN101613530B - Resin composition and application thereof - Google Patents
Resin composition and application thereof Download PDFInfo
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- CN101613530B CN101613530B CN 200810100492 CN200810100492A CN101613530B CN 101613530 B CN101613530 B CN 101613530B CN 200810100492 CN200810100492 CN 200810100492 CN 200810100492 A CN200810100492 A CN 200810100492A CN 101613530 B CN101613530 B CN 101613530B
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Abstract
The present invention provides a resin composition, which comprises a solvent and a solid matter dissolved in the solvent, wherein the solid matter does not contain a phenolic resin; and the solid matter comprises a phosphorous epoxy resin and a benzoxazine resin. The weight ratio of the benzoxazine resin to the epoxy resin is about 0.6:1 to 3.0: 1. The invention also discloses a substrate and a copper-clad plate made of the resin composition.
Description
Technical field
The present invention relates to a kind of composition, and particularly relate to a kind of resin combination.
Background technology
The printed circuit board (PCB) development is the history of existing many decades so far.Be accompanied by the exploitation of various Novel electronic products, the use of printed circuit board (PCB) also gets over extensively.
In present printed circuit board (PCB) FEOL, mainly be to carry out the steps such as etching, boring in the copper-clad plate that comprises resin layer and Copper Foil, with the conducting wire on the formation printed circuit board (PCB) and via between layers.Be to improve the yield of printed circuit board technology, for thermal properties and the mechanical properties of resin layer in the aforementioned copper-clad plate specific requirement is arranged all.Therefore, developing various resin combinations of different nature is one of directions of present industry effort.
Summary of the invention
The embodiment of the invention proposes a kind of resin combination.
According to one embodiment of the invention, a kind of resin combination is proposed.This resin combination comprises solvent and the solid substance that is dissolved in the solvent.Solid substance does not contain resol, and this solid substance comprises phosphorous type Resins, epoxy and benzoxazine resin.The weight ratio of benzoxazine resin and phosphorous type Resins, epoxy is about 0.6: 1～and 3.0: 1.
According to another embodiment of the present invention, a kind of substrate is proposed.This substrate comprises strongthener and the hardening of resin thing that coats strongthener.Wherein, the hardening of resin thing is to be solidified by the described resin combination of previous embodiment to form.
According to yet another embodiment of the invention, a kind of copper-clad plate is proposed.This copper-clad plate comprises the described substrate of previous embodiment and Copper Foil.Copper Foil is arranged on the hardening of resin thing of substrate.
The described resin combination of the above embodiment of the present invention and copper-clad plate have heat-resistant quality and the dissipation loss characteristic of the copper-clad plate that is better than known resin composition and made thereof, can further improve the shipment quality of product.
Description of drawings
For above and other objects of the present invention, feature, advantage and embodiment can be become apparent, being described in detail as follows of accompanying drawing:
Fig. 1 illustrates the profile construction schematic diagram according to the described copper-clad plate of one embodiment of the invention;
Fig. 2 illustrates the indenture schematic diagram that produces in the described toughness test process of the embodiment of the invention.
Embodiment
Fig. 1 illustrates the profile construction schematic diagram according to the described copper-clad plate of one embodiment of the invention.In Fig. 1, copper-clad plate 100 comprises substrate 110, Copper Foil 120a and Copper Foil 120b.Substrate 110 comprises strongthener 112 and hardening of resin thing 114, and wherein, hardening of resin thing 114 coats strongthener 112.Copper Foil 120a and Copper Foil 120b lay respectively on the relative two sides of substrate 110.
The aforementioned resin hardening thing is to be solidified by resin combination to form.This resin combination comprises solvent and the solid substance that is dissolved in the solvent.Do not contain resol in the composition of solid substance, with the shipment quality (for example toughness or thermal properties) that improves its made hardening of resin thing.The composition of solid substance can comprise phosphorous type Resins, epoxy and benzoxazine resin (Benzoxazine resin), wherein, the weight ratio of benzoxazine resin and phosphorous type Resins, epoxy is about 0.6: 1～and 3.0: 1.Particularly, the content of phosphorous type Resins, epoxy is about 20～50wt% of solid substance (% by weight), and the content of benzoxazine resin is about 30～60wt% of solid substance.
Above-mentioned phosphorous type Resins, epoxy has the structure as shown in the formula I.A among the formula I and the chemical structure of B are as shown in the formula shown in the II.
The molecular-weight average of above-mentioned benzoxazine resin is about 800～1800.The benzoxazine resin is polymkeric substance, can have the structure shown in following formula III or the formula IV in its structure.
Above-mentioned resin combination also can comprise inorganic filler, and this inorganic filler for example can be silicon-dioxide, aluminium hydroxide, magnesium hydroxide, talcum powder or mica.The addition of above-mentioned inorganic filler is less than the 26wt% of the solid substance in the resin combination, so that the resin combination of suitable viscosity to be provided, with the making of convenient subsequent substrate 110.
In addition, for improving the dispersion effect of solid substance in solvent in the resin combination, also can further comprise dispersion agent, this dispersion agent for example can be silane coupling agent.In addition, this resin combination also can further comprise curing catalyst, and to improve the solidification effect of resin combination, this curing catalyst for example can be glyoxal ethyline (2-Methylimidazole; 2-MI (Z)), 2-phenylimidazole (2-Phenylimidazole; 2-PI (Z)) or 2-ethyl-4-methylimidazole (2-ethyl-4-methylimidazole; 2-E4MI (Z)).
Embodiment
Described according to the above-mentioned resin combination embodiment of the present invention, carry out the preparation of resin combination.At first, with phosphorous type Resins, epoxy, benzoxazine resin, curing catalyst 2-MI and solvent DMF (N, N-Dimethyl formamide; DMF) mix.Wherein, the molecular-weight average of benzoxazine resin is about 1000～1400, has the as above structure shown in the formula III in the resin structure.Phosphorous epoxy resin is the product of selecting the numbering LX6302 of Shanxi one chemical company series.
Then utilize stirrer to stir, and add as one feels fit dispersion agent silane coupling agent and inorganic filler and continue to stir, to finish the making of resin combination.Wherein, the solid content of resin combination is about 65wt%.
After above-mentioned resin combination completes, can carry out the making of follow-up copper-clad plate, production method is as described below.At first, glass-fiber-fabric is soaked in the resin combination.The glass-fiber-fabric that then, will soak again resin combination toasts.Afterwards, more aforementioned glass-fiber-fabric and the Copper Foil of finishing baking carried out hot pressing, to make double face copper or multilayer copper-clad plate.
After above-mentioned resin combination/copper-clad plate completes, further carry out water-intake rate, thermal properties, stripping strength, dielectric properties, combustioncharacteristics and toughness test, the property detection mode is as described below.
The test of water-intake rate is that the copper-clad plate that preparation is finished is placed 121 ℃ and 1.1kgf/cm
2Lower 1 hour of pressure cooker, test again its changes in weight.
The thermal properties test comprises thermotolerance, thermo-cracking temperature (thermal decomposition temperature; Td), glass transformation temperature (glass transition temperature; Tg) with the thermal expansion character test.Thermotolerance test is the multilayer copper-clad plate to be placed under 288 ℃ the tin stove time of test multi-ply wood generation layering plate bursting.The thermo-cracking temperature is according to the IPC-TM650 standard, the temperature when producing 5wt% weight loss with the TGA test material.Glass transformation temperature is according to the IPC-TM650 standard, tests with DSC.Thermal expansion character is according to the IPC-TM650 standard, tests the thickness increment rate the when copper-clad plate of testing experiment material is warming up to 260 ℃ by 50 ℃ with TMA.
Stripping strength is according to the IPC-TM650 standard, utilizes the property of following of Copper Foil and substrate in the omnipotent puller system test copper-clad plate.Dielectric properties is to test according to the IPC-TM650 standard.Combustioncharacteristics is to test according to UL94 vertical combustion mode.
The mode of toughness test is that the smelting tool with similar cross screw screwdriver is set up in omnipotent puller system, and the sensor of omnipotent puller system (load cell) is 1kN, and tool is apart from copper-clad plate 10mm.Follow the speed decline smelting tool with 20mm/min.When smelting tool decline 15mm, stop, and with the indenture of visual inspection material.
Fig. 2 illustrates the indenture schematic diagram that aforementioned toughness test produces.If cross by seeing in the indenture, then represent material tool toughness.As for the quantization degree of toughness, the size of the crack areas that is caused when then producing with the cross indenture is judged.At first, as shown in Figure 2, mark the zone of area A according to the cross indenture.Then,,, if then being considered as good toughness, institute's value≤20% represents with " O " divided by area A with the crack areas in the zone of area A, otherwise, then with " X " expression poor toughness.
Property analysis
Table 1 is listed the composition of solid substance in above-described embodiment, and (E1～E6) also provides the composition (R1～R3) as comparative example of the solid substance of the known resin composition that contains resol simultaneously.Table 2 is listed every character that the copper-clad plate that comprises resin combination that table 1 solid substance forms and made thereof records through the aforesaid properties test mode.
The composition of solid substance in table 1, the resin combination
| Composition | E1 | E2 | E3 | E4 | E5 | E6 | R1 | R2 | R3 |
| A. benzoxazine resin (wt%) | 59.8 | 47.9 | 47.9 | 35.1 | 35.1 | 26.9 | 49.8 | 41.6 | 20.8 |
| B. Resins, epoxy (wt%) | 21.6 | 33.3 | 33.3 | 45.7 | 45.7 | 53.7 | 22.2 | 34.7 | 60.6 |
| A, B weight resin ratio | 2.76 | 1.44 | 1.44 | 0.77 | 0.77 | 0.5 | 2.24 | 1.2 | 0.34 |
| Resol (wt%) | 0 | 0 | 0 | 0 | 0 | 0 | 11.6 | 10.4 | 5.2 |
| Aluminium hydroxide (wt%) | 15.5 | 11.5 | 4.2 | 0 | 16 | 16.1 | 15.9 | 13 | 13 |
| Silicon-dioxide (wt%) | 0 | 4.2 | 11.5 | 16 | 0 | 0 | 0 | 0 | 0 |
| Curing catalyst (wt%) | 3.1 | 3.1 | 3.1 | 3.2 | 3.2 | 3.2 | 0.35 | 0.35 | 0.35 |
| Dispersion agent (weight part/other solid substance of 100 weight parts) | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 |
The character of table 2, resin combination/copper-clad plate
Thickness increment rate when coefficient of thermal expansion refers to that copper-clad plate is warming up to 260 ℃ by 50 ℃.
While reference table 1 and table 2, the copper-clad plate of embodiment of the invention E1～E5 made has the water-intake rate that is lower than comparative example R1～R3, can make the copper-clad plate of better quality.Though the water-intake rate of embodiment E 6 is higher than comparative example R1～R2, but still lower than R3.
In heat-resisting test, do not contain time 〉=3 minute of multi-ply wood generation layering plate bursting of embodiment E 1～E6 made of resol, be better than the heat-resistant quality of comparative example R1～R3.And by embodiment E 2 and E3, and E4 and E5 relatively in, can find with silicon-dioxide can to obtain than the better heat-resistant quality of aluminium hydroxide as inorganic filler.
In the test of thermo-cracking temperature, glass transformation temperature and thermal expansion character, embodiment E 1～E5 has thermo-cracking temperature and the glass transformation temperature higher than comparative example R1～R3, and the coefficient of thermal expansion that is lower than comparative example R1～R3, has better thermostability.By the raising of thermostability, can make the copper-clad plate of its made bear higher technological temperature and service temperature.By in table 1 and the table 2 also as can be known, along with the decline (embodiment E 6) of the ratio of benzocyclobutene resin and Resins, epoxy, the situation that descends also appears in thermostability, but still is better than comparative example R3.
In the test of dielectric properties, the copper-clad plate of embodiment of the invention E1～E6 made has the dissipation loss coefficient Df that is lower than comparative example R1～R3.When the copper-clad plate of aforementioned low dissipation loss coefficient was applied to the high-frequency signals transmission, the situation that can avoid signal loss and signal to be disturbed occured.
On peel strength test, the resin combination of embodiment E 1～E6 made and the bond strength of Copper Foil also are better than comparative example R1～R3.On combustioncharacteristics, embodiment E 1～E6 can reach the grade of V-0.
On toughness test, by the diagram result as can be known, the indenture that the copper-clad plate of embodiment of the invention E1～E6 and comparative example R1～R3 made produces in test process all can be seen cross, has toughness to a certain degree.If further comparing embodiment E1～E6 and the cross of comparative example R1～R3 are found the crack areas less in the cross zone that consists of of E4～E5.Can know by inference thus, when the weight ratio of benzoxazine resin and phosphorous type Resins, epoxy is adjusted to approximately 0.77, the toughness of the copper-clad plate of its made the is increased to grade of " excellence ".
Although disclose the present invention by above-mentioned example; yet it is not to limit the present invention; any those skilled in the art can do various changes and modification without departing from the spirit and scope of the present invention, so protection scope of the present invention should be as the criterion with the content that claims were defined.
Claims (9)
1. resin combination comprises:
Solvent; And
Be dissolved in the solid substance in this solvent, wherein said solid substance does not contain resol, and described solid substance comprises:
Phosphorous type Resins, epoxy, the content of wherein said phosphorous type Resins, epoxy are 20～50wt% of described solid substance; And
The benzoxazine resin, the content of described benzoxazine resin is 30～60wt% of described solid substance, and the weight ratio of described benzoxazine resin and described phosphorous type Resins, epoxy is 0.77: 1, and described benzoxazine resin comprises the structure shown in the following Formulae II:
2. resin combination as claimed in claim 1 also comprises inorganic filler, and the addition of described inorganic filler is less than the 26wt% of described solid substance.
3. resin combination as claimed in claim 2, wherein said inorganic filler is silicon-dioxide, aluminium hydroxide, magnesium hydroxide, talcum powder or mica.
4. resin combination as claimed in claim 1 also comprises dispersion agent, and described dispersion agent is silane coupling agent.
5. resin combination as claimed in claim 1 also comprises curing catalyst, and described curing catalyst is selected from glyoxal ethyline, 2-phenylimidazole and 2-ethyl-4-methylimidazole.
6. substrate comprises:
Strongthener; And
Coat the hardening of resin thing of described strongthener, described hardening of resin thing is formed by each described resin combination curing in the claim 1～5.
7. substrate as claimed in claim 6, wherein said strongthener is glass-fiber-fabric.
8. copper-clad plate comprises:
Substrate, it comprises:
Strongthener; And
Coat the hardening of resin thing of described strongthener, described hardening of resin thing is formed by each described resin combination curing in the claim 1～5; And
Copper Foil is arranged on the described hardening of resin thing of described substrate.
9. copper-clad plate as claimed in claim 8, wherein said strongthener is glass-fiber-fabric.
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| CN 200810100492 CN101613530B (en) | 2008-06-23 | 2008-06-23 | Resin composition and application thereof |
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| CN 200810100492 CN101613530B (en) | 2008-06-23 | 2008-06-23 | Resin composition and application thereof |
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| CN101613530A CN101613530A (en) | 2009-12-30 |
| CN101613530B true CN101613530B (en) | 2013-01-02 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102373621B (en) * | 2010-08-20 | 2014-01-22 | 南亚塑胶工业股份有限公司 | Resin varnish composition with high temperature of glass transition for glass fiber laminated plate use |
| CN102002235B (en) * | 2010-11-15 | 2012-07-25 | 烟台德邦电子材料有限公司 | Method for reducing thermal expansion coefficient of polybenzoxazine-based underfill |
| CN102838729B (en) * | 2011-06-22 | 2015-02-11 | 台燿科技股份有限公司 | Resin composition and prepreg and laminated board prepared from same |
| CN103554437B (en) * | 2013-09-04 | 2016-08-17 | 东莞联茂电子科技有限公司 | A kind of IC encapsulation halogen-free epoxy resin composition |
| CN103963414B (en) * | 2014-05-27 | 2016-03-23 | 铜陵浩荣华科复合基板有限公司 | The fire-retardant High Tg CCL preparation method of a kind of halogen-free and lead-free |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5945222A (en) * | 1996-02-09 | 1999-08-31 | Hitachi Chemical Company, Ltd. | Thermosetting resin composition, cured product, prepreg, metal-clad laminate and wiring board |
| CN1548473A (en) * | 2003-05-09 | 2004-11-24 | 广州宏仁电子工业有限公司 | Glue liquid no-halide fire-retardant copper-clad plate with the glue liquid and its making process |
| CN1667073A (en) * | 2005-03-23 | 2005-09-14 | 中山大学 | Halogen-free flame resistant adhesive for preparing laminated sheet |
| CN100999145A (en) * | 2005-12-31 | 2007-07-18 | 四川东材企业集团有限公司 | Preparation method of glass transition temperature halogenless fire retardant glass cloth laminated board |
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2008
- 2008-06-23 CN CN 200810100492 patent/CN101613530B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5945222A (en) * | 1996-02-09 | 1999-08-31 | Hitachi Chemical Company, Ltd. | Thermosetting resin composition, cured product, prepreg, metal-clad laminate and wiring board |
| CN1548473A (en) * | 2003-05-09 | 2004-11-24 | 广州宏仁电子工业有限公司 | Glue liquid no-halide fire-retardant copper-clad plate with the glue liquid and its making process |
| CN1667073A (en) * | 2005-03-23 | 2005-09-14 | 中山大学 | Halogen-free flame resistant adhesive for preparing laminated sheet |
| CN100999145A (en) * | 2005-12-31 | 2007-07-18 | 四川东材企业集团有限公司 | Preparation method of glass transition temperature halogenless fire retardant glass cloth laminated board |
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Effective date of registration: 20180117 Address after: Xishan Economic Development Zone, Wuxi, Jiangsu Patentee after: Lianmao (Wuxi) Electronics Technology Co., Ltd. Address before: Taiwan Taoyuan County Pingjhen City Industrial Road No. 22 Chinese Patentee before: Iteq Electronic Co., Ltd. |