CN102775735B - Halogen-free resin composition, resin coated copper foil prepared from same, and copper clad laminate - Google Patents
Halogen-free resin composition, resin coated copper foil prepared from same, and copper clad laminate Download PDFInfo
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- CN102775735B CN102775735B CN201210290617.2A CN201210290617A CN102775735B CN 102775735 B CN102775735 B CN 102775735B CN 201210290617 A CN201210290617 A CN 201210290617A CN 102775735 B CN102775735 B CN 102775735B
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Abstract
The invention provides a halogen-free resin composition. The halogen-free resin composition comprises the following components in parts by weight: 15-25 parts of bisphenol A-type epoxy resin, 10-20 parts of alicyclic epoxy resin, 40-50 parts of anhydride, 8-20 parts of phosphorus-containing phenoxy and 5-8 parts of phosphorus-containing flame retardant. The invention also provides resin coated copper foil which is prepared from the halogen-free resin composition and comprises copper foil and the halogen-free resin composition which is attached on one or two faces of the copper foil after being coated and dried by roasting. The invention also provides a copper clad laminate prepared from the resin coated copper foil and comprises two pieces of resin coated copper foil and an epoxy resin bonding sheet positioned between the two pieces of resin coated copper foil. The resin coated copper foil and the copper clad laminate have a comparative tracking index (CTI) of being greater than or equal to 600V, are excellent in heat resistance and alkali resistance, and meet the halogen-free and flame-retardant requirements.
Description
Technical field
The present invention relates to copper-clad laminate field, relate in particular to a kind of halogen-free resin composition and use its resin coated copper foil of preparing and copper-clad laminate.
Background technology
Copper-clad laminate is widely used in various electronics, electric product as the insulating substrate of printed circuit board.Along with people more and more pay attention to the safe reliability of electronics, electric product, to the safe reliability of copper-clad laminate is corresponding more and more higher requirement proposed, wherein proof tracking is exactly an important reliability index of copper-clad laminate, and the poor copper-clad laminate of proof tracking is the potential risk that electronics, electric product fire produce.So copper-clad laminate must improve its proof tracking, have compared with its safe reliability of high phase ratio creepage tracking index (CTI) value guarantee.
Traditional resin coated copper foil with high phase ratio creepage tracking index and the making method of copper-clad laminate are to realize by adding the resin combination of filling aluminium hydrate, resin coated copper foil and the copper-clad laminate of the high phase ratio creepage tracking index (phase ratio creepage tracking index value is greater than 600V) of this kind of method making need to add a large amount of filling aluminium hydrates, make the decline of sheet material processibility, thermotolerance and alkali resistance poor.
Existing copper-clad laminate with in ordinary epoxy resin owing to containing a large amount of phenyl ring, make common FR-4(epoxy glass fiber cloth veneer sheet) anti creepage trace performance poor, phase ratio creepage tracking index value generally can not surpass 250V.
Summary of the invention
The object of the present invention is to provide a kind of halogen-free resin composition, it has excellent proof tracking, thermotolerance and alkali resistance.
Another object of the present invention is to provide a kind of resin coated copper foil and copper-clad laminate, the phase ratio creepage tracking index of this resin coated copper foil and copper-clad laminate (CTI) >=600V, good heat resistance, alkali resistance are excellent, and reach halogen-free flameproof requirement.
For achieving the above object, the invention provides a kind of halogen-free resin composition, comprise component and weight part is as follows: bisphenol A type epoxy resin, 15-25 weight part; Cycloaliphatic epoxy resin, 10-20 weight part; Acid anhydrides, 40-50 weight part; Phosphorous phenoxy resin, 8-20 weight part; Phosphonium flame retardant, 5-8 weight part.
The epoxy equivalent (weight) of described bisphenol A type epoxy resin is 350-550g/eq.
The epoxy equivalent (weight) of described cycloaliphatic epoxy resin is 100-200g/eq, and its molecular structural formula is as follows:
The phosphorus content of described phosphorous phenoxy resin is 3.0%-6.0%, and its molecular weight is 1-10 ten thousand.
Described acid anhydrides is tung oil acid anhydride, alkylene Succinic anhydried, methyl hexahydrophthalic acid anhydride, hydrogenation methyl carbic anhydride, Pyroglutaric acid, poly-nonane diacid acid anhydride, poly-petrosilane diacid anhydride or modified poly acid anhydrides, and its anhydride equivalent is 500-800g/eq.
Described acid anhydrides is preferably modified poly acid anhydrides.
Described halogen-free resin composition also comprises promotor and solvent, and described promotor is glyoxal ethyline or 2-ethyl-4-methylimidazole, and its weight part is 0.01-0.5 part; Described solvent is butanone, and its weight part is 30-100 part.
Cycloaliphatic epoxy resin (epoxidation alicyclic olefin compound) is the low molecular compound that contains two alicyclic ring epoxy group(ing), itself is not polymkeric substance, but with solidifying agent effect after can generate the polymkeric substance of the three-dimensional three dimensional structure of excellent performance.Its composition principle is different from Racemic glycidol type epoxy resin, and the epoxy group(ing) in molecule is to utilize the double bond epoxidation of unsaturated lipid cyclic cpds to form.Industrially normally by the alicyclic olefin compound that contains two two keys, through the oxygenizement of superoxide (as peroxidation acetic acid), form epoxidation alicyclic olefin compound.In the molecular structure of cycloaliphatic epoxy resin, there is no phenyl ring and hydroxyl, and not chloride and sodium plasma in building-up process, so good electrical property, especially anti creepage trace performance are excellent.
In halogen-free resin composition of the present invention, by bisphenol A type epoxy resin and cycloaliphatic epoxy resin collocation are used, and pass through anhydride-cured, can be used for the copper-clad laminate that preparation has the resin coated copper foil of high phase ratio creepage tracking index (phase ratio creepage tracking index value is greater than 600V) and uses its making, and this copper-clad laminate has thermotolerance, the excellent feature of alkali resistance, reaches the requirement of halogen-free flameproof.
The present invention also provides a kind of resin coated copper foil that uses described halogen-free resin composition to prepare, and comprises Copper Foil and applies the rear dry halogen-free resin composition on Copper Foil one or both sides that is attached to that toasts.
The present invention also provides a kind of copper-clad laminate that uses described resin coated copper foil to prepare, and comprises two described resin coated copper foils and the epoxy bond sheet between two described resin coated copper foils.
Described epoxy bond sheet is epoxy glass fiber cloth bonding sheet.
Beneficial effect of the present invention: 1. described halogen-free resin composition is by bisphenol A type epoxy resin, phosphorous phenoxy resin and cycloaliphatic epoxy resin collocation, and add acid anhydrides as solidifying agent, make this halogen-free resin composition there is excellent proof tracking, thermotolerance and alkali resistance; 2. described resin coated copper foil and copper-clad laminate, use above-mentioned halogen-free resin composition to prepare, the phase ratio creepage tracking index of this resin coated copper foil and copper-clad laminate (CTI) >=600V, good heat resistance, alkali resistance are excellent, and reach halogen-free flameproof requirement; 3. described halogen-free resin composition and using in its resin coated copper foil of preparing and copper-clad laminate containing filler, thus avoided adding the problem that processibility, thermotolerance and alkalescence that filler brings decline.
In order further to understand feature of the present invention and technology contents, refer to following relevant detailed description of the present invention.
Embodiment
Technique means and the effect thereof for further setting forth the present invention, taked, be described in detail below in conjunction with the preferred embodiments of the present invention.
The invention provides a kind of halogen-free resin composition, comprise component and weight part is as follows: bisphenol A type epoxy resin, 15-25 weight part; Cycloaliphatic epoxy resin, 10-20 weight part; Acid anhydrides, 40-50 weight part; Phosphorous phenoxy resin, 8-20 weight part; Phosphonium flame retardant, 5-8 weight part.
The epoxy equivalent (weight) of described bisphenol A type epoxy resin is 350-550g/eq.
The epoxy equivalent (weight) of described cycloaliphatic epoxy resin is 100-200g/eq, and its molecular structural formula is as follows:
The phosphorus content of described phosphorous phenoxy resin is 3.0%-6.0%, and its molecular weight is 1-10 ten thousand.
Described acid anhydrides is tung oil acid anhydride, alkylene Succinic anhydried, methyl hexahydrophthalic acid anhydride, hydrogenation methyl carbic anhydride, Pyroglutaric acid, poly-nonane diacid acid anhydride, poly-petrosilane diacid anhydride or modified poly acid anhydrides, and its anhydride equivalent is 500-800g/eq.
Described acid anhydrides is preferably modified poly acid anhydrides.
Described halogen-free resin composition also comprises promotor and solvent, and described promotor is glyoxal ethyline or 2-ethyl-4-methylimidazole, and its weight part is 0.01-0.5 part; Described solvent is butanone, and its weight part is 30-100 part.
The present invention also provides a kind of resin coated copper foil that uses described halogen-free resin composition to prepare, and comprises Copper Foil and applies the rear dry halogen-free resin composition on Copper Foil one or both sides that is attached to that toasts.
The present invention also provides a kind of copper-clad laminate that uses described resin coated copper foil to prepare, and comprises two described resin coated copper foils and the epoxy bond sheet between two described resin coated copper foils.Described epoxy bond sheet is epoxy glass fiber cloth bonding sheet.
Several epoxy glass fiber cloth bonding sheets are superimposed, then two resin coated copper foils with halogen-free resin composition one side are superimposed on respectively on the upper and lower surface of the epoxy glass fiber cloth bonding sheet after superimposed.
For the copper-clad laminate of above-mentioned preparation, test the performances such as its phase ratio creepage tracking index (CTI), resistance to immersed solder, thermal shocking number of times, alkali resistance and incendivity, as following embodiment further describes in detail and describes.
Embodiment 1:
The halogen-free resin composition that is total up to 100 weight parts comprises: bisphenol A type epoxy resin (HEXION, Epikote1001) 15 parts, cycloaliphatic epoxy resin (DOW Chemical, ERL-4221D) 20 parts, acid anhydrides (DOW Chemical, XUR-16) 50 parts, phosphorous phenoxy resin (Nippon Steel's chemistry, ERF-001) 8 parts, 7 parts of phosphonium flame retardants (Clariant, EXOLIT OP935).In said composition, add again promotor (glyoxal ethyline) 0.2 weight part and solvent (butanone) 50 weight parts can be made into glue, on coating machine, scattered glue is coated on electrolytic copper foil, at 155 ℃, baking oven, toasts and within 6 minutes, obtain resin coated copper foil.Get epoxy glass fiber cloth bonding sheet (SHENGYI SCI.TECH, model: S0155) 8, each attached above-mentioned resin coated copper foil of making up and down, in laminating machine, the condition laminated of 190 ℃ obtains copper-clad laminate for 90 minutes.
Embodiment 2:
The resin combination that is total up to 100 weight parts comprises: bisphenol A type epoxy resin (HEXION, Epikote1001) 20 parts, cycloaliphatic epoxy resin (DOW Chemical, ERL-4221D) 15 parts, acid anhydrides (DOW Chemical, XUR-16) 45 parts, phosphorous phenoxy resin (Nippon Steel's chemistry, ERF-001) 12 parts, 8 parts of phosphonium flame retardants (Clariant, EXOLIT OP935).In said composition, add again promotor (glyoxal ethyline) 0.1 weight part and solvent (butanone) 50 weight parts can be made into glue, on coating machine, scattered glue is coated on electrolytic copper foil, at 155 ℃, baking oven, toasts and within 6 minutes, obtain resin coated copper foil.Get epoxy glass fiber cloth bonding sheet (SHENGYI SCI.TECH, model: S0155) 8, each attached above-mentioned resin coated copper foil of making up and down, in laminating machine, the condition laminated of 190 ℃ obtains copper-clad laminate for 90 minutes.
Embodiment 3:
The resin combination that is total up to 100 weight parts comprises: bisphenol A type epoxy resin (HEXION, Epikote1001) 25 parts, cycloaliphatic epoxy resin (DOW Chemical, ERL-4221D) 10 parts, acid anhydrides (DOW Chemical, XUR-16) 40 parts, phosphorous phenoxy resin (Nippon Steel's chemistry, ERF-001) 20 parts, 5 parts of phosphonium flame retardants (Clariant, EXOLIT OP935).In said composition, add again promotor (2-ethyl-4-methylimidazole) 0.08 weight part and solvent (butanone) 50 weight parts can be made into glue, on coating machine, scattered glue is coated on electrolytic copper foil, at 155 ℃, baking oven, toasts and within 6 minutes, obtain resin coated copper foil.Get epoxy glass fiber cloth bonding sheet (SHENGYI SCI.TECH, model: S0155) 8, each attached above-mentioned resin coated copper foil of making up and down, in laminating machine, the condition laminated of 190 ℃ obtains copper-clad laminate for 90 minutes.
Comparative example 1:
The resin combination that is total up to 100 weight parts comprises: phosphorous epoxy resin (DOW Chemical, XZ92530) 30 parts, bisphenol A epoxide resin (HEXION, Epikote1001) 23.5 parts, 10 parts of phenoxy resins (EPONOLResin53-BH-35), 35 parts of filling aluminium hydrates, 1.5 parts of Dyhard RU 100s.In said composition, adding promotor (glyoxal ethyline) 0.03 weight part and solvent (butanone) 40 weight parts can be made into glue, by above-mentioned liquid cement agitation 1 hour, and pass through fillers dispersed equipment high speed shear after 20 minutes, on coating machine, scattered glue is coated on electrolytic copper foil, at 155 ℃, baking oven, toasts and within 6 minutes, obtain resin coated copper foil.Get epoxy glass fiber cloth bonding sheet (SHENGYI SCI.TECH, model: S0155) 8, each attached above-mentioned resin coated copper foil of making up and down, in laminating machine, the condition laminated of 190 ℃ obtains copper-clad laminate for 90 minutes.
Comparative example 2:
The resin combination that is total up to 100 weight parts comprises: phosphorous epoxy resin (DOW Chemical, XZ92530) 20 parts, bisphenol A epoxide resin (HEXION, Epikote1001) 19 parts, 10 parts of phenoxy resins (EPONOLResin53-BH-35), 50 parts of filling aluminium hydrates, 1 part of Dyhard RU 100.In said composition, adding promotor (2-ethyl-4-methylimidazole) 0.02 weight part and solvent (butanone) 35 weight parts can be made into glue, by above-mentioned liquid cement agitation 1 hour, and pass through fillers dispersed equipment high speed shear after 20 minutes, on coating machine, scattered glue is coated on electrolytic copper foil, at 155 ℃, baking oven, toasts and within 6 minutes, obtain resin coated copper foil.Get epoxy glass fiber cloth bonding sheet (SHENGYI SCI.TECH, model: S0155) 8, each attached above-mentioned resin coated copper foil of making up and down, in laminating machine, the condition laminated of 190 ℃ obtains copper-clad laminate for 90 minutes.
The physical datas such as the phase ratio creepage tracking index of copper-clad laminate prepared by above-described embodiment and comparative example (CTI), resistance to immersed solder, thermal shocking number of times, alkali resistance and incendivity are as shown in table 1.
The physical data of copper-clad laminate prepared by table 1. embodiment and comparative example
Note: it is that lineae ablicantes phenomenon appears in sheet material that alkali resistance is tested unsanctioned performance.
The testing method of above physical property is as follows:
(1) phase ratio creepage tracking index (CTI):
(2) resistance to immersed solder:
(3) thermal shocking number of times:
(4) alkali resistance:
And incendivity Physical Property Analysis (5):
From the result of embodiment and comparative example, to recently, meet at the same time under the prerequisite of high phase ratio creepage tracking index (CTI>600V), embodiment all can test by alkali resistance, and comparative example all can not be tested by alkali resistance; From several Heat-tolerant indexes such as thermal shocking number of times and resistance to immersed solder times, the test result of embodiment is all apparently higher than comparative example.Therefore, copper-clad laminate prepared by halogen-free resin composition of the present invention, providing under the prerequisite of high phase ratio creepage tracking index, also has excellent alkali resistance and thermotolerance, reaches the requirement of halogen-free flameproof simultaneously.
In sum, halogen-free resin composition of the present invention is by bisphenol A type epoxy resin, phosphorous phenoxy resin and cycloaliphatic epoxy resin collocation, and add acid anhydrides as solidifying agent, make this halogen-free resin composition in the situation that not adding filler, there is excellent proof tracking, thermotolerance and alkali resistance; Described resin coated copper foil and copper-clad laminate, used above-mentioned halogen-free resin composition to prepare, and the phase ratio creepage tracking index of this resin coated copper foil and copper-clad laminate (CTI) >=600V, good heat resistance, alkali resistance are excellent, and reach halogen-free flameproof requirement.
The above, for the person of ordinary skill of the art, can make other various corresponding changes and distortion according to technical scheme of the present invention and technical conceive, and all these changes and distortion all should belong to the protection domain of the claims in the present invention.
Claims (7)
1. a halogen-free resin composition, is characterized in that, comprises component and weight part is as follows: bisphenol A type epoxy resin, 15-25 weight part; Cycloaliphatic epoxy resin, 10-20 weight part; Acid anhydrides, 40-50 weight part; Phosphorous phenoxy resin, 8-20 weight part; Phosphonium flame retardant, 5-8 weight part;
The epoxy equivalent (weight) of described bisphenol A type epoxy resin is 350-550g/eq;
The epoxy equivalent (weight) of described cycloaliphatic epoxy resin is 100-200g/eq, and its molecular structural formula is as follows:
Described acid anhydrides is tung oil acid anhydride, alkylene Succinic anhydried, methyl hexahydrophthalic acid anhydride, hydrogenation methyl carbic anhydride, Pyroglutaric acid, poly-nonane diacid acid anhydride, poly-petrosilane diacid anhydride or modified poly acid anhydrides, and its anhydride equivalent is 500-800g/eq;
While measuring according to GB4207-84, use the resin coated copper foil of this halogen-free resin composition making and phase ratio creepage tracking index (the CTI) >=600V of copper-clad laminate.
2. halogen-free resin composition as claimed in claim 1, is characterized in that, the phosphorus content of described phosphorous phenoxy resin is 3.0%-6.0%, and its molecular weight is 1-10 ten thousand.
3. halogen-free resin composition as claimed in claim 1, is characterized in that, described acid anhydrides is preferably modified poly acid anhydrides.
4. halogen-free resin composition as claimed in claim 1, is characterized in that, also comprises promotor and solvent, and described promotor is glyoxal ethyline or 2-ethyl-4-methylimidazole, and its weight part is 0.01-0.5 part; Described solvent is butanone, and its weight part is 30-100 part.
5. a resin coated copper foil that uses halogen-free resin composition as claimed in claim 1 to prepare, is characterized in that, comprises Copper Foil and applies the rear dry halogen-free resin composition on Copper Foil one or both sides that is attached to that toasts.
6. a copper-clad laminate that uses resin coated copper foil as claimed in claim 5 to prepare, is characterized in that, comprises two described resin coated copper foils and the epoxy bond sheet between two described resin coated copper foils.
7. the copper-clad laminate that prepared by use resin coated copper foil as claimed in claim 6, is characterized in that, described epoxy bond sheet is epoxy glass fiber cloth bonding sheet.
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| CN201210290617.2A CN102775735B (en) | 2012-08-15 | 2012-08-15 | Halogen-free resin composition, resin coated copper foil prepared from same, and copper clad laminate |
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| CN201210290617.2A CN102775735B (en) | 2012-08-15 | 2012-08-15 | Halogen-free resin composition, resin coated copper foil prepared from same, and copper clad laminate |
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| CN105348740A (en) * | 2015-11-27 | 2016-02-24 | 广东生益科技股份有限公司 | Resin composition and copper-clad plate and PCB made of same |
| CN105542395B (en) * | 2015-12-24 | 2020-04-14 | 中国电力科学研究院 | A toughened and reinforced epoxy resin composition |
| CN109401654B (en) * | 2017-09-12 | 2021-04-06 | 广东生益科技股份有限公司 | A package carrier tape base material, dual interface carrier tape and manufacturing method thereof |
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| CN101457012B (en) * | 2008-12-31 | 2011-06-15 | 广东生益科技股份有限公司 | Resin composition and copper clad laminate prepared by metal foil coated with resin composition |
| CN102051023B (en) * | 2010-12-09 | 2012-07-04 | 广东生益科技股份有限公司 | Halogen-free resin composition and resin-coated copper foil and copper-clad plate prepared from same |
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